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Sample records for bifunctional ruii complex-modified

  1. Bifunctional RuII -Complex-Catalysed Tandem C-C Bond Formation: Efficient and Atom Economical Strategy for the Utilisation of Alcohols as Alkylating Agents.

    Science.gov (United States)

    Roy, Bivas Chandra; Chakrabarti, Kaushik; Shee, Sujan; Paul, Subhadeep; Kundu, Sabuj

    2016-12-12

    Catalytic activities of a series of functional bipyridine-based Ru II complexes in β-alkylation of secondary alcohols using primary alcohols were investigated. Bifunctional Ru II complex (3 a) bearing 6,6'-dihydroxy-2,2'-bipyridine (6DHBP) ligand exhibited the highest catalytic activity for this reaction. Using significantly lower catalyst loading (0.1 mol %) dehydrogenative carbon-carbon bond formation between numerous aromatic, aliphatic and heteroatom substituted alcohols were achieved with high selectivity. Notably, for the synthesis of β-alkylated secondary alcohols this protocol is a rare one-pot strategy using a metal-ligand cooperative Ru II system. Remarkably, complex 3 a demonstrated the highest reactivity compared to all the reported transition metal complexes in this reaction. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Synthesis and characterization of new bifunctional nanocomposites possessing upconversion and oxygen-sensing properties

    International Nuclear Information System (INIS)

    Liu Lina; Li Bin; Qin Ruifei; Zhao Haifeng; Ren Xinguang; Su Zhongmin

    2010-01-01

    A new type of bifunctional nanocomposites for biomedical applications, upconversion NaY F 4 :Y b 3+ , Tm 3+ nanoparticles coated with Ru(II) complex chemically doped SiO 2 , has been developed by combining the useful functions of upconversion and oxygen-sensing properties into one nanoparticle. NaY F 4 :Y b 3+ , Tm 3+ nanoparticles were successfully coated with an Ru(II) complex doped SiO 2 shell with a thickness of ∼ 30 nm, and the surface of the SiO 2 was functionalized with amines. The obtained nanocomposites exhibited bright blue upconversion emission, and the luminescent emission intensity of the Ru(II) complex in the nanocomposites was sensitive to oxygen. Compared with the simple mixture of Ru(II) complex and SiO 2 , the core-shell nanocomposites showed better linearity between emission intensity of Ru(II) complex and oxygen concentrations. These bifunctional nanocomposites may find applications in biochemical and biomedical fields, such as biolabels and optical oxygen sensors, which can measure the oxygen concentrations in biological fluids.

  3. pH-induced photocurrent switching based on a highly stable drop-casting film of imidazole moiety-containing dinuclear Ru(II) Complex

    International Nuclear Information System (INIS)

    Xue, Long-Xin; Duan, Zhi-Ming; Jia, Jia; Wang, Ke-Zhi; Haga, Masa-aki

    2014-01-01

    Graphical abstract: > Solvent-casting Ru(II) complex modified electrode. > Positive shifting of half-wave potentials of Ru(III)/Ru(II) by pH decreases. > Greatly enhanced cathodic photocurrents by pH decreases. - Highlights: • Solvent-casting Ru(II) complex modified electrode. • Positive shifting of half-wave potentials of Ru(III)/Ru(II) by pH decreases. • Greatly enhanced cathodic photocurrents by pH decreases. - Abstract: A new dinuclear Ru(II) complex of [(H 2 L 1 )Ru(H 2 L 2 )Ru(H 2 L 1 )](ClO 4 ) 4 {H 2 L 1 = 2,6-bis(2-benzimidazolyl)pyridine; H 2 L 2 = 2,6-bis(4-([2,2′:6′,2″-terpyridin]-4′-yl)phenyl)-1,5- dihydrobenzo[1,2-d:4,5-d’]diimidazole} is synthesized and characterized. The Ru(II) complex modified indium-tin oxide electrode prepared using a drop-casting method, exhibited a couple of stable surface-confined Ru(III)/Ru(II)-based redox waves centered at +0.65 V vs saturated calomel electrode that were almost unchanged after 50 consecutive cyclic voltammetry scanning. The modified electrode showed pH-dependent redox behaviors with the formal potential being decreased by 430 mV due to the occurrance of the proton-coupled redox reactions. The cathodic photocurrent generation of the modified electrode was also found to be highly pH-dependent, switching from an “off” state at pH ∼11.0 to an “on” state at pH = 2.20 with an enhancement factor of 18. The modified electrode was shown to have promising applications as photoelectrochemical pH sensing and switching devices

  4. A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration.

    Science.gov (United States)

    Geri, Jacob B; Szymczak, Nathaniel K

    2015-10-14

    A new bifunctional pincer ligand framework bearing pendent proton-responsive hydroxyl groups was prepared and metalated with Ru(II) and subsequently isolated in four discrete protonation states. Stoichiometric reactions with H2 and HBPin showed facile E-H (E = H or BPin) activation across a Ru(II)-O bond, providing access to unusual Ru-H species with strong interactions with neighboring proton and boron atoms. These complexes were found to promote the catalytic hydroboration of ketones and nitriles under mild conditions, and the activity was highly dependent on the ligand's protonation state. Mechanistic experiments revealed a crucial role of the pendent hydroxyl groups for catalytic activity.

  5. A novel dinuclear Ru(II) complex having a bridging ligand of a rigid and extended structure. Incorporation of an anthraquinone unit and efficient emission quenching

    International Nuclear Information System (INIS)

    Mishra, L.; Choi, Chang-Shik; Araki, Koji

    1997-01-01

    Dinuclear Ru(II) complex having extended conjugation within the bridging ligand was prepared by coupling of the Ru(II) polypyridyl complex having a benzoyl-substituted phenazine unit with diaminoanthraquinone in one step, in which emission from the excited Ru(II) center was efficiently quenched through the anthraquinone unit. (author)

  6. Bifunctional redox flow battery

    International Nuclear Information System (INIS)

    Wen, Y.H.; Cheng, J.; Xun, Y.; Ma, P.H.; Yang, Y.S.

    2008-01-01

    A new bifunctional redox flow battery (BRFB) system, V(III)/V(II)-L-cystine(O 2 ), was systematically investigated by using different separators. It is shown that during charge, water transfer is significantly restricted with increasing the concentration of HBr when the Nafion 115 cation exchange membrane is employed. The same result can be obtained when the gas diffusion layer (GDL) hot-pressed separator is used. The organic electro-synthesis is directly correlated with the crossover of vanadium. When employing the anion exchange membrane, the electro-synthesis efficiency is over 96% due to a minimal crossover of vanadium. When the GDL hot-pressed separator is applied, the crossover of vanadium and water transfer are noticeably prevented and the electro-synthesis efficiency of over 99% is obtained. Those impurities such as vanadium ions and bromine can be eliminated through the purification of organic electro-synthesized products. The purified product is identified to be L-cysteic acid by IR spectrum. The BRFB shows a favorable discharge performance at a current density of 20 mA cm -2 . Best discharge performance is achieved by using the GDL hot-pressed separator. The coulombic efficiency of 87% and energy efficiency of about 58% can be obtained. The cause of major energy losses is mainly associated with the cross-contamination of anodic and cathodic active electrolytes

  7. Synthesis of 3-(4,5-dihydroimidazol-1-YL)propyltriethoxysilane bound Ru(II) complex bearing viologen segment

    International Nuclear Information System (INIS)

    Gurbuz, N.; Seckin, T.; Ozdemir, I.; Cetinkaya, B.

    2005-01-01

    The nanostructured metallopolymers consisting of the partially quaternized 3-(4,5-dihydroimidazol-1-yl)propyl having the viologen group linked covalently through the alkyl spacer its Ru(II) complex have been prepared by sol-gel method. Structural elucidation was done with Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and differential thermal analysis (DTA) [ru

  8. Optimization of Temperature Sensing with Polymer-Embedded Luminescent Ru(II Complexes

    Directory of Open Access Journals (Sweden)

    Nelia Bustamante

    2018-02-01

    Full Text Available Temperature is a key parameter in many fields and luminescence-based temperature sensing is a solution for those applications in which traditional (mechanical, electrical, or IR-based thermometers struggle. Amongst the indicator dyes for luminescence thermometry, Ru(II polyazaheteroaromatic complexes are an appealing option to profit from the widespread commercial technologies for oxygen optosensing based on them. Six ruthenium dyes have been studied, engineering their structure for both photostability and highest temperature sensitivity of their luminescence. The most apt Ru(II complex turned out to be bis(1,10-phenanthroline(4-chloro-1,10-phenanthrolineruthenium(II, due to the combination of two strong-field chelating ligands (phen and a substituent with electron withdrawing effect on a conjugated position of the third ligand (4-Clphen. In order to produce functional sensors, the dye has been best embedded into poly(ethyl cyanoacrylate, due to its low permeability to O2, high temperature sensitivity of the indicator dye incorporated into this polymer, ease of fabrication, and excellent optical quality. Thermosensitive elements have been fabricated thereof as optical fiber tips for macroscopic applications (water courses monitoring and thin spots for microscopic uses (temperature measurements in cell culture-on-a-chip. With such dye/polymer combination, temperature sensing based on luminescence lifetime measurements allows 0.05 °C resolution with linear response in the range of interest (0–40 °C.

  9. Synthesis and characterization of Ru(II) complexes with polyfunctional quinazoline-(3H)-4-ones

    International Nuclear Information System (INIS)

    Prabhakar, B.; Lingaiah, P.; Laxma Reddy, K.

    1991-01-01

    Few Ru(II) complexes of the type Ru(O-N-O) 2 with tridentate O-N-O donors and of the type RuCl 2 (O-N) 2 with bidentate O-O and O-N donors have been synthesized and characterized on the basis of analytical, conductivity, thermal, magnetic, IR, electronic and PMR spectral data. The IR and PMR spectral data of the metal complexes indicate that the lignads like 2-methyl/phenyl-3-(2'-hydroxybenzalamino) quinazoline-(3H)-4-one(MHBQ/PHBQ) act as uninegative tridentate, 2-methyl/phenyl-3-(carboxymethyl) quinazoline(3H)-4-one (MCMQ/PCMQ) as uninegative bidentate and 2-methyl/phenyl-3-(furfuralamino) quinazoline-(3H)-4-one (MFQ/PFQ), 2-methyl/phenyl-3-(acetamino) quinazoline-(3H)-4-one (MAQ/PAQ), 2-methyl/phenyl3-(uramino)quinazoline-(3H)-4-one (MUQ/PUQ) and 2-methyl/phenyl-3-thiouramino)quinazoline-(3H)-4-one-(MTUQ/PTUQ) as neutral bidentate ligands. The electronic spectral data of the complexes indicate that the arrangement around Ru(II) is octahedral. (author). 25 refs., 2 tabs

  10. Unprecedented Self-Organized Monolayer of a Ru(II) Complex by Diazonium Electroreduction.

    Science.gov (United States)

    Nguyen, Van Quynh; Sun, Xiaonan; Lafolet, Frédéric; Audibert, Jean-Frédéric; Miomandre, Fabien; Lemercier, Gilles; Loiseau, Frédérique; Lacroix, Jean-Christophe

    2016-08-03

    A new heteroleptic polypyridyle Ru(II) complex was synthesized and deposited on surface by the diazonium electroreduction process. It yields to the covalent grafting of a monolayer. The functionalized surface was characterized by XPS, electrochemistry, AFM, and STM. A precise organization of the molecules within the monolayer is observed with parallel linear stripes separated by a distance of 3.8 nm corresponding to the lateral size of the molecule. Such organization suggests a strong cooperative process in the deposition process. This strategy is an original way to obtain well-controlled and stable functionalized surfaces for potential applications related to the photophysical properties of the grafted chromophore. As an exciting result, it is the first example of a self-organized monolayer (SOM) obtained using diazonium electroreduction.

  11. Fat & fabulous: bifunctional lipids in the spotlight.

    Science.gov (United States)

    Haberkant, Per; Holthuis, Joost C M

    2014-08-01

    Understanding biological processes at the mechanistic level requires a systematic charting of the physical and functional links between all cellular components. While protein-protein and protein-nucleic acid networks have been subject to many global surveys, other critical cellular components such as membrane lipids have rarely been studied in large-scale interaction screens. Here, we review the development of photoactivatable and clickable lipid analogues-so-called bifunctional lipids-as novel chemical tools that enable a global profiling of lipid-protein interactions in biological membranes. Recent studies indicate that bifunctional lipids hold great promise in systematic efforts to dissect the elaborate crosstalk between proteins and lipids in live cells and organisms. This article is part of a Special Issue entitled Tools to study lipid functions. Copyright © 2014 Elsevier B.V. All rights reserved.

  12. Identifying and annotating human bifunctional RNAs reveals their versatile functions.

    Science.gov (United States)

    Chen, Geng; Yang, Juan; Chen, Jiwei; Song, Yunjie; Cao, Ruifang; Shi, Tieliu; Shi, Leming

    2016-10-01

    Bifunctional RNAs that possess both protein-coding and noncoding functional properties were less explored and poorly understood. Here we systematically explored the characteristics and functions of such human bifunctional RNAs by integrating tandem mass spectrometry and RNA-seq data. We first constructed a pipeline to identify and annotate bifunctional RNAs, leading to the characterization of 132 high-confidence bifunctional RNAs. Our analyses indicate that bifunctional RNAs may be involved in human embryonic development and can be functional in diverse tissues. Moreover, bifunctional RNAs could interact with multiple miRNAs and RNA-binding proteins to exert their corresponding roles. Bifunctional RNAs may also function as competing endogenous RNAs to regulate the expression of many genes by competing for common targeting miRNAs. Finally, somatic mutations of diverse carcinomas may generate harmful effect on corresponding bifunctional RNAs. Collectively, our study not only provides the pipeline for identifying and annotating bifunctional RNAs but also reveals their important gene-regulatory functions.

  13. Bifunctional organocatalysts for the asymmetric synthesis of axially chiral benzamides

    Directory of Open Access Journals (Sweden)

    Ryota Miyaji

    2017-08-01

    Full Text Available Bifunctional organocatalysts bearing amino and urea functional groups in a chiral molecular skeleton were applied to the enantioselective synthesis of axially chiral benzamides via aromatic electrophilic bromination. The results demonstrate the versatility of bifunctional organocatalysts for the enantioselective construction of axially chiral compounds. Moderate to good enantioselectivities were afforded with a range of benzamide substrates. Mechanistic investigations were also carried out.

  14. Astaxanthin diferulate as a bifunctional antioxidant

    DEFF Research Database (Denmark)

    Papa, T.B.R.; Pinho, V.D.; Nascimento, E.P. do

    2015-01-01

    Abstract Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(- 1)s(- 1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(- 1)s(- 1). The ferulate moiety in the astaxanthin diester is a better radical....... The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability....

  15. Bifunctional electrodes for unitised regenerative fuel cells

    International Nuclear Information System (INIS)

    Altmann, Sebastian; Kaz, Till; Friedrich, Kaspar Andreas

    2011-01-01

    Research highlights: → Different oxygen electrode configurations for the operation in a unitised reversible fuel cell were tested. → Polarisation curves and EIS measurements were recorded. → The mixture of catalysts performs best for the present stage of electrode development. → Potential improvements for the different compositions are discussed. - Abstract: The effects of different configurations and compositions of platinum and iridium oxide electrodes for the oxygen reaction of unitised regenerative fuel cells (URFC) are reported. Bifunctional oxygen electrodes are important for URFC development because favourable properties for the fuel cell and the electrolysis modes must be combined into a single electrode. The bifunctional electrodes were studied under different combinations of catalyst mixtures, multilayer arrangements and segmented configurations with single catalyst areas. Distinct electrochemical behaviour was observed for both modes and can be explained on the basis of impedance spectroscopy. The mixture of both catalysts performs best for the present stage of electrode development. Also, the multilayer electrodes yielded good results with the potential for optimisation. The influence of ionic and electronic resistances on the relative performance is demonstrated. However, penalties due to cross currents in the heterogeneous electrodes were identified and explained by comparing the performance curves with electrodes composed of a single catalyst. Potential improvements for the different compositions are discussed.

  16. Cellobiose dehydrogenase entrapped within specifically designed Os-complex modified electrodeposition polymers as potential anodes for biofuel cells

    International Nuclear Information System (INIS)

    Shao, Minling; Guschin, Dmitrii A.; Kawah, Zahma; Beyl, Yvonne; Stoica, Leonard; Ludwig, Roland; Schuhmann, Wolfgang; Chen, Xingxing

    2014-01-01

    Electron-transfer pathways between cellobiose dehydrogenase from Myriococcum thermophilum (MtCDH) and the related flavodehydrogenase domain (FAD-MtCDH) and electrodes were evaluated using specifically designed Os-complex modified electrodeposition paints (EDPs). The properties of the Os-complex modified EDPs were varied by variation of the monomer composition, the coordination sphere of the polymer-bound Os-complexes, and the length and flexibility of the spacer chain between Os complex and polymer backbone. The MtCDH-to-EDP weight ratio, the pH value, as well as the operational temperature have been optimized

  17. A new synthesis route for Os-complex modified redox polymers for potential biofuel cell applications.

    Science.gov (United States)

    Pöller, Sascha; Beyl, Yvonne; Vivekananthan, Jeevanthi; Guschin, Dmitrii A; Schuhmann, Wolfgang

    2012-10-01

    A new synthesis route for Os-complex modified redox polymers was developed. Instead of ligand exchange reactions for coordinative binding of suitable precursor Os-complexes at the polymer, Os-complexes already exhibiting the final ligand shell containing a suitable functional group were bound to the polymer via an epoxide opening reaction. By separation of the polymer synthesis from the ligand exchange reaction at the Os-complex, the modification of the same polymer backbone with different Os-complexes or the binding of the same Os-complex to a number of different polymer backbones becomes feasible. In addition, the Os-complex can be purified and characterized prior to its binding to the polymer. In order to further understand and optimize suitable enzyme/redox polymer systems concerning their potential application in biosensors or biofuel cells, a series of redox polymers was synthesized and used as immobilization matrix for Trametes hirsuta laccase. The properties of the obtained biofuel cell cathodes were compared with similar biocatalytic interfaces derived from redox polymers obtained via ligand exchange reaction of the parent Os-complex with a ligand integrated into the polymer backbone during the polymer synthesis. Copyright © 2011 Elsevier B.V. All rights reserved.

  18. PROSPECTS FOR APPLICATION OF COMPLEX-MODIFIED SAND ASPHALT CONCRETE IN ROAD CONSTRUCTION

    Directory of Open Access Journals (Sweden)

    D. Yu. Alexandrov

    2017-01-01

    Full Text Available The paper considers a possibility to use sand asphalt concrete as a material for protection of asphalt concrete and cement concrete road pavements against affection of external destructive factors. Advantages and disadvantages of sand asphalt concrete road pavements have been determined in the paper. The paper provides recommendations on improvement of sand asphalt concrete properties and contains an analysis of possible variants for usage of complex-modified sand asphalt concrete in the road construction. It has been noted that according to its potentially possible physical and mechanical properties activated quartz sand being micro-reinforced by dispersive industrial wastes is considered as an efficient component for creation of constructive layers in road asphalt concrete pavements. The paper reveals only specific aspects of the efficient application of quartz sand in road asphalt concrete. The subject of the paper loоks rather interesting for regions where there are no rock deposits for obtaining broken-stone ballast but there is rather significant spreading of local quarts sand. Its successful application is connected with the necessity to develop special equipment for physical and chemical activation of sand grain surface that permits strongly to increase an adhesive strength in the area of phase separation within the “bitumen–SiO2” system. The considered problem is a topical one and its solution will make it possible to local sand in a maximum way and partially to exclude application of broken stone in road construction.

  19. Reversible and pH dependent photophysical properties of mixed-ligand Ru(II) complexes containing 2,20-bipyridine and nitrosobarbiturate: Experimental and theoretical approach

    Czech Academy of Sciences Publication Activity Database

    Dixit, N.; Záliš, Stanislav; Maiti, B.; Mishra, L.

    2013-01-01

    Roč. 404, AUG 2013 (2013), s. 123-130 ISSN 0020-1693 Institutional support: RVO:61388955 Keywords : Mixed-ligand Ru(II) complex * spectroscopy * X-ray diffraction Subject RIV: CF - Physical ; The oretical Chemistry Impact factor: 2.041, year: 2013

  20. Molecularly Engineered Ru(II) Sensitizers Compatible with Cobalt(II/III) Redox Mediators for Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Wu, Kuan-Lin; Huckaba, Aron J; Clifford, John N; Yang, Ya-Wen; Yella, Aswani; Palomares, Emilio; Grätzel, Michael; Chi, Yun; Nazeeruddin, Mohammad Khaja

    2016-08-01

    Thiocyanate-free isoquinazolylpyrazolate Ru(II) complexes were synthesized and applied as sensitizers in dye-sensitized solar cells (DSCs). Unlike most other successful Ru sensitizers, Co-based electrolytes were used, and resulting record efficiency of 9.53% was obtained under simulated sunlight with an intensity of 100 mW cm(-2). Specifically, dye 51-57dht.1 and an electrolyte based on Co(phen)3 led to measurement of a JSC of 13.89 mA cm(-2), VOC of 900 mV, and FF of 0.762 to yield 9.53% efficiency. The improved device performances were achieved by the inclusion of 2-hexylthiophene units onto the isoquinoline subunits, in addition to lengthening the perfluoroalkyl chain on the pyrazolate chelating group, which worked to increase light absorption and decrease recombination effects when using the Co-based electrolyte. As this study shows, Ru(II) sensitizers bearing sterically demanding ligands can allow successful utilization of important Co electrolytes and high performance.

  1. Bifunctional Phosphorus Dendrimers and Their Properties.

    Science.gov (United States)

    Caminade, Anne-Marie; Majoral, Jean-Pierre

    2016-04-23

    Dendrimers are hyperbranched and monodisperse macromolecules, generally considered as a special class of polymers, but synthesized step-by-step. Most dendrimers have a uniform structure, with a single type of terminal function. However, it is often desirable to have at least two different functional groups. This review will discuss the case of bifunctional phosphorus-containing dendrimers, and the consequences for their properties. Besides the terminal functions, dendritic structures may have also a function at the core, or linked off-center to the core, or at the core of dendrons (dendritic wedges). Association of two dendrons having different terminal functions leads to Janus dendrimers (two faces). The internal structure can also possess functional groups on one layer, or linked to one layer, or on several layers. Finally, there are several ways to have two types of terminal functions, besides the case of Janus dendrimers: either each terminal function bears two functions sequentially, or two different functions are linked to each terminal branching point. Examples of each type of structure will be given in this review, as well as practical uses of such sophisticated structures in the fields of fluorescence, catalysis, nanomaterials and biology.

  2. Synthesis, photophysical and electrochemical characterization of terpyridine-functionalized dendritic oligothiophenes and their Ru(II complexes

    Directory of Open Access Journals (Sweden)

    Amaresh Mishra

    2013-05-01

    Full Text Available Pd-catalyzed Sonogashira cross-coupling reactions were used to synthesize novel π-conjugated oligothienylene-ethynylene dendrons and their corresponding terpyridine-based ligands. Their complexation with Ru(II led to interesting novel metallodendrimers with rich spectroscopic properties. All new compounds were fully characterized by 1H and 13C NMR, as well as MALDI–TOF mass spectra. Density functional theory (DFT calculations performed on these complexes gave more insight into the molecular orbital distributions. Photophysical and electrochemical studies were carried out in order to elucidate structure–property relationships and the effect of the dendritic structure on the metal complexes. Photophysical studies of the complexes revealed broad absorption spectra covering from 250 to 600 nm and high molar extinction coefficients. The MLCT emission of these complexes were significantly red-shifted (up to 115 nm compared to the parent [Ru(tpy2]2+ complex.

  3. Carbon in bifunctional air electrodes in alkaline solution

    International Nuclear Information System (INIS)

    Tryk, D.; Aldred, W.; Yeager, E.

    1983-01-01

    Bifunctional O 2 electrodes can be used both to reduce and to generate O 2 in rechargeable metal-air batteries and fuel cells. The factors controlling the O 2 reduction and generation reactions in gas-diffusional bifunctional O 2 electrodes are discussed. The resistance of such electrodes, as established from voltammetry curves, has been found to increase markedly during anodic polarization and to be dependent upon the electrode fabrication technique. Carbon blacks with more graphitic structure than Shawinigan black have been found to be more resistant to electro-oxidation. The further extension of cycle life of bifunctional electrodes using carbon is critically dependent on finding more oxidation-resistant carbons that at the same time have other surface properties meeting the requirements for catalyzed gas-diffusion electrodes

  4. Main regularities of radiolytic transformations of bifunctional organic compounds

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Shadyro, O.I.

    1985-01-01

    General regularities of the radiolysis of bifunctional organic compounds (α-diols, ethers of α-diols, amino alcohols, hydroxy aldehydes and hydroxy asids) in aqueous solutions from the early stages of the process to formation of finite products are traced. It is pointed out that the most characteristic course of radiation-chemical, transformation of bifunctional compounds in agueous solutions in the fragmentation process with monomolecular decomposition of primary radicals of initial substrances and simultaneous scission of two vicinal in respect to radical centre bonds via five-membered cyclic transient state. The data obtained are of importance for molecular radiobiology

  5. New Ru(II) complexes for dual photoreactivity: ligand exchange and (1)O2 generation.

    Science.gov (United States)

    Knoll, Jessica D; Albani, Bryan A; Turro, Claudia

    2015-08-18

    Uncovering the factors that govern the electronic structure of Ru(II)-polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and (1)O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field ((3)LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer ((3)MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2](2+) (bpy = 2,2'-bipyridine; L = CH3CN or py). This suggests that population of the (3)LF state proceeds from the vibrationally excited (3)MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the (3)LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)](2+) complexes (tpy = 2,2':6',2″-terpyridine; NN = bpy, 6,6'-dimethyl-2,2'-bipyridine (Me2bpy), 2,2'-biquinoline (biq)) increases by 2-3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the (3)LF state within 3-7 ps when NN is bulky, and density functional theory calculations support stabilized (3)LF states. Dual activity via ligand dissociation and (1)O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2](2+) (dppn = benzo[i]dipyrido[3,2-a:2',3'-c]phenazine) and [Ru(tpy)(Me2dppn)(py)](2+) (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2',3'-c]phenazine) introduces

  6. New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

    Science.gov (United States)

    Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

    2016-01-01

    CONSPECTUS Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer (3MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2]2+ (bpy = 2,2′-bipyridine; L = CH3CN or py). This suggests that population of the 3LF state proceeds from the vibrationally excited 3MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the 3LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)]2+ complexes (tpy = 2,2′:6′,2″-terpyridine; NN = bpy, 6,6′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-biquinoline (biq)) increases by 2–3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the 3LF state within 3–7 ps when NN is bulky, and density functional theory calculations support stabilized 3LF states. Dual activity via ligand dissociation and 1O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2]2+ (dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) and [Ru(tpy)(Me2dppn)(py)]2+ (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2′,3

  7. Mixed-ligand Ru(II) complexes with 2,2'-bipyridine and aryldiazo-beta-diketonato auxillary ligands: synthesis, physico-chemical study and antitumour properties.

    Science.gov (United States)

    Mishra, Lallan; Yadaw, Ajay K; Bhattacharya, Subrato; Dubey, Santosh K

    2005-05-01

    The complexes of Ru(II)-2,2'-bipyridyl with substituted diazopentane-2,4-diones (L1H-L5H) were synthesized and characterized by elemental analyses, conductance, FAB (fast atom bombardment) mass and spectral (IR, UV/Vis (UV/visible), NMR) studies. Molecular geometry optimization of the complexes was also made. None of the complexes luminesce. However, facilitated oxidation of Ru(II) to Ru(III) was evidenced from their lower reduction potential data. The ligands and their complexes were tested for their antitumour activity against a variety of tumour cell lines. Though activity is found to vary with the type of tumour cell lines used, yet complex 5 with naphtyldiazopentane-2,4-dione as co-ligand was found to be a potential compound as it showed in general significant activity against all cell lines studied.

  8. Synthesis of 4‧-substituted-2,2‧;6‧,2″-terpyridine Ru(II) complexes electrochemical, fluorescence quenching and antibacterial studies

    Science.gov (United States)

    Ezhilarasu, Tamilarasu; Sathiyaseelan, Anbazhagan; Kalaichelvan, Pudupalayam Thangavelu; Balasubramanian, Sengottuvelan

    2017-04-01

    Three new Ru(II) terpyridine complexes viz. [Ru(BBtpy)2](PF6)2 [Ru(L1)] (BBtpy = 4‧-(4-benzyloxybenzaldehyde)-2,2‧:6‧,2″-terpyridine), [Ru(BMBtpy)2](PF6)2 [Ru(L2)] (BMBtpy = 4‧-(4-benzyloxy-3-methoxybenzaldehyde)-2,2‧:6‧,2″-terpyridine) and [Ru(BEBtpy)2](PF6)2 [Ru(L3)] (BEBtpy = 4‧-(4-benzyloxy-3-ethoxybenzaldehyde)-2,2‧:6‧,2″-terpyridine) have been synthesized and characterized. The MALDI-TOF/MS fragmentation pattern of [Ru(BMBtpy)2](PF6)2 complex exhibits a molecular ion peak at m/z = 987.09 [M-2PF6]2+ fragment. These Ru(II) complexes are redox active, show both metal centered oxidation and ligand centered reduction processes. The peak potential and peak current Ipa and Ipc also undergo definite shift and increase with increase in the scan rate (20-120 mV/s). The fluorescence of Ru(II) complexes [Ru(L1)], [Ru(L2)] and [Ru(L3)] are effectively quenched by 1,4-benzoquinone and 1,4-naphthoquinone in acetonitrile. The antibacterial activity of ruthenium(II) complexes were screened against four human pathogens both gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus) and gram negative bacteria (Escherichia coli, Klebsiella pneumonia) by the well diffusion method. The antibacterial activity of Ru(II) complexes is comparable to that of standard antibiotics like tetracycline.

  9. DNA-binding, catalytic oxidation, C—C coupling reactions and antibacterial activities of binuclear Ru(II thiosemicarbazone complexes: Synthesis and spectral characterization

    Directory of Open Access Journals (Sweden)

    Arumugam Manimaran

    2012-07-01

    Full Text Available New hexa-coordinated binuclear Ru(II thiosemicarbazone complexes of the type {[(B(EPh3(COClRu]2L} (where, E = P or As; B = PPh3 or AsPh3 or pyridine; L = mononucleating NS donor of N-substituted thiosemicarbazones have been synthesized and characterized by elemental analysis, FT-IR, UV–vis and 31P{1H} NMR cyclic voltammetric studies. The DNA-binding studies of Ru(II complexes with calf thymus DNA (CT-DNA were investigated by UV–vis, viscosity measurements, gel-electrophoresis and fluorescence spectroscopy. The new complexes have been used as catalysts in C—C coupling reaction and in the oxidation of alcohols to their corresponding carbonyl compounds by using NMO as co-oxidant and molecular oxygen (O2 atmosphere at ambient temperature. Further, the new binucleating thiosemicarbazone ligands and their Ru(II complexes were also screened for their antibacterial activity against Klebsiella pneumoniae, Shigella sp., Micrococcus luteus, Escherichia coli and Salmonella typhi. From this study, it was found out that the activity of the complexes almost reaches the effectiveness of the conventional bacteriocide.

  10. Experimental and density functional theory (DFT) studies on the interactions of Ru(II) polypyridyl complexes with the RAN triplex poly(U)˙poly(A)*poly(U).

    Science.gov (United States)

    Zhang, Hong; Liu, Xuewen; He, Xiaojun; Liu, Ying; Tan, Lifeng

    2014-11-01

    There is renewed interest in investigating triple helices because these novel structures have been implicated as a possible means of controlling cellular processes by endogenous or exogenous mechanisms. Due to the Hoogsteen base pairing, triple helices are, however, thermodynamically less stable than the corresponding duplexes. The poor stability of triple helices limits their practical applications under physiological conditions. In contrast to DNA triple helices, small molecules stabilizing RNA triple helices at present are less well established. Furthermore, most of these studies are limited to organic compounds and, to a far lesser extent, to metal complexes. In this work, two Ru(II) complexes, [Ru(bpy)2(btip)](2+) (Ru1) and [Ru(phen)2(btip)](2+) (Ru2), have been synthesized and characterized. The binding properties of the two metal complexes with the triple RNA poly(U)˙poly(A)*poly(U) were studied by various biophysical and density functional theory methods. The main results obtained here suggest that the slight binding difference in Ru1 and Ru2 may be attributed to the planarity of the intercalative ligand and the LUMO level of Ru(II) complexes. This study further advances our knowledge on the triplex RNA-binding by metal complexes, particularly Ru(II) complexes.

  11. Crystallization of bi-functional ligand protein complexes.

    Science.gov (United States)

    Antoni, Claudia; Vera, Laura; Devel, Laurent; Catalani, Maria Pia; Czarny, Bertrand; Cassar-Lajeunesse, Evelyn; Nuti, Elisa; Rossello, Armando; Dive, Vincent; Stura, Enrico Adriano

    2013-06-01

    Homodimerization is important in signal transduction and can play a crucial role in many other biological systems. To obtaining structural information for the design of molecules able to control the signalization pathways, the proteins involved will have to be crystallized in complex with ligands that induce dimerization. Bi-functional drugs have been generated by linking two ligands together chemically and the relative crystallizability of complexes with mono-functional and bi-functional ligands has been evaluated. There are problems associated with crystallization with such ligands, but overall, the advantages appear to be greater than the drawbacks. The study involves two matrix metalloproteinases, MMP-12 and MMP-9. Using flexible and rigid linkers we show that it is possible to control the crystal packing and that by changing the ligand-enzyme stoichiometric ratio, one can toggle between having one bi-functional ligand binding to two enzymes and having the same ligand bound to each enzyme. The nature of linker and its point of attachment on the ligand can be varied to aid crystallization, and such variations can also provide valuable structural information about the interactions made by the linker with the protein. We report here the crystallization and structure determination of seven ligand-dimerized complexes. These results suggest that the use of bi-functional drugs can be extended beyond the realm of protein dimerization to include all drug design projects. Copyright © 2013 Elsevier Inc. All rights reserved.

  12. Environmentally Benign Bifunctional Solid Acid and Base Catalysts

    NARCIS (Netherlands)

    Elmekawy, A.; Shiju, N.R.; Rothenberg, G.; Brown, D.R.

    2014-01-01

    Solid bifunctional acid-​base catalysts were prepd. in two ways on an amorphous silica support: (1) by grafting mercaptopropyl units (followed by oxidn. to propylsulfonic acid) and aminopropyl groups to the silica surface (NH2-​SiO2-​SO3H)​, and (2) by grafting only aminopropyl groups and then

  13. Bifunctional xylanases and their potential use in biotechnology

    Digital Repository Service at National Institute of Oceanography (India)

    Khandeparker, R.; Numan, M.Th.

    . J Chromatography 919:389–394 33. Hong SY, Lee JS, Cho KM, Math RK, Kim YH, Hong SJ, Cho YU, Kim H, Yun HD (2006) Assembling a novel bifunctional cel- lulase–xylanase from Thermotoga maritima by end-to-end fusion. Biotechnol Lett 28:1857–1862 34...

  14. Single flexible nanofiber to simultaneously realize electricity-magnetism bifunctionality

    International Nuclear Information System (INIS)

    Yang, Ming; Sheng, Shujuan; Ma, Qianli; Lv, Nan; Yu, Wensheng; Wang, Jinxian; Dong, Xiangting; Liu, Guixia

    2016-01-01

    In order to develop new-typed multifunctional composite nanofibers, PANI/Fe 3 O 4 /PVP flexible bifunctional composite nanofibers with simultaneous electrical conduction and magnetism have been successfully fabricated via a facile electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of polyaniline (PANI) and Fe 3 O 4 nanoparticles (NPs). The bifunctional composite nanofibers simultaneously possess excellent electrical conductivity and magnetic properties. The electrical conductivity reaches up to the order of 10 -3 S·cm -1 . The electrical conductivity and saturation magnetization of the composite nanofibers can be respectively tuned by adding various amounts of PANI and Fe 3 O 4 NPs. The obtained electricity-magnetism bifunctional composite nanofibers are expected to possess many potential applications in areas such as electromagnetic interference shielding, special coating, microwave absorption, molecular electronics and future nanomechanics. More importantly, the design concept and construct technique are of universal significance to fabricate other bifunctional one-dimensional nanostructures. (author)

  15. Single flexible nanofiber to simultaneously realize electricity-magnetism bifunctionality

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ming; Sheng, Shujuan; Ma, Qianli; Lv, Nan; Yu, Wensheng; Wang, Jinxian; Dong, Xiangting; Liu, Guixia, E-mail: wenshengyu2009@sina.com, E-mail: dongxiangting888@163.com [Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, Changchun University of Science and Technology, Changchun (China)

    2016-03-15

    In order to develop new-typed multifunctional composite nanofibers, PANI/Fe{sub 3}O{sub 4}/PVP flexible bifunctional composite nanofibers with simultaneous electrical conduction and magnetism have been successfully fabricated via a facile electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of polyaniline (PANI) and Fe{sub 3}O{sub 4} nanoparticles (NPs). The bifunctional composite nanofibers simultaneously possess excellent electrical conductivity and magnetic properties. The electrical conductivity reaches up to the order of 10{sup -3} S·cm{sup -1}. The electrical conductivity and saturation magnetization of the composite nanofibers can be respectively tuned by adding various amounts of PANI and Fe{sub 3}O{sub 4} NPs. The obtained electricity-magnetism bifunctional composite nanofibers are expected to possess many potential applications in areas such as electromagnetic interference shielding, special coating, microwave absorption, molecular electronics and future nanomechanics. More importantly, the design concept and construct technique are of universal significance to fabricate other bifunctional one-dimensional nanostructures. (author)

  16. Design of Ru(II) sensitizers endowed by three anchoring units for adsorption mode and light harvesting optimization

    International Nuclear Information System (INIS)

    Lobello, Maria Grazia; Fantacci, Simona; Manfredi, Norberto; Coluccini, Carmine; Abbotto, Alessandro; Nazeeruddin, Mohammed K.; De Angelis, Filippo

    2014-01-01

    We report the design, synthesis and computational investigation of a class of Ru(II)-dyes based on mixed bipyridine ligands for use in dye-sensitized solar cells. These dyes are designed to preserve the optimal anchoring mode of the prototypical N719 sensitizer by three carboxylic groups, yet allowing for tunable optimization of their electronic and optical properties by selective substitution at one of the 4-4′ positions of a single bipyridine ligand with π-excessive heteroaromatic groups. We used Density Functional Theory/Time Dependent Density Functional Theory calculations to analyze the electronic structure and optical properties of the dye and to investigate the dye adsorption mode on a TiO 2 nanoparticle model. Our results show that we are effectively able to introduce three carboxylic anchoring units into the dye and achieve at the same time an enhanced dye light harvesting, demonstrating the design concept. As a drawback of this type of dyes, the synthesis leads to a mixture of dye isomers, which are rather tedious to separate. - Highlights: • We designed heteroleptic Ru(II) sensitizers with three carboxylic anchoring groups. • The three carboxylic anchoring groups are essential for high open circuit potentials. • Introduction of the mixed bipyridine ligand increases the dye light absorption. • Computational simulations confirm the three anchoring sites on TiO 2

  17. Design of Ru(II) sensitizers endowed by three anchoring units for adsorption mode and light harvesting optimization

    Energy Technology Data Exchange (ETDEWEB)

    Lobello, Maria Grazia; Fantacci, Simona [Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), Istituto CNR di Scienze e Tecnologie Molecolari, Via elce di Sotto 8, I-06213 Perugia (Italy); Manfredi, Norberto; Coluccini, Carmine [Department of Materials Science and Milano-Bicocca Solar Energy Research Center-MIB-Solar, University of Milano-Bicocca and INSTM, Via Cozzi 53, I-20125 Milano (Italy); Abbotto, Alessandro, E-mail: alessandro.abbotto@unimib.it [Department of Materials Science and Milano-Bicocca Solar Energy Research Center-MIB-Solar, University of Milano-Bicocca and INSTM, Via Cozzi 53, I-20125 Milano (Italy); Nazeeruddin, Mohammed K., E-mail: mdkhaja.nazeeruddin@epfl.ch [Laboratory for Photonics and Interfaces, Station 6, Institute of Chemical Sciences and Engineering, School of Basic Sciences, Swiss Federal Institute of Technology, CH-1015 Lausanne (Switzerland); De Angelis, Filippo, E-mail: filippo@thch.unipg.it [Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), Istituto CNR di Scienze e Tecnologie Molecolari, Via elce di Sotto 8, I-06213 Perugia (Italy)

    2014-06-02

    We report the design, synthesis and computational investigation of a class of Ru(II)-dyes based on mixed bipyridine ligands for use in dye-sensitized solar cells. These dyes are designed to preserve the optimal anchoring mode of the prototypical N719 sensitizer by three carboxylic groups, yet allowing for tunable optimization of their electronic and optical properties by selective substitution at one of the 4-4′ positions of a single bipyridine ligand with π-excessive heteroaromatic groups. We used Density Functional Theory/Time Dependent Density Functional Theory calculations to analyze the electronic structure and optical properties of the dye and to investigate the dye adsorption mode on a TiO{sub 2} nanoparticle model. Our results show that we are effectively able to introduce three carboxylic anchoring units into the dye and achieve at the same time an enhanced dye light harvesting, demonstrating the design concept. As a drawback of this type of dyes, the synthesis leads to a mixture of dye isomers, which are rather tedious to separate. - Highlights: • We designed heteroleptic Ru(II) sensitizers with three carboxylic anchoring groups. • The three carboxylic anchoring groups are essential for high open circuit potentials. • Introduction of the mixed bipyridine ligand increases the dye light absorption. • Computational simulations confirm the three anchoring sites on TiO{sub 2}.

  18. Luminescent pH sensor of a novel imidazole-containing hexanuclear Ru(II) polypyridyl complex

    Science.gov (United States)

    Cheng, Feixiang; Tang, Ning; Chen, Jishu; Chen, Guang

    2013-10-01

    Hexapodal ligand H6L containing imidazole rings has been prepared by the reaction of 1,10-phenanthroline-5,6-dione with 1,2,3,4,5,6-hexakis[(3-formylphenoxy)methyl]benzene. The Ru(II) polypyridyl complex [{Ru(bpy)2}6(μ6-H6L)](PF6)12 (bpy = 2,2'-bipyridine) has been synthesized by the reaction of Ru(bpy)2Cl2·2H2O with ligand H6L. The pH effects on the UV-vis absorption and emission spectra of the complex have been studied. The ground- and excited-state ionization constants of the acid-base equilibria have been calculated according to the absorbance and emission data. The complex acts as an off-on-off luminescent pH sensor through two successive deprotonation processes of imidazole rings, with a maximum on-off ratio of 5 in buffer solution.

  19. The aminoindanol core as a key scaffold in bifunctional organocatalysts

    Directory of Open Access Journals (Sweden)

    Isaac G. Sonsona

    2016-03-01

    Full Text Available The 1,2-aminoindanol scaffold has been found to be very efficient, enhancing the enantioselectivity when present in organocatalysts. This may be explained by its ability to induce a bifunctional activation of the substrates involved in the reaction. Thus, it is easy to find hydrogen-bonding organocatalysts ((thioureas, squaramides, quinolinium thioamide, etc. in the literature containing this favored structural core. They have been successfully employed in reactions such as Friedel–Crafts alkylation, Michael addition, Diels–Alder and aza-Henry reactions. However, the 1,2-aminoindanol core incorporated into proline derivatives has been scarcely explored. Herein, the most representative and illustrative examples are compiled and this review will be mainly focused on the cases where the aminoindanol moiety confers bifunctionality to the organocatalysts.

  20. Bifunctional chelates of Rh-105 and Au-199 as potential radiotherapeutic agents

    International Nuclear Information System (INIS)

    Troutner, D.E.; Schlemper, E.O.

    1990-01-01

    Since last year we have: continued the synthesis of pentadentate bifunctional chelating agents based on diethylene triamine; studied the chelation Rh-105, Au-198 (as model for Au-199) and Tc-99m with these agents as well as chelation of Pd-109, Cu-67, In-111, and Co-57 with some of them; synthesized a new class of potential bifunctional chelating agents based on phenylene diamine; investigated the behavior of Au-198 as a model for Au-199; begun synthesis of bifunctional chelating agents based on terpyridly and similar ligands; and continued attempts to produce tetradentate bifunctional chelates based on diaminopropane. Each of these will be addressed in this report

  1. [Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

    International Nuclear Information System (INIS)

    1991-01-01

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III)

  2. [Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents

    Energy Technology Data Exchange (ETDEWEB)

    1991-12-31

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  3. (Bifunctional chelates of Rh-105, Au-199, and other metallic radionuclides as potential radiotherapeutic agents)

    Energy Technology Data Exchange (ETDEWEB)

    1991-01-01

    Progress during this period is reported under the following headings: Diethylenetriamine based and related bifunctional chelating agents and their complexation with Rh-105, Au-198, Pd-109, cu-67, In-111, and Co-57; studies of Pd-109, Rh-105 and Tc-99m with bifunctional chelates based on phenylenediamine; establishment of an appropriate protein assay method for conjugated proteins; studies of new bifunctional Bi, Tri and tetradentate amine oxime ligands with Rh-105; IgG and antibody B72.3 conjugation studies by HPLC Techniques with bifunctional metal chelates; and progress on ligand systems for Au(III).

  4. Nanoscale intimacy in bifunctional catalysts for selective conversion of hydrocarbons

    Science.gov (United States)

    Zecevic, Jovana; Vanbutsele, Gina; de Jong, Krijn P.; Martens, Johan A.

    2015-12-01

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts. Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon sources to provide high-quality diesel fuel. Such bifunctional hydrocracking catalysts contain metal sites and acid sites, and for more than 50 years the so-called intimacy criterion has dictated the maximum distance between the two types of site, beyond which catalytic activity decreases. A lack of synthesis and material-characterization methods with nanometre precision has long prevented in-depth exploration of the intimacy criterion, which has often been interpreted simply as ‘the closer the better’ for positioning metal and acid sites. Here we show for a bifunctional catalyst—comprising an intimate mixture of zeolite Y and alumina binder, and with platinum metal controllably deposited on either the zeolite or the binder—that closest proximity between metal and zeolite acid sites can be detrimental. Specifically, the selectivity when cracking large hydrocarbon feedstock molecules for high-quality diesel production is optimized with the catalyst that contains platinum on the binder, that is, with a nanoscale rather than closest intimacy of the metal and acid sites. Thus, cracking of the large and complex hydrocarbon molecules that are typically derived from alternative sources, such as gas-to-liquid technology, vegetable oil or algal oil, should benefit especially from bifunctional catalysts that avoid locating platinum on the zeolite (the traditionally assumed optimal location). More generally, we anticipate that the ability demonstrated here to spatially organize different active sites at the nanoscale will benefit the further development and optimization of the emerging generation of multifunctional catalysts.

  5. A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

    Science.gov (United States)

    Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

    2012-01-01

    A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

  6. Chiral analysis of alpha-diimine Ru(II) and Fe(II) complexes by capillary electrophoresis using sulfated cyclodextrins as stereoselectors

    Czech Academy of Sciences Publication Activity Database

    Sázelová, Petra; Koval, Dušan; Severa, Lukáš; Teplý, Filip; Kašička, Václav

    2017-01-01

    Roč. 38, č. 15 (2017), s. 1913-1921 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA15-01948S; GA ČR GA13-32974S; GA ČR GA13-19213S Institutional support: RVO:61388963 Keywords : binding constant * capillary electrophoresis * chiral separation * polypyridyl Fe(II) complex * polypyridyl Ru(II) complex Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 2.744, year: 2016

  7. An irresolute linker: separation, and structural and spectroscopic characterization of the two linkage isomers of a Ru(ii)-(2-(2'-pyridyl)pyrimidine-4-carboxylic acid) complex.

    Science.gov (United States)

    Iengo, E; Demitri, N; Balducci, G; Alessio, E

    2014-08-28

    For the first time the two linkage isomers of a Ru(ii) complex with 2-(2'-pyridyl)pyrimidine-4-carboxylic acid (cppH) - that form in comparable amounts - have been fully characterized individually. The X-ray structure of each isomer is related to its NMR spectrum in solution.

  8. Synthesis and Characterization of a Ru(II Complex with Functionalized Phenanthroline Ligands Having Single-Double Linked Anthracenyl and 1-Methoxy-1-buten-3-yne Moieties

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2010-10-01

    Full Text Available Two series of bidentate polypyridine ligands, made of phenanthroline chelating subunits having substituted mono-and di-anthracenyl groups, and 1-methoxy-1-buten-3-yne at the 4 and 7-positions with the corresponding heteroleptic Ru(II complex have been synthesized and characterized. The complex is formulated as [(Ru(L1(L2(NCS2], (where L1 = 4-(9-dianthracenyl-10-(2,3-dimethylacrylic acid-7-(9-anthracenyl-10-(2,3-dimethylacrylic acid-1,10-phenanthroline and L2 = 4,7-bis(1-methoxy-1-buten-3-yne-1,10-phenanthroline. The Ru(II complex shows characteristic broad and intense metal-to-ligand charge transfer (MLCT bands absorption and appreciable photoluminescence spanning the visible region. The ligands and complex were characterized by FT-IR, 1H, 13C NMR spectroscopy, UV-Vis, photoluminescence and elemental analysis (see in supplementary materials. The anchoring groups in both ligands have allowed an extended delocalization of acceptor orbital of the metal-to-ligand charge-transfer (MLCT excited state.

  9. Achieving bifunctional cloak via combination of passive and active schemes

    Science.gov (United States)

    Lan, Chuwen; Bi, Ke; Gao, Zehua; Li, Bo; Zhou, Ji

    2016-11-01

    In this study, a simple and delicate approach to realizing manipulation of multi-physics field simultaneously through combination of passive and active schemes is proposed. In the design, one physical field is manipulated with passive scheme while the other with active scheme. As a proof of this concept, a bifunctional device is designed and fabricated to behave as electric and thermal invisibility cloak simultaneously. It is found that the experimental results are consistent with the simulated ones well, confirming the feasibility of our method. Furthermore, the proposed method could also be extended to other multi-physics fields, which might lead to potential applications in thermal, electric, and acoustic areas.

  10. Perspectives in the development of hybrid bifunctional antitumour agents.

    Science.gov (United States)

    Musso, Loana; Dallavalle, Sabrina; Zunino, Franco

    2015-08-15

    In spite of the development of a large number of novel target-specific antitumour agents, the single-agent therapy is in general not able to provide an effective durable control of the malignant process. The limited efficacy of the available agents (both conventional cytotoxic and novel target-specific) reflects not only the expression of defence mechanisms, but also the complexity of tumour cell alterations and the redundancy of survival pathways, thus resulting in tumour cell ability to survive under stress conditions. A well-established strategy to improve the efficacy of antitumour therapy is the rational design of drug combinations aimed at achieving synergistic effects and overcoming drug resistance. An alternative strategy could be the use of agents designed to inhibit simultaneously multiple cellular targets relevant to tumour growth/survival. Among these novel agents are hybrid bifunctional drugs, i.e. compounds resulting by conjugation of different drugs or containing the pharmocophores of different drugs. This strategy has been pursued using various conventional or target-specific agents (with DNA damaging agents and histone deacetylase inhibitors as the most exploited compounds). A critical overview of the most representative compounds is provided with emphasis on the HDAC inhibitor-based hybrid agents. In spite of some promising results, the actual pharmacological advantages of the hybrid agents remain to be defined. This commentary summarizes the recent advances in this field and highlights the pharmacological basis for a rational design of hybrid bifunctional agents. Copyright © 2015. Published by Elsevier Inc.

  11. Multichromophoric hybrid species made of perylene bisimide derivatives and Ru(ii) and Os(ii) polypyridine subunits.

    Science.gov (United States)

    Nastasi, Francesco; La Ganga, Giuseppina; Campagna, Sebastiano; Syrgiannis, Zois; Rigodanza, Francesco; Vitale, Stefania; Licciardello, Antonino; Prato, Maurizio

    2017-05-31

    Herein, the synthesis and the photophysical and redox properties of a new perylene bisimide (PBI) species (L), bearing two 1,10-phenanthroline (phen) ligands at the two imide positions of the PBI, and its dinuclear Ru(ii) and Os(ii) complexes, [(bpy) 2 Ru(μ-L)Ru(bpy) 2 ](PF 6 ) 4 (Ru2; bpy = 2,2'-bipyridine) and [(Me 2 -bpy) 2 Os(μ-L)Os(Me 2 -bpy) 2 ](PF 6 ) 4 (Os2; Me 2 -bpy = (4,4'-dimethyl)-2,2'-bipyridine), are reported. The absorption spectra of the compounds are dominated by the structured bands of the PBI subunit due to the lowest-energy spin-allowed π-π* transition. The spin-allowed MLCT transitions in Ru2 and Os2 are inferred by the absorption at 350-470 nm, where the PBI absorption is negligible. The absorption band extends towards the red region for Os2 due to the spin-forbidden MLCT transitions, intensified by the heavy osmium center. The reduction processes of the compounds are dominated by two successive mono-electronic PBI-based processes, which in the metal complexes are slightly shifted compared to the free ligand. On oxidation, both metal complexes undergo an apparent bi-electronic process (at 1.31 V vs. SCE for Ru2 and 0.77 V for Os2), attributed to the simultaneous one-electron oxidation of the two weakly-interacting metal centers. In Ru2 and Os2, the intense fluorescence of L subunit (λ max , 535 nm; τ, 4.3 ns; Φ, 0.91) is fully quenched, mainly by photoinduced electron transfer from the metal centers, on the ps timescale (time constant, 11 ps in Ru2 and 3 ps in Os2). Such photoinduced electron transfer leads to the formation of a charge-separated state, which directly decays to the ground state in about 70 ps in Os2, but produces the triplet π-π* state of the PBI subunit in 35 ps in Ru2. The results provide information on the excited-state processes of the hybrid species combining two dominant classes of chromophore/luminophore species, the PBI and the metal polypyridine complexes, and can be used for future design on new hybrid

  12. Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

    Science.gov (United States)

    Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

    2015-01-01

    A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

  13. Towards the Development of Functionalized PolypyridineLigands for Ru(II Complexes as Photosensitizers inDye-Sensitized Solar Cells (DSSCs

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2014-08-01

    Full Text Available A number of novel ruthenium(II polypyridine complexes have been designedand synthesized for use as photosensitizers in dye-sensitized solar cells (DSSCs due totheir rich photophysical properties such as intense absorption, long-lived lifetimes, highemission quantum yields and unique redox characteristics. Many of these complexesexhibit photophysical behavior that can be readily controlled through a careful choice ofligands and/or substituents. With this perspective, we review the design and general syntheticmethods of some polypyridine ligands based on bipyridine, phenanthroline, terpyridine andquaterpyridine with/without anchoring groups with a view to correlate functionality ofligand structures with the observed photophysical, electroredox and power conversionefficiency of some examples of Ru(II polypyridyl complexes that have been reported andparticularly used in the DSSCs applications. The main interest, however, is focused onshowing the development of new polypyridine ligand materials containing long-rangeelectron transfer motifs such as the alkenyl, alkynyl and polyaromatic donor functionalities.

  14. Biomedical Applications of Gold Nanoparticles Functionalized Using Hetero-Bifunctional Poly(ethylene glycol) Spacer

    National Research Council Canada - National Science Library

    Fu, Wei; Shenoy, Dinesh; Li, Jane; Crasto, Curtis; Jones, Graham; Dimarzio, Charles; Sridhar, Srinivas; Amiji, Mansoor

    2005-01-01

    To increase the targeting potential, circulation time, and the flexibility of surface-attached biomedically-relevant ligands on gold nanoparticles, hetero-bifunctional poly(ethylene glycol) (PEG, MW 1,500...

  15. Bifunctional chelating agent for the design and development of site specific radiopharmaceuticals and biomolecule conjugation strategy

    Science.gov (United States)

    Katti, Kattesh V.; Prabhu, Kandikere R.; Gali, Hariprasad; Pillarsetty, Nagavara Kishore; Volkert, Wynn A.

    2003-10-21

    There is provided a method of labeling a biomolecule with a transition metal or radiometal in a site specific manner to produce a diagnostic or therapeutic pharmaceutical compound by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radio metal or a transition metal, and covalently linking the resulting metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. Also provided is a method of synthesizing the --PR.sub.2 containing biomolecules by synthesizing a P.sub.2 N.sub.2 -bifunctional chelating agent intermediate, complexing the intermediate with a radiometal or a transition metal, and covalently linking the resulting radio metal-complexed bifunctional chelating agent with a biomolecule in a site specific manner. There is provided a therapeutic or diagnostic agent comprising a --PR.sub.2 containing biomolecule.

  16. Design and Testing of Bi-Functional, P-Loop-Targeted MDM2 Inhibitors

    National Research Council Canada - National Science Library

    Prives, Carol L; Stockwell, Brent R

    2007-01-01

    Our proposal is to design and evaluate a novel class of bifunctional MDM2 inhibitors, based on the discovery that nucleotides can bind to the P-loop of MDM2 and cause its relocalization to the nucleolus...

  17. Design and Testing of Bi-Functional, P-Loop-Targeted MDM2 Inhibitors

    National Research Council Canada - National Science Library

    Prives, Carol L

    2006-01-01

    This proposal is to design and evaluate a novel class of bifunctional MDM2 inhibitors, based on the discovery that nucleotides can bind to the P-loop of MDM2 and cause its relocalization to the nucleolus...

  18. Triple Quenching of a Novel Self-Enhanced Ru(II) Complex by Hemin/G-Quadruplex DNAzymes and Its Potential Application to Quantitative Protein Detection.

    Science.gov (United States)

    Zhao, Min; Liao, Ni; Zhuo, Ying; Chai, Ya-Qin; Wang, Ji-Peng; Yuan, Ruo

    2015-08-04

    Herein, a novel "on-off" electrochemiluminescence (ECL) aptasensor for highly sensitive determination of thrombin has been constructed based on the triple quenching of the effect of hemin/G-quadruplex DNAzymes upon the Ru(II) complex-based ECL system. First, a strong initial ECL signal was achieved by the dual amplification strategies of (i) intramolecular coreaction of a self-enhanced Ru(II)-based molecule (PTCA-PEI-Ru(II)) and (ii) intermolecular coreaction between PTCA-PEI-Ru(II) and nicotinamide adenine dinucleotide (NADH), which was named the signal-on state. Then, a novel triple quenching of the effect of multifunctional hemin/G-quadruplex DNAzymes upon the Ru(II) complex-based ECL system was designed to realize the desirable signal-off state, which was outlined as follows: (i) the hemin/G-quadruplex DNAzymes mimicked NADH oxidase to oxidize NADH and in situ generate the H2O2, consuming the coreactant of NADH; (ii) its active center of hemin could oxidize the excited state PTCA-PEI-Ru(II)* to PTCA-PEI-Ru(III), making the energy and electron transfer quench; (iii) it also acted as horseradish peroxidase (HRP) to catalyze the H2O2 for in situ producing the quencher of O2. Based on triple quenching of the effect of hemin/G-quadruplex DNAzymes, the highly sensitive "on-off" thrombin aptasensor was developed with a wide linear detection range of 1.0 × 10(-14) M to 1.0 × 10(-10) M and a detection limit down to the femtomolar level.

  19. Microwave-Assisted Synthesis of Arene Ru(II Complexes Induce Tumor Cell Apoptosis Through Selectively Binding and Stabilizing bcl-2 G-Quadruplex DNA

    Directory of Open Access Journals (Sweden)

    Yanhua Chen

    2016-05-01

    Full Text Available A series of arene Ru(II complexes coordinated with phenanthroimidazole derivatives, [(η6-C6H6Ru(lCl]Cl(1b L = p-ClPIP = 2-(4-Chlorophenylimidazole[4,5f] 1,10-phenanthroline; 2b L = m-ClPIP = 2-(3-Chlorophenylimidazole[4,5f] 1,10-phenanthroline; 3b L = p-NPIP = 2-(4-Nitrophenylimidazole[4,5f] 1,10-phenanthroline; 4b L = m-NPIP = 2-(3-Nitrophenyl imidazole [4,5f] 1,10-phenanthroline were synthesized in yields of 89.9%–92.7% under conditions of microwave irradiation heating for 30 min to liberate four arene Ru(II complexes (1b, 2b, 3b, 4b. The anti-tumor activity of 1b against various tumor cells was evaluated by MTT assay. The results indicated that this complex blocked the growth of human lung adenocarcinoma A549 cells with an IC50 of 16.59 μM. Flow cytometric analysis showed that apoptosis of A549 cells was observed following treatment with 1b. Furthermore, the in vitro DNA-binding behaviors that were confirmed by spectroscopy indicated that 1b could selectively bind and stabilize bcl-2 G-quadruplex DNA to induce apoptosis of A549 cells. Therefore, the synthesized 1b has impressive bcl-2 G-quadruplex DNA-binding and stabilizing activities with potential applications in cancer chemotherapy.

  20. Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

    Science.gov (United States)

    Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

    2015-12-21

    Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Anticancer activities of self-assembled molecular bowls containing a phenanthrene-based donor and Ru(II acceptors

    Directory of Open Access Journals (Sweden)

    Kim I

    2015-08-01

    Full Text Available Inhye Kim,1,* Young Ho Song,2,* Nem Singh,2 Yong Joon Jeong,3 Jung Eun Kwon,3 Hyunuk Kim,4 Young Mi Cho,3 Se Chan Kang,3 Ki-Whan Chi2 1Laboratory of Bio-Resources, Yongin-si, Gyeonggi-Do, 2Department of Chemistry, University of Ulsan, Ulsan, 3Department of Life Science, Gachon University, Seongnam, 4Energy Materials Lab, Korea Institute of Energy Research, Daejeon, Republic of Korea *These authors contributed equally to this work Abstract: Nano-sized multinuclear ruthenium complexes have rapidly emerged as promising therapeutic candidates with unique anticancer activities. Here, we describe the coordination-driven self-assembly and anticancer activities of a set of three organometallic tetranuclear Ru(II molecular bowls. [2+2] Coordination-driven self-assembly of 3,6-bis(pyridin-3-ylethynylphenanthrene (bpep (1 and one of the three dinuclear arene ruthenium clips, [(ƞ6-p-iPrC6H4Me2Ru2-(OO\\OO][OTf]2 (OO\\OO =2,5-dioxido-1,4-benzoquinonato, OTf = triflate (2, 5,8-dioxido-1,4-naphthoquinonato (3, or 6,11-dioxido-5,12-naphthacenediona (4, resulted in three molecular bowls 5–7 of general formula [{(ƞ6-p-iPrC6H4Me2Ru2-(OO\\OO}2(bpep2][OTf]4. All molecular bowls were obtained as triflate salts in very good yields (>90% and were fully characterized using multinuclear nuclear magnetic resonance (NMR, electrospray ionization–mass spectrometry (ESI-MS, and elemental analysis. The structure of the representative molecular bowl 5 was confirmed by single-crystal X-ray diffraction analysis. The anticancer activities of molecular bowls 5–7 were determined by 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide, autophagy, and Western blot analysis. Bowl 6 showed the strongest cytotoxicity in AGS human gastric carcinoma cells and was more cytotoxic than doxorubicin. In addition, autophagic activity and the ratio of apoptotic cell death increased in AGS cells by treatment with bowl 6. Bowl 6 also induced autophagosome formation via upregulation

  2. Synthesis of deuterium-labeled analogs of the lipid hydroperoxide-derived bifunctional electrophile 4-oxo-2(E)-nonenal

    OpenAIRE

    Arora, Jasbir S.; Oe, Tomoyuki; Blair, Ian A.

    2011-01-01

    Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2(E)-nonenal and 4-oxo-2(E)-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α,β-unsaturated aldehyde that can react in multiple ways and w...

  3. Mechanish of dTTP Inhibition of the Bifunctional dCTP Deaminase:dUTPase Encoded by Mycobacterium tuberculosis

    DEFF Research Database (Denmark)

    Helt, Signe Smedegaard; Thymark, Majbritt; Harris, Pernille

    2008-01-01

    Recombinant deoxycytidine triphosphate (dCTP) deaminase from Mycobacterium tuberculosis was produced in Escherichia coli and purified. The enzyme proved to be a bifunctional dCTP deaminase:deoxyuridine triphosphatase. As such, the M. tuberculosis enzyme is the second bifunctional enzyme to be cha......Recombinant deoxycytidine triphosphate (dCTP) deaminase from Mycobacterium tuberculosis was produced in Escherichia coli and purified. The enzyme proved to be a bifunctional dCTP deaminase:deoxyuridine triphosphatase. As such, the M. tuberculosis enzyme is the second bifunctional enzyme...

  4. Bifunctional avidin with covalently modifiable ligand binding site.

    Directory of Open Access Journals (Sweden)

    Jenni Leppiniemi

    Full Text Available The extensive use of avidin and streptavidin in life sciences originates from the extraordinary tight biotin-binding affinity of these tetrameric proteins. Numerous studies have been performed to modify the biotin-binding affinity of (streptavidin to improve the existing applications. Even so, (streptavidin greatly favours its natural ligand, biotin. Here we engineered the biotin-binding pocket of avidin with a single point mutation S16C and thus introduced a chemically active thiol group, which could be covalently coupled with thiol-reactive molecules. This approach was applied to the previously reported bivalent dual chain avidin by modifying one binding site while preserving the other one intact. Maleimide was then coupled to the modified binding site resulting in a decrease in biotin affinity. Furthermore, we showed that this thiol could be covalently coupled to other maleimide derivatives, for instance fluorescent labels, allowing intratetrameric FRET. The bifunctional avidins described here provide improved and novel tools for applications such as the biofunctionalization of surfaces.

  5. Bioinspired Bifunctional Membrane for Efficient Clean Water Generation.

    Science.gov (United States)

    Liu, Yang; Lou, Jinwei; Ni, Mengtian; Song, Chengyi; Wu, Jianbo; Dasgupta, Neil P; Tao, Peng; Shang, Wen; Deng, Tao

    2016-01-13

    Solving the problems of water pollution and water shortage is an urgent need for the sustainable development of modern society. Different approaches, including distillation, filtration, and photocatalytic degradation, have been developed for the purification of contaminated water and the generation of clean water. In this study, we explored a new approach that uses solar light for both water purification and clean water generation. A bifunctional membrane consisting of a top layer of TiO2 nanoparticles (NPs), a middle layer of Au NPs, and a bottom layer of anodized aluminum oxide (AAO) was designed and fabricated through multiple filtration processes. Such a design enables both TiO2 NP-based photocatalytic function and Au NP-based solar-driven plasmonic evaporation. With the integration of these two functions into a single membrane, both the purification of contaminated water through photocatalytic degradation and the generation of clean water through evaporation were demonstrated using simulated solar illumination. Such a demonstration should also help open up a new strategy for maximizing solar energy conversion and utilization.

  6. Plutonium and americium extraction studies with bifunctional organophosphorus extractants

    International Nuclear Information System (INIS)

    Navratil, J.D.

    1985-01-01

    Neutral bifunctional organophosphorus extractants, such as octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP), are under study at the Rocky Flats Plant (RFP) to remove plutonium and americium from the 7M nitric acid waste. These compounds extract trivalent actinides from strong nitric acid, a property which distinguishes them from monofunctional organiphosphorus reagents. Furthermore, the reagents extract hydroytic plutonium (IV) polymer which is present in the acid waste stream. The compounds extract trivalent actinides with a 3:1 stoichiometry, whereas tetra- and hexavalent actinides extract with a stoichiometry of 2:1. Preliminary studies indicate that the extracted plutonium polymer complex contains one to two molecules of CMP per plutonium ion and the plutonium(IV) maintains a polymeric structure. Recent studies by Horwitz and co-workers conclude that the CMPO and CMP reagents behave as monodentate ligands. At RFP, three techniques are being tested for using CMP and CMPO to remove plutonium and americium from nitric acid waste streams. The different techniques are liquid-liquid extraction, extraction chromatography, and solid-supported liquid membranes. Recent tests of the last two techniques will be briefly described. In all the experiments, CMP was an 84% pure material from Bray Oil Co. and CMPO was 98% pure from M and T Chemicals

  7. A conserved regulatory mechanism in bifunctional biotin protein ligases.

    Science.gov (United States)

    Wang, Jingheng; Beckett, Dorothy

    2017-08-01

    Class II bifunctional biotin protein ligases (BirA), which catalyze post-translational biotinylation and repress transcription initiation, are broadly distributed in eubacteria and archaea. However, it is unclear if these proteins all share the same molecular mechanism of transcription regulation. In Escherichia coli the corepressor biotinoyl-5'-AMP (bio-5'-AMP), which is also the intermediate in biotin transfer, promotes operator binding and resulting transcription repression by enhancing BirA dimerization. Like E. coli BirA (EcBirA), Staphylococcus aureus, and Bacillus subtilis BirA (Sa and BsBirA) repress transcription in vivo in a biotin-dependent manner. In this work, sedimentation equilibrium measurements were performed to investigate the molecular basis of this biotin-responsive transcription regulation. The results reveal that, as observed for EcBirA, Sa, and BsBirA dimerization reactions are significantly enhanced by bio-5'-AMP binding. Thus, the molecular mechanism of the Biotin Regulatory System is conserved in the biotin repressors from these three organisms. © 2017 The Protein Society.

  8. Dark and bright solitons for the two-dimensional complex modified Korteweg-de Vries and Maxwell-Bloch system with time-dependent coefficient

    Science.gov (United States)

    Shaikhova, G.; Ozat, N.; Yesmakhanova, K.; Bekova, G.

    2018-02-01

    In this work, we present Lax pair for two-dimensional complex modified Korteweg-de Vries and Maxwell-Bloch (cmKdV-MB) system with the time-dependent coefficient. Dark and bright soliton solutions for the cmKdV-MB system with variable coefficient are received by Darboux transformation. Moreover, the determinant representation of the one-fold and two-fold Darboux transformation for the cmKdV-MB system with time-dependent coefficient is presented.

  9. Single flexible nanofiber to achieve simultaneous photoluminescence-electrical conductivity bifunctionality.

    Science.gov (United States)

    Sheng, Shujuan; Ma, Qianli; Dong, Xiangting; Lv, Nan; Wang, Jinxian; Yu, Wensheng; Liu, Guixia

    2015-02-01

    In order to develop new-type multifunctional composite nanofibers, Eu(BA)3 phen/PANI/PVP bifunctional composite nanofibers with simultaneous photoluminescence and electrical conductivity have been successfully fabricated via electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of Eu(BA)3 phen and polyaniline (PANI). X-Ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), fluorescence spectroscopy and a Hall effect measurement system are used to characterize the morphology and properties of the composite nanofibers. The results indicate that the bifunctional composite nanofibers simultaneously possess excellent photoluminescence and electrical conductivity. Fluorescence emission peaks of Eu(3+) ions are observed in the Eu(BA)3 phen/PANI/PVP photoluminescence-electrical conductivity bifunctional composite nanofibers. The electrical conductivity reaches up to the order of 10(-3)  S/cm. The luminescent intensity and electrical conductivity of the composite nanofibers can be tuned by adjusting the amounts of Eu(BA)3 phen and PANI. The obtained photoluminescence-electrical conductivity bifunctional composite nanofibers are expected to possess many potential applications in areas such as microwave absorption, molecular electronics, biomedicine and future nanomechanics. More importantly, the design concept and construction technique are of universal significance to fabricate other bifunctional one-dimensional naonomaterials. Copyright © 2014 John Wiley & Sons, Ltd.

  10. Half-Sandwich Ru(II and Os(II Bathophenanthroline Complexes Containing a Releasable Dichloroacetato Ligand

    Directory of Open Access Journals (Sweden)

    Pavel Štarha

    2018-02-01

    Full Text Available We report on the preparation and thorough characterization of cytotoxic half-sandwich complexes [Ru(η6-pcym(bphen(dca]PF6 (Ru-dca and [Os(η6-pcym(bphen(dca]PF6 (Os-dca containing dichloroacetate(1– (dca as the releasable O-donor ligand bearing its own cytotoxicity; pcym = 1-methyl-4-(propan-2-ylbenzene (p-cymene, bphen = 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline. Complexes Ru-dca and Os-dca hydrolyzed in the water-containing media, which led to the dca ligand release (supported by 1H NMR and electrospray ionization mass spectra. Mass spectrometry studies revealed that complexes Ru-dca and Os-dca do not interact covalently with the model proteins cytochrome c and lysozyme. Both complexes exhibited slightly higher in vitro cytotoxicity (IC50 = 3.5 μM for Ru-dca, and 2.6 μM for Os-dca against the A2780 human ovarian carcinoma cells than cisplatin (IC50 = 5.9 μM, while their toxicity on the healthy human hepatocytes was found to be IC50 = 19.1 μM for Ru-dca and IC50 = 19.7 μM for Os-dca. Despite comparable cytotoxicity of complexes Ru-dca and Os-dca, both the complexes modified the cell cycle, mitochondrial membrane potential, and mitochondrial cytochrome c release by a different way, as revealed by flow cytometry experiments. The obtained results point out the different mechanisms of action between the complexes.

  11. Synthesis, characterization and catalytic activity of acid-base bifunctional materials through protection of amino groups

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Yanqiu [College of Chemistry, Jilin University, Changchun 130023 (China); College of Chemistry, Mudanjiang Normal University, Mudanjiang 157012 (China); Liu, Heng; Yu, Xiaofang [College of Chemistry, Jilin University, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China); Kan, Qiubin, E-mail: qkan@mail.jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China)

    2012-03-15

    Graphical abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. Highlights: Black-Right-Pointing-Pointer The acid-base bifunctional material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized through protection of amino groups. Black-Right-Pointing-Pointer The obtained bifunctional material was tested for aldol condensation. Black-Right-Pointing-Pointer The SO{sub 3}H-SBA-15-NH{sub 2} catalyst containing amine and sulfonic acid groups exhibited excellent acid-basic properties. -- Abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N{sub 2} adsorption-desorption, transmission electron micrographs (TEM), back titration, {sup 13}C magic-angle spinning (MAS) NMR and {sup 29}Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO{sub 3}H-SBA-15 and SBA-15-NH{sub 2}, the bifunctional sample of SO{sub 3}H-SBA-15-NH{sub 2} containing amine and sulfonic acid groups exhibited excellent acid-basic properties, which make it possess high activity for the aldol condensation.

  12. Reaction Current Phenomenon in Bifunctional Catalytic Metal-Semiconductor Nanostructures

    Science.gov (United States)

    Hashemian, Mohammad Amin

    Energy transfer processes accompany every elementary step of catalytic chemical processes on material surface including molecular adsorption and dissociation on atoms, interactions between intermediates, and desorption of reaction products from the catalyst surface. Therefore, detailed understanding of these processes on the molecular level is of great fundamental and practical interest in energy-related applications of nanomaterials. Two main mechanisms of energy transfer from adsorbed particles to a surface are known: (i) adiabatic via excitation of quantized lattice vibrations (phonons) and (ii) non-adiabatic via electronic excitations (electron/hole pairs). Electronic excitations play a key role in nanocatalysis, and it was recently shown that they can be efficiently detected and studied using Schottky-type catalytic nanostructures in the form of measureable electrical currents (chemicurrents) in an external electrical circuit. These nanostructures typically contain an electrically continuous nanocathode layers made of a catalytic metal deposited on a semiconductor substrate. The goal of this research is to study the direct observations of hot electron currents (chemicurrents) in catalytic Schottky structures, using a continuous mesh-like Pt nanofilm grown onto a mesoporous TiO2 substrate. Such devices showed qualitatively different and more diverse signal properties, compared to the earlier devices using smooth substrates, which could only be explained on the basis of bifunctionality. In particular, it was necessary to suggest that different stages of the reaction are occurring on both phases of the catalytic structure. Analysis of the signal behavior also led to discovery of a formerly unknown (very slow) mode of the oxyhydrogen reaction on the Pt/TiO2(por) system occurring at room temperature. This slow mode was producing surprisingly large stationary chemicurrents in the range 10--50 microA/cm2. Results of the chemicurrent measurements for the bifunctional

  13. Monodisperse Magneto-Fluorescent Bifunctional Nanoprobes for Bioapplications

    Science.gov (United States)

    Zhang, Hongwang; Huang, Heng; Pralle, Arnd; Zeng, Hao

    2013-03-01

    We present the work on the synthesis of dye-doped monodisperse Fe/SiO2 core/shell nanoparticles as bifunctional probes for bioapplications. Magnetic nanoparticles (NP) have been widely studied as nano-probes for bio-imaging, sensing as well as for cancer therapy. Among all the NPs, Fe NPs have been the focus because they have very high magnetization. However, Fe NPs are usually not stable in ambient due to the fast surface oxidation of the NPs. On the other hand, dye molecules have long been used as probes for bio-imaging. But they are sensitive to environmental conditions. It requires passivation for both so that they can be stable for applications. In this work, monodisperse Fe NPs with sizes ranging from 13-20 nm have been synthesized through the chemical thermal-decomposition in a solution. Silica shells were then coated on the Fe NPs by a two-phase oil-in-water method. Dye molecules were first bonded to a silica precursor and then encapsulated into the silica shell during the coating process. The silica shells protect both the Fe NPs and dye molecules, which makes them as robust probes. The dye doped Fe/SiO2 core/shell NPs remain both highly magnetic and highly fluorescent. The stable dye doped Fe/SiO2NPs have been used as a dual functional probe for both magnetic heating and local nanoscale temperature sending, and their performance will be reported. Research supported by NSF DMR 0547036, DMR1104994.

  14. Synthesis, Photophysical and Electrochemical Properties of a Mixed Bipyridyl-Phenanthrolyl Ligand Ru(II Heteroleptic Complex Having trans-2-Methyl-2-butenoic Acid Functionalities

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2011-09-01

    Full Text Available In this work, two ligands: 4-(trans-2-Methyl-2-butenoic acid-2,2'-bipyridine (L1 and 5-(trans-2-methyl-2-butenoic acid-1,10-phenanthroline (L2, with the corresponding mixed-ligand heteroleptic Ru(II complex were synthesized and characterized by FT-IR, 1H-, 13C-NMR spectroscopy and elemental analysis. The influence of the mixed functionalized polypyridyl ruthenium(II complex on the photophysical and electrochemical properties were investigated and compared to individual single-ligand homoleptic complexes. Interestingly, the mixed-ligand complex formulated as [RuL1L2(NCS2] exhibits broad and intense metal-to-ligand charge transfer (MLCT absorption with a high molar extinction coefficient (λmax = 514 nm, ε = 69,700 M−1 cm−1, better than those of individual single-ligand complexes, [Ru(L12(NCS2] and [Ru(L22(NCS2], and a strong photoluminescence intensity ratio in the red region at λem = 686 nm. The electrochemical properties of the complex indicated that the redox processes are ligand-based.

  15. A new Kaempferol-based Ru(II) coordination complex, Ru(kaem)Cl(DMSO){sub 3}: Structure and absorption-emission spectroscopy study

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Ming Wei; Gang, Jong Back; Kim, Sang Ho; Yoon, Min Young [Gachon University, Sungnam (Korea, Republic of)

    2016-10-15

    Recent interest in developing a new anticancer drug with low side effects has led to the study of the combination of two new anticancer drugs. Although both kaempferol (kaem) and Ru-based metal complexes have not been proven as effective drugs, their unique anticancer activities with reduced side effects have drawn our attention to the need for further studies on their potential in anticancer application. Herein, we report the synthesis, characterization, structure, and spectroscopic properties of a kaem-based Ru (II) complex, RuCl(kaem)(DMSO){sub 3} (1). Because of the presence of a catechol-like functional group in its dihydropyran ring, kaem can strongly bind to the Ru(II) metal center in a basic medium. The molecular structure of the complex was characterized by spectroscopic studies and X-ray crystal structure analysis. In addition, the complex forms a molecular dimer as a result of the cooperative effect of H-bonding and π–π stacking interactions. Moreover, the molecular dimer forms a ladder-like one-dimensional network structure by water mediated H-bonding that further extended into a three-dimensional packing structure. UV–Vis spectroscopy studies of the complex demonstrated the appearance of a strong metal to ligand charge transfer (MLCT) band in the visible region with strong fluorescence emission derived from the MLCT. Further studies are now in progress to demonstrate synergetic anticancer activity.

  16. A new Kaempferol-based Ru(II) coordination complex, Ru(kaem)Cl(DMSO)3: Structure and absorption-emission spectroscopy study

    International Nuclear Information System (INIS)

    Shao, Ming Wei; Gang, Jong Back; Kim, Sang Ho; Yoon, Min Young

    2016-01-01

    Recent interest in developing a new anticancer drug with low side effects has led to the study of the combination of two new anticancer drugs. Although both kaempferol (kaem) and Ru-based metal complexes have not been proven as effective drugs, their unique anticancer activities with reduced side effects have drawn our attention to the need for further studies on their potential in anticancer application. Herein, we report the synthesis, characterization, structure, and spectroscopic properties of a kaem-based Ru (II) complex, RuCl(kaem)(DMSO) 3 (1). Because of the presence of a catechol-like functional group in its dihydropyran ring, kaem can strongly bind to the Ru(II) metal center in a basic medium. The molecular structure of the complex was characterized by spectroscopic studies and X-ray crystal structure analysis. In addition, the complex forms a molecular dimer as a result of the cooperative effect of H-bonding and π–π stacking interactions. Moreover, the molecular dimer forms a ladder-like one-dimensional network structure by water mediated H-bonding that further extended into a three-dimensional packing structure. UV–Vis spectroscopy studies of the complex demonstrated the appearance of a strong metal to ligand charge transfer (MLCT) band in the visible region with strong fluorescence emission derived from the MLCT. Further studies are now in progress to demonstrate synergetic anticancer activity

  17. Development of a Novel Cu(II Complex Modified Electrode and a Portable Electrochemical Analyzer for the Determination of Dissolved Oxygen (DO in Water

    Directory of Open Access Journals (Sweden)

    Salvatore Gianluca Leonardi

    2016-04-01

    Full Text Available The development of an electrochemical dissolved oxygen (DO sensor based on a novel Cu(II complex-modified screen printed carbon electrode is reported. The voltammetric behavior of the modified electrode was investigated at different scan rates and oxygen concentrations in PBS (pH = 7. An increase of cathodic current (at about −0.4 vs. Ag/AgCl with the addition of oxygen was observed. The modified Cu(II complex electrode was demonstrated for the determination of DO in water using chronoamperometry. A small size and low power consumption home-made portable electrochemical analyzer based on custom electronics for sensor interfacing and operating in voltammetry and amperometry modes has been also designed and fabricated. Its performances in the monitoring of DO in water were compared with a commercial one.

  18. Asymmetric organocatalytic Michael addition of Meldrum's acid to nitroalkenes: probing the mechanism of bifunctional thiourea organocatalysts

    OpenAIRE

    Kataja, Antti O.; Koskinen, Ari M.P.

    2010-01-01

    The asymmetric Michael addition of Meldrum’s acid to nitroalkenes was studied using a novel type of Cinchona alkaloid-based bifunctional thiourea organocatalyst. The functionality of the thiourea catalysts was also probed by preparing and testing thiourea-N-methylated analogues of the well-known bis-(3,5-trifluoromethyl)phenyl-substituted catalyst. Peer reviewed

  19. Synthesis, characterization and use of ATRP bifunctional initiator with trichloromethyl end-groups

    Czech Academy of Sciences Publication Activity Database

    Toman, Luděk; Janata, Miroslav; Spěváček, Jiří; Masař, Bohumil; Vlček, Petr; Látalová, Petra

    2002-01-01

    Roč. 43, č. 2 (2002), s. 18-19 ISSN 0032-3934 R&D Projects: GA ČR GA203/01/0513 Institutional research plan: CEZ:AV0Z4050913 Keywords : bifunctional initiator * ATRP polymerization * trichloromethyl end-groups Subject RIV: CD - Macromolecular Chemistry

  20. Bi-functional glycosyltransferases catalyze both extension and termination of pectic galactan oligosaccharides

    DEFF Research Database (Denmark)

    Laursen, Tomas; Stonebloom, Solomon H; Pidatala, Venkataramana R

    2018-01-01

    . Transfer of Arap to galactan prevents further addition of galactose residues, resulting in a lower degree of polymerization. We show that this dual activity occurs both in vitro and in vivo. The herein described bi-functionality of AtGALS1 may suggest that plants can produce the incredible structural...

  1. High surface area carbon for bifunctional air electrodes applied in zinc-air batteries

    Energy Technology Data Exchange (ETDEWEB)

    Arai, H [on leave from NTT Laboratories (Japan); Mueller, S; Haas, O [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    Bifunctional air electrodes with high surface area carbon substrates showed low reduction overpotential, thus are promising for enhancing the energy efficiency and power capability of zinc-air batteries. The improved performance is attributed to lower overpotential due to diffusion of the reaction intermediate, namely the peroxide ion. (author) 1 fig., 2 refs.

  2. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    DEFF Research Database (Denmark)

    Li, Hu; Khokarale, Santosh Govind; Kotni, Ramakrishna

    2014-01-01

    carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl...

  3. D-bifunctional protein deficiency associated with drug resistant infantile spasms

    NARCIS (Netherlands)

    Buoni, Sabrina; Zannolli, Raffaella; Waterham, Hans; Wanders, Ronald; Fois, Alberto

    2007-01-01

    Peroxisomal disorders appear with a frequency of about 1:5000 in newborns. Peroxisomal D-bifunctional protein (D-BP), encoded by the HSD17B4 gene (gene ID: 3294; locus tag: HGNC:5213, chromosome 5q2; official symbol: HSD17B4; name: hydroxysteroid (17-beta) dehydrogenase; gene type: protein coding)

  4. Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts.

    Science.gov (United States)

    Hong, Do-Young; Miller, Stephen J; Agrawal, Pradeep K; Jones, Christopher W

    2010-02-21

    Pt supported on HY zeolite is successfully used as a bifunctional catalyst for phenol hydrodeoxygenation in a fixed-bed configuration at elevated hydrogen pressures, leading to hydrogenation-hydrogenolysis ring-coupling reactions producing hydrocarbons, some with enhanced molecular weight.

  5. Efficient hydrodeoxygenation of biomass-derived ketones over bifunctional Pt-polyoxometalate catalyst.

    Science.gov (United States)

    Alotaibi, Mshari A; Kozhevnikova, Elena F; Kozhevnikov, Ivan V

    2012-07-21

    Acidic heteropoly salt Cs(2.5)H(0.5)PW(12)O(40) doped with Pt nanoparticles is a highly active and selective catalyst for one-step hydrogenation of methyl isobutyl and diisobutyl ketones to the corresponding alkanes in the gas phase at 100 °C with 97-99% yield via metal-acid bifunctional catalysis.

  6. Liquid phase in situ hydrodeoxygenation of biomass-derived phenolic compounds to hydrocarbons over bifunctional catalysts

    Science.gov (United States)

    Junfeng Feng; Chung-yun Hse; Zhongzhi Yang; Kui Wang; Jianchun Jiang; Junming Xu

    2017-01-01

    The objective of this study was to find an effective method for converting renewable biomass-derived phenolic compounds into hydrocarbons bio-fuel via in situ catalytic hydrodeoxygenation. The in situ hydrodeoxygenation of biomass-derived phenolic compounds was carried out in methanol-water solvent over bifunctional catalysts of Raney Ni and HZSM-5 or H-Beta. In the in...

  7. Bifunctional Interface of Au and Cu for Improved CO2 Electroreduction.

    Science.gov (United States)

    Back, Seoin; Kim, Jun-Hyuk; Kim, Yong-Tae; Jung, Yousung

    2016-09-07

    Gold is known currently as the most active single-element electrocatalyst for CO2 electroreduction reaction to CO. In this work, we combine Au with a second metal element, Cu, to reduce the amount of precious metal content by increasing the surface-to-mass ratio and to achieve comparable activity to Au-based catalysts. In particular, we demonstrate that the introduction of a Au-Cu bifunctional "interface" is more beneficial than a simple and conventional homogeneous alloying of Au and Cu in stabilizing the key intermediate species, *COOH. The main advantages of the proposed metal-metal bifunctional interfacial catalyst over the bimetallic alloys include that (1) utilization of active materials is improved, and (2) intrinsic properties of metals are less affected in bifunctional catalysts than in alloys, which can then facilitate a rational bifunctional design. These results demonstrate for the first time the importance of metal-metal interfaces and morphology, rather than the simple mixing of the two metals homogeneously, for enhanced catalytic synergies.

  8. Bifunctional catalysts for the direct production of liquid fuels from syngas

    NARCIS (Netherlands)

    Sartipi, S.

    2014-01-01

    Design and development of catalyst formulations that maximize the direct production of liquid fuels by combining Fischer-Tropsch synthesis (FTS), hydrocarbon cracking, and isomerization into one single catalyst particle (bifunctional FTS catalyst) have been investigated in this thesis. To achieve

  9. Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

    Science.gov (United States)

    Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

    2017-08-09

    Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

  10. Boosting Bifunctional Oxygen Electrocatalysis with 3D Graphene Aerogel-Supported Ni/MnO Particles.

    Science.gov (United States)

    Fu, Gengtao; Yan, Xiaoxiao; Chen, Yifan; Xu, Lin; Sun, Dongmei; Lee, Jong-Min; Tang, Yawen

    2018-02-01

    Electrocatalysts for oxygen-reduction and oxygen-evolution reactions (ORR and OER) are crucial for metal-air batteries, where more costly Pt- and Ir/Ru-based materials are the benchmark catalysts for ORR and OER, respectively. Herein, for the first time Ni is combined with MnO species, and a 3D porous graphene aerogel-supported Ni/MnO (Ni-MnO/rGO aerogel) bifunctional catalyst is prepared via a facile and scalable hydrogel route. The synthetic strategy depends on the formation of a graphene oxide (GO) crosslinked poly(vinyl alcohol) hydrogel that allows for the efficient capture of highly active Ni/MnO particles after pyrolysis. Remarkably, the resulting Ni-MnO/rGO aerogels exhibit superior bifunctional catalytic performance for both ORR and OER in an alkaline electrolyte, which can compete with the previously reported bifunctional electrocatalysts. The MnO mainly contributes to the high activity for the ORR, while metallic Ni is responsible for the excellent OER activity. Moreover, such bifunctional catalyst can endow the homemade Zn-air battery with better power density, specific capacity, and cycling stability than mixed Pt/C + RuO 2 catalysts, demonstrating its potential feasibility in practical application of rechargeable metal-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Structure and potential applications of amido lanthanide complexes chelated by bifunctional b-diketiminate ligand

    Czech Academy of Sciences Publication Activity Database

    Olejník, R.; Padělková, Z.; Fridrichová, A.; Horáček, Michal; Merna, J.; Růžička, A.

    2014-01-01

    Roč. 759, JUN 2014 (2014), s. 1-10 ISSN 0022-328X R&D Projects: GA ČR GAP106/10/0924 Institutional support: RVO:61388955 Keywords : Bifunctional b-diketiminates * lanthanides * hydroamination Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.173, year: 2014

  12. Direct catalytic transformation of carbohydrates into 5-ethoxymethylfurfural with acid–base bifunctional hybrid nanospheres

    International Nuclear Information System (INIS)

    Li, Hu; Govind, Khokarale Santosh; Kotni, Ramakrishna; Shunmugavel, Saravanamurugan; Riisager, Anders; Yang, Song

    2014-01-01

    Graphical abstract: Catalytic conversion of carbohydrates into HMF and EMF in ethanol/DMSO with acid–base bifunctional hybrid nanospheres prepared from self-assembly of corresponding basic amino acids and HPA. - Highlights: • Acid–base bifunctional nanospheres were efficient for production of EMF from sugars. • Synthesis of EMF in a high yield of 76.6% was realized from fructose. • Fructose based biopolymers could also be converted into EMF with good yields. • Ethyl glucopyranoside was produced in good yields from glucose in ethanol. - Abstract: A series of acid–base bifunctional hybrid nanospheres prepared from the self-assembly of basic amino acids and phosphotungstic acid (HPA) with different molar ratios were employed as efficient and recyclable catalysts for synthesis of liquid biofuel 5-ethoxymethylfurfural (EMF) from various carbohydrates. A high EMF yield of 76.6%, 58.5%, 42.4%, and 36.5% could be achieved, when fructose, inulin, sorbose, and sucrose were used as starting materials, respectively. Although, the acid–base bifunctional nanocatalysts were inert for synthesis of EMF from glucose based carbohydrates, ethyl glucopyranoside in good yields could be obtained from glucose in ethanol. Moreover, the nanocatalyst functionalized with acid and basic sites was able to be reused several times with no significant loss in catalytic activity

  13. Comparison of bifunctional chelates for {sup 64}Cu antibody imaging

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Cara L.; Crisp, Sarah; Bensimon, Corinne [MDS Nordion, Vancouver, BC (Canada); Yapp, Donald T.T.; Ng, Sylvia S.W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); University of British Columba, The Faculty of Pharmaceutical Sciences, Vancouver, BC (Canada); Sutherland, Brent W. [British Columbia Cancer Agency Research Centre, Vancouver, BC (Canada); Gleave, Martin [Prostate Centre at Vancouver General Hospital, Vancouver, BC (Canada); Jurek, Paul; Kiefer, Garry E. [Macrocyclics Inc., Dallas, TX (United States)

    2010-11-15

    Improved bifunctional chelates (BFCs) are needed to facilitate efficient {sup 64}Cu radiolabeling of monoclonal antibodies (mAbs) under mild conditions and to yield stable, target-specific agents. The utility of two novel BFCs, 1-Oxa-4,7,10-triazacyclododecane-5-S-(4-isothiocyanatobenzyl)-4,7,10-triacetic acid (p-SCN-Bn-Oxo-DO3A) and 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-4-S-(4-isothiocyanatobenzyl)-3,6,9-triacetic acid (p-SCN-Bn-PCTA), for mAb imaging with {sup 64}Cu were compared to the commonly used S-2-(4-isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane-tetraacetic acid (p-SCN-Bn-DOTA). The BFCs were conjugated to trastuzumab, which targets the HER2/neu receptor. {sup 64}Cu radiolabeling of the conjugates was optimized. Receptor binding was analyzed using flow cytometry and radioassays. Finally, PET imaging and biodistribution studies were done in mice bearing either HER2/neu-positive or HER2/neu-negative tumors. {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab were prepared at room temperature in >95% radiochemical yield (RCY) in <30 min, compared to only 88% RCY after 2 h for the preparation of {sup 64}Cu-DOTA-trastuzumab under the same conditions. Cell studies confirmed that the immunoreactivity of the mAb was retained for each of the bioconjugates. In vivo studies showed that {sup 64}Cu-Oxo-DO3A- and PCTA-trastuzumab had higher uptake than the {sup 64}Cu-DOTA-trastuzumab at 24 h in HER2/neu-positive tumors, resulting in higher tumor to background ratios and better tumor images. By 40 h all three of the {sup 64}Cu-BFC-trastuzumab conjugates allowed for clear visualization of the HER2/neu-positive tumors but not the negative control tumor. The antibody conjugates of PCTA and Oxo-DO3A were shown to have superior {sup 64}Cu radiolabeling efficiency and stability compared to the analogous DOTA conjugate. In addition, {sup 64}Cu-PCTA and Oxo-DO3A antibody conjugates may facilitate earlier imaging with greater target to background ratios than

  14. Synthesis and Biological Evaluation of Ru(II) and Pt(II) Complexes Bearing Carboxyl Groups as Potential Anticancer Targeted Drugs.

    Science.gov (United States)

    Martínez, Ma Ángeles; Carranza, M Pilar; Massaguer, Anna; Santos, Lucia; Organero, Juan A; Aliende, Cristina; de Llorens, Rafael; Ng-Choi, Iteng; Feliu, Lidia; Planas, Marta; Rodríguez, Ana M; Manzano, Blanca R; Espino, Gustavo; Jalón, Félix A

    2017-11-20

    The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at λ = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in

  15. Crystal structure of a mononuclear Ru(II) complex with a back-to-back terpyridine ligand: [RuCl(bpy)(tpy-tpy)](.).

    Science.gov (United States)

    Rein, Francisca N; Chen, Weizhong; Scott, Brian L; Rocha, Reginaldo C

    2015-09-01

    We report the structural characterization of [6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine](2,2'-bi-pyridine)-chlorido-ruthenium(II) hexa-fluorido-phosphate, [RuCl(C10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2'-bi-pyridine (bpy) and the tridendate ligand 6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine (tpy-tpy). The [RuCl(bpy)(tpy-tpy)](+) monocation has a distorted octa-hedral geometry at the central Ru(II) ion due to the restricted bite angle [159.32 (16)°] of the tridendate ligand. The Ru-bound tpy and bpy moieties are nearly planar and essentially perpendicular to each other with a dihedral angle of 89.78 (11)° between the least-squares planes. The lengths of the two Ru-N bonds for bpy are 2.028 (4) and 2.075 (4) Å, with the shorter bond being opposite to Ru-Cl. For tpy-tpy, the mean Ru-N distance involving the outer N atoms trans to each other is 2.053 (8) Å, whereas the length of the much shorter bond involving the central N atom is 1.936 (4) Å. The Ru-Cl distance is 2.3982 (16) Å. The free uncoordinated moiety of tpy-tpy adopts a trans,trans conformation about the inter-annular C-C bonds, with adjacent pyridyl rings being only approximately coplanar. The crystal packing shows significant π-π stacking inter-actions based on tpy-tpy. The crystal structure reported here is the first for a tpy-tpy complex of ruthenium.

  16. Silica Aerogels Doped with Ru(II) Tris 1,l0-Phenanthro1ine)-Electron Acceptor Dyads: Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Oxygen Sensors

    Science.gov (United States)

    Kevebtusm Bucgikas; Rawashdeh, Abdel M.; Elder, Ian A.; Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia

    2005-01-01

    Complexes 1 and 2 were characterized in fluid and frozen solution and as dopants of silica aerogels. The intramolecular quenching efficiency of pendant 4-benzoyl-N-methylpyridinium group (4BzPy) is solvent dependent: emission is quenched completely in acetonitrile but not in alcohols. On the other hand, N-benzyl-N'-methylviologen (BzMeV) quenches the emission in all solvents completely. The differences are traced electrochemically to a stronger solvation effect by the alcohol in the case of 1. In fiozen matrices or absorbed on the surfaces of silica aerogel, both 1 and 2 are photoluminescent. The lack of quenching has been traced to the environmental rigidity. When doped aerogels are cooled to 77K, the emission shifts to the blue and its intensity increases in analogy to what is observed with Ru(II) complexes in media undergoing fluid-to-rigid transition. The photoluminescence of 1 and 2 from the aerogel is quenched by oxygen diffusing through the pores. In the presence of oxygen, aerogels doped with 1 can modulate their emission over a wider dynamic range than aerogels doped with 2, and both are more sensitive than aerogels doped with Ru(II) tris(1,l0- phenanthroline). In contrast to frozen solutions, the luminescent moieties in the bulk of aerogels kept at 77K are still accessible, leading to more sensitive platforms for oxygen sensors than other ambient temperature configurations.

  17. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili

    2014-08-19

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Sorption of Pu(IV) from nitric acid by bifunctional anion-exchange resins

    International Nuclear Information System (INIS)

    Bartsch, R.A.; Zhang, Z.Y.; Elshani, S.; Zhao, W.; Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.; Chamberlin, R.M.

    1999-01-01

    Anion exchange is attractive for separating plutonium because the Pu(IV) nitrate complex is very strongly sorbed and few other metal ions form competing anionic nitrate complexes. The major disadvantage of this process has been the unusually slow rate at which the Pu(IV) nitrate complex is sorbed by the resin. The paper summarizes the concept of bifunctional anion-exchange resins, proposed mechanism for Pu(IV) sorption, synthesis of the alkylating agent, calculation of K d values from Pu(IV) sorption results, and conclusions from the study of Pu(IV) sorption from 7M nitric acid by macroporous anion-exchange resins including level of crosslinking, level of alkylation, length of spacer, and bifunctional vs. monofunctional anion-exchange resins

  19. Tethering metal ions to photocatalyst particulate surfaces by bifunctional molecular linkers for efficient hydrogen evolution

    KAUST Repository

    Yu, Weili; Isimjan, Tayirjan T.; Del Gobbo, Silvano; Anjum, Dalaver Hussain; Abdel-Azeim, Safwat; Cavallo, Luigi; Garcia Esparza, Angel T.; Domen, Kazunari; Xu, Wei; Takanabe, Kazuhiro

    2014-01-01

    A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species.

    Science.gov (United States)

    Needham, Lisa-Maria; Weber, Judith; Fyfe, James W B; Kabia, Omaru M; Do, Dung T; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M; Ghandi, Sonia; Bohndiek, Sarah E; Snaddon, Thomas N; Lee, Steven F

    2018-02-01

    Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H 2 O 2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H 2 O 2 . We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H 2 O 2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease.

  1. Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species

    Science.gov (United States)

    Needham, Lisa-Maria; Weber, Judith; Fyfe, James W. B.; Kabia, Omaru M.; Do, Dung T.; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M.; Ghandi, Sonia; Bohndiek, Sarah E.; Snaddon, Thomas N.; Lee, Steven F.

    2018-02-01

    Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H2O2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H2O2. We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H2O2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease.

  2. Loop Replacement Enhances the Ancestral Antibacterial Function of a Bifunctional Scorpion Toxin

    Directory of Open Access Journals (Sweden)

    Shangfei Zhang

    2018-06-01

    Full Text Available On the basis of the evolutionary relationship between scorpion toxins targeting K+ channels (KTxs and antibacterial defensins (Zhu S., Peigneur S., Gao B., Umetsu Y., Ohki S., Tytgat J. Experimental conversion of a defensin into a neurotoxin: Implications for origin of toxic function. Mol. Biol. Evol. 2014, 31, 546–559, we performed protein engineering experiments to modify a bifunctional KTx (i.e., weak inhibitory activities on both K+ channels and bacteria via substituting its carboxyl loop with the structurally equivalent loop of contemporary defensins. As expected, the engineered peptide (named MeuTXKα3-KFGGI remarkably improved the antibacterial activity, particularly on some Gram-positive bacteria, including several antibiotic-resistant opportunistic pathogens. Compared with the unmodified toxin, its antibacterial spectrum also enlarged. Our work provides a new method to enhance the antibacterial activity of bifunctional scorpion venom peptides, which might be useful in engineering other proteins with an ancestral activity.

  3. Chiral 2-Aminobenzimidazole as Bifunctional Catalyst in the Asymmetric Electrophilic Amination of Unprotected 3-Substituted Oxindoles

    Directory of Open Access Journals (Sweden)

    Llorenç Benavent

    2018-06-01

    Full Text Available The use of readily available chiral trans-cyclohexanediamine-benzimidazole derivatives as bifunctional organocatalysts in the asymmetric electrophilic amination of unprotected 3-substituted oxindoles is presented. Different organocatalysts were evaluated; the most successful one contained a dimethylamino moiety (5. With this catalyst under optimized conditions, different oxindoles containing a wide variety of substituents at the 3-position were aminated in good yields and with good to excellent enantioselectivities using di-tert-butylazodicarboxylate as the aminating agent. The procedure proved to be also efficient for the amination of 3-substituted benzofuranones, although with moderate results. A bifunctional role of the catalyst, acting as Brønsted base and hydrogen bond donor, is proposed according to the experimental results observed.

  4. 67Ga(NODASA): a new potential bifunctional radioligand for coupling to peptides

    International Nuclear Information System (INIS)

    Andre, J.P.; Maecke, H.R.; Zehnder, M.; Macko, L.; Kaspar, A.

    1998-01-01

    A new bifunctional chelator NODASA (1,4,7-triazacyclononane-1-succinic acid-4,7-diacetic acid) has been synthesised and its Ga(III) complex was crystallographically characterized by X-ray diffraction. The complex showed to be stable in serum and in acidic conditions and its stability constant was determined using a competition method with an auxiliary ligand. The conjugation of Ga(NODASA) to a model aminoacidamide proved the feasibility of a prelabelling approach. (author)

  5. Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiaofang [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Zou, Yongcun [State Key Laboratory of Inoranic Synthesis and Preparative Chemistryg, College of Chemistry, Jilin University, Changchun 130012 (China); Wu, Shujie; Liu, Heng [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China); Kan, Qiubin, E-mail: qkan@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023 (China)

    2011-06-15

    Graphical abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst. The obtained sample of SO{sub 3}H-MCM-41-NH{sub 2} containing amine and sulfonic acids exhibits excellent catalytic activity in aldol condensation reaction. Research highlights: {yields} Synthesize acid-base bifunctional mesoporous materials SO{sub 3}H-MCM-41-NH{sub 2}. {yields} Oxidation and then thermolysis to generate acidic site and basic site. {yields} Exhibit good catalytic performance in aldol condensation reaction between acetone and various aldehydes. -- Abstract: A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO{sub 3}H-MCM-41-NH{sub 2}. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state {sup 13}C CP/MAS NMR and solid-state {sup 29}Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO{sub 3}H-MCM-41-NH{sub 2}) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.

  6. Radiation Induced Crosslinking of Polyethylene in the Presence of Bifunctional Vinyl Monomers

    DEFF Research Database (Denmark)

    Joshi, M. S.; Singer, Klaus Albert Julius; Silverman, J.

    1977-01-01

    Several reports have been published showing that the radiation induced grafting of bifunctional vinyl monomers to low density polyethylene results in a product with an unusually high density of crosslinks. The same grafting reactions are shown to reduce the incipient gel dose by more than a factor...... of fifty. This paper is concerned with the apparent crosslinking produced by the radiation grafting of two monomers to polyethylene: acrylic acid and acrylonitrile....

  7. Collagen/chitosan based two-compartment and bi-functional dermal scaffolds for skin regeneration

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Feng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Wang, Mingbo [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); She, Zhending [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China); Fan, Kunwu; Xu, Cheng [Department of Plastic Surgery and Burns, Shenzhen Second People' s Hospital, Shenzhen 518035 (China); Chu, Bin; Chen, Changsheng [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shi, Shengjun, E-mail: shengjunshi@yahoo.com [The Burns Department of Zhujiang Hospital, Southern Medical University, Guangzhou 510280 (China); Tan, Rongwei, E-mail: tanrw@landobiom.com [Key Laboratory of Biomedical Materials and Implants, Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057 (China); Shenzhen Lando Biomaterials Co., Ltd., Shenzhen 518057 (China)

    2015-07-01

    Inspired from the sophisticated bilayer structures of natural dermis, here, we reported collagen/chitosan based two-compartment and bi-functional dermal scaffolds. Two functions refer to mediating rapid angiogenesis based on recombinant human vascular endothelial growth factor (rhVEGF) and antibacterial from gentamicin, which were encapsulated in PLGA microspheres. The gentamicin and rhVEGF encapsulated PLGA microspheres were further combined with collagen/chitosan mixtures in low (lower layer) and high (upper layer) concentrations, and molded to generate the two-compartment and bi-functional scaffolds. Based on morphology and pore structure analyses, it was found that the scaffold has a distinct double layered porous and connective structure with PLGA microspheres encapsulated. Statistical analysis indicated that the pores in the upper layer and in the lower layer have great variations in diameter, indicative of a two-compartment structure. The release profiles of gentamicin and rhVEGF exceeded 28 and 49 days, respectively. In vitro culture of mouse fibroblasts showed that the scaffold can facilitate cell adhesion and proliferation. Moreover, the scaffold can obviously inhibit proliferation of Staphylococcus aureus and Serratia marcescens, exhibiting its unique antibacterial effect. The two-compartment and bi-functional dermal scaffolds can be a promising candidate for skin regeneration. - Highlights: • The dermal scaffold is inspired from the bilayer structures of natural dermis. • The dermal scaffold has two-compartment structures. • The dermal scaffold containing VEGF and gentamicin encapsulated PLGA microspheres • The dermal scaffold can facilitate cell adhesion and proliferation.

  8. Bifunctional bridging linker-assisted synthesis and characterization of TiO{sub 2}/Au nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Žunič, Vojka, E-mail: vojka.zunic@ijs.si, E-mail: vojka13@gmail.com; Kurtjak, Mario; Suvorov, Danilo [Jožef Stefan Institute, Advanced Materials Department (Slovenia)

    2016-11-15

    Using a simple organic bifunctional bridging linker, titanium dioxide (TiO{sub 2}) nanoparticles were coupled with the Au nanoparticles to form TiO{sub 2}/Au nanocomposites with a variety of Au loadings. This organic bifunctional linker, meso-2,3-dimercaptosuccinic acid, contains two types of functional groups: (i) the carboxyl group, which enables binding to the TiO{sub 2}, and (ii) the thiol group, which enables binding to the Au. In addition, the organic bifunctional linker acts as a stabilizing agent to prevent the agglomeration and growth of the Au particles, resulting in the formation of highly dispersed Au nanoparticles. To form the TiO{sub 2}/Au nanocomposites in a simple way, we deliberately applied a synthetic method that simultaneously ensures: (i) the capping of the Au nanoparticles and (ii) the binding of different amounts of Au to the TiO{sub 2}. The TiO{sub 2}/Au nanocomposites formed with this method show enhanced UV and Vis photocatalytic activities when compared to the pure TiO{sub 2} nanopowders.Graphical Abstract.

  9. Collagen/chitosan based two-compartment and bi-functional dermal scaffolds for skin regeneration

    International Nuclear Information System (INIS)

    Wang, Feng; Wang, Mingbo; She, Zhending; Fan, Kunwu; Xu, Cheng; Chu, Bin; Chen, Changsheng; Shi, Shengjun; Tan, Rongwei

    2015-01-01

    Inspired from the sophisticated bilayer structures of natural dermis, here, we reported collagen/chitosan based two-compartment and bi-functional dermal scaffolds. Two functions refer to mediating rapid angiogenesis based on recombinant human vascular endothelial growth factor (rhVEGF) and antibacterial from gentamicin, which were encapsulated in PLGA microspheres. The gentamicin and rhVEGF encapsulated PLGA microspheres were further combined with collagen/chitosan mixtures in low (lower layer) and high (upper layer) concentrations, and molded to generate the two-compartment and bi-functional scaffolds. Based on morphology and pore structure analyses, it was found that the scaffold has a distinct double layered porous and connective structure with PLGA microspheres encapsulated. Statistical analysis indicated that the pores in the upper layer and in the lower layer have great variations in diameter, indicative of a two-compartment structure. The release profiles of gentamicin and rhVEGF exceeded 28 and 49 days, respectively. In vitro culture of mouse fibroblasts showed that the scaffold can facilitate cell adhesion and proliferation. Moreover, the scaffold can obviously inhibit proliferation of Staphylococcus aureus and Serratia marcescens, exhibiting its unique antibacterial effect. The two-compartment and bi-functional dermal scaffolds can be a promising candidate for skin regeneration. - Highlights: • The dermal scaffold is inspired from the bilayer structures of natural dermis. • The dermal scaffold has two-compartment structures. • The dermal scaffold containing VEGF and gentamicin encapsulated PLGA microspheres • The dermal scaffold can facilitate cell adhesion and proliferation

  10. Gas-phase behaviour of Ru(II) cyclopentadienyl-derived complexes with N-coordinated ligands by electrospray ionization mass spectrometry: fragmentation pathways and energetics.

    Science.gov (United States)

    Madeira, Paulo J Amorim; Morais, Tânia S; Silva, Tiago J L; Florindo, Pedro; Garcia, M Helena

    2012-08-15

    The gas-phase behaviour of six Ru(II) cyclopentadienyl-derived complexes with N-coordinated ligands, compounds with antitumor activities against several cancer lines, was studied. This was performed with the intent of establishing fragmentation pathways and to determine the Ru-L(N) and Ru-L(P) ligand bond dissociation energies. Such knowledge can be an important tool for the postulation of the mechanisms of action of these anticancer drugs. Two types of instruments equipped with electrospray ionisation were used (ion trap and a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer). The dissociation energies were determined using energy-variable collision-induced dissociation measurements in the ion trap. The FTICR instrument was used to perform MS(n) experiments on one of the compounds and to obtain accurate mass measurements. Theoretical calculations were performed at the density functional theory (DFT) level using two different functionals (B3LYP and M06L) to estimate the dissociation energies of the complexes under study. The influence of the L(N) on the bond dissociation energy (D) of RuCp compounds with different nitrogen ligands was studied. The lability order of L(N) was: imidazole<1-butylimidazole<5-phenyl-1H-tetrazole<1-benzylimidazole. Both the functionals used gave the following ligand lability order: imidazole<1-benzylimidazole<5-phenyl-1H-tetrazole<1-butylimidazole. It is clear that there is an inversion between 1-benzylimidazole and 1-butylimidazole for the experimental and theoretical lability orders. The M06L functional afforded values of D closer to the experimental values. The type of phosphane (L(P) ) influenced the dissociation energies, with values of D being higher for Ru-L(N) with 1-butylimidazole when the phosphane was 1,2-bis(diphenylphosphino)ethane. The Ru-L(P) bond dissociation energy for triphenylphosphane was independent of the type of complex. The D values of Ru-L(N) and Ru-L(P) were determined for all six compounds and

  11. Ocular Toxicity Profile of ST-162 and ST-168 as Novel Bifunctional MEK/PI3K Inhibitors.

    Science.gov (United States)

    Smith, Andrew; Pawar, Mercy; Van Dort, Marcian E; Galbán, Stefanie; Welton, Amanda R; Thurber, Greg M; Ross, Brian D; Besirli, Cagri G

    2018-04-30

    ST-162 and ST-168 are small-molecule bifunctional inhibitors of MEK and PI3K signaling pathways that are being developed as novel antitumor agents. Previous small-molecule and biologic MEK inhibitors demonstrated ocular toxicity events that were dose limiting in clinical studies. We evaluated in vitro and in vivo ocular toxicity profiles of ST-162 and ST-168. Photoreceptor cell line 661W and adult retinal pigment epithelium cell line ARPE-19 were treated with increasing concentrations of bifunctional inhibitors. Western blots, cell viability, and caspase activity assays were performed to evaluate MEK and PI3K inhibition and dose-dependent in vitro toxicity, and compared with monotherapy. In vivo toxicity profile was assessed by intravitreal injection of ST-162 and ST-168 in Dutch-Belted rabbits, followed by ocular examination and histological analysis of enucleated eyes. Retinal cell lines treated with ST-162 or ST-168 exhibited dose-dependent inhibition of MEK and PI3K signaling. Compared with inhibition by monotherapies and their combinations, bifunctional inhibitors demonstrated reduced cell death and caspase activity. In vivo, both bifunctional inhibitors exhibited a more favorable toxicity profile when compared with MEK inhibitor PD0325901. Novel MEK and PI3K bifunctional inhibitors ST-162 and ST-168 demonstrate favorable in vitro and in vivo ocular toxicity profiles, supporting their further development as potential therapeutic agents targeting multiple aggressive tumors.

  12. Benzimidazolyl methyliminodiacetic acids: new bifunctional chelators of technetium for hepatobiliary scintigraphy

    International Nuclear Information System (INIS)

    Hunt, F.C.; Wilson, J.G.; Maddalena, D.J.

    1979-01-01

    Dimethyl- and chloro- substituted benzimidazolyl methyliminodiacetic acids have been synthesized and evaluated as new bifunctional chelators of /sup 99m/Tc. Stannous chelates of these compounds were prepared as freeze-dried kits and labeled with /sup 99m/Tc. The radiopharmaceuticals thus prepared were rapidly excreted by the hepatobiliary system of rats and rabbits with little urinary excretion. The chloro- compound had a higher biliary and lesser urinary excretion than the dimethyl- however both technetium complexes provided good scintigraphic images of the hepatobiliary system in animals. The compounds behaved similarly to the /sup 99m/Tc-lidocaine iminodiacetic acid [HIDA] complexes with respect to their biliary elimination

  13. Bifunctional groups grafted polyethersulfone magnetic beads for selective sequestration of plutonium

    International Nuclear Information System (INIS)

    Paul, Sumana; Aggarwal, S.K.; Pandey, A.K.

    2014-01-01

    The present study involves synthesis of polyethersulfone (PES) beads grafted with two different monomers viz. 2-hydroxyethylmethacrylate phosphoric acid ester (HEMP) and 2-acrylamido-2-methyl-1-propane sulphonic acid (AMPS) by photo-induced free radical polymerization method. The selection of bifunctional polymer was based on our previous studies, which indicated its efficacy for selective preconcentration of Pu from 3-4 mol L -1 HNO 3 . The HEMP-co-AMPS grafted PES beads were used for selective extraction of plutonium from dissolver solution

  14. Recent Advances in Dynamic Kinetic Resolution by Chiral Bifunctional (Thiourea- and Squaramide-Based Organocatalysts

    Directory of Open Access Journals (Sweden)

    Pan Li

    2016-10-01

    Full Text Available The organocatalysis-based dynamic kinetic resolution (DKR process has proved to be a powerful strategy for the construction of chiral compounds. In this feature review, we summarized recent progress on the DKR process, which was promoted by chiral bifunctional (thiourea and squaramide catalysis via hydrogen-bonding interactions between substrates and catalysts. A wide range of asymmetric reactions involving DKR, such as asymmetric alcoholysis of azlactones, asymmetric Michael–Michael cascade reaction, and enantioselective selenocyclization, are reviewed and demonstrate the efficiency of this strategy. The (thiourea and squaramide catalysts with dual activation would be efficient for more unmet challenges in dynamic kinetic resolution.

  15. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.; Smith, Colin D.; Wang, Yong

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  16. Bifunctional electrode performance for zinc-air flow cells with pulse charging

    International Nuclear Information System (INIS)

    Pichler, Birgit; Weinberger, Stephan; Reščec, Lucas; Grimmer, Ilena; Gebetsroither, Florian; Bitschnau, Brigitte; Hacker, Viktor

    2017-01-01

    Highlights: •Manufacture of bi-catalyzed bifunctional air electrodes via scalable process. •Direct synthesis of NiCo 2 O 4 on carbon nanofibers or nickel powder support. •450 charge and discharge cycles over 1000 h at 50 mA cm −2 demonstrated. •Pulse charging with 150 mA cm −2 is successfully applied on air electrodes. •Charge and discharge ΔV of <0.8 V at 50 mA cm −2 when supplied with O 2. -- Abstract: Bifunctional air electrodes with tuned composition consisting of two precious metal-free oxide catalysts are manufactured for application in rechargeable zinc-air flow batteries and electrochemically tested via long-term pulse charge and discharge cycling experiments at 50 mA cm −2 (mean). NiCo 2 O 4 spinel, synthesized via direct impregnation on carbon nanofibers or nickel powder and characterized by energy dispersive X-ray spectroscopy and X-ray diffraction experiments, shows high activity toward oxygen evolution reaction with low charge potentials of < 2.0 V vs. Zn/Zn 2+ . La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 perovskite exhibits bifunctional activity and outperforms the NiCo 2 O 4 spinel in long-term stability tenfold. By combining the catalysts in one bi-catalyzed bifunctional air electrode, stable performances of more than 1000 h and 450 cycles are achieved when supplied with oxygen and over 650 h and 300 cycles when supplied with synthetic air. In addition, the pulse charging method, which is beneficial for compact zinc deposition, is successfully tested on air electrodes during long-term operation. The oxygen evolution potentials during pulse, i.e. at tripled charge current density of 150 mA cm −2 , are only 0.06–0.08 V higher compared to constant charging current densities. Scanning electron microscopy confirms that mechanical degradation caused by bubble formation during oxygen evolution results in slowly decreasing discharge potentials.

  17. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    –titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

  18. Basic evaluation of 67Ga labeled digoxin derivative as a metal-labeled bifunctional radiopharmaceutical

    International Nuclear Information System (INIS)

    Fujibayashi, Yasuhisa; Konishi, Junji; Takemura, Yasutaka; Taniuchi, Hideyuki; Iijima, Naoko; Yokoyama, Akira.

    1993-01-01

    To develop metal-labeled digoxin radiopharmaceuticals with affinity with anti-digoxin antibody as well as Na + , K + -ATPase, a digoxin derivative conjugated with deferoxamine was synthesized. The derivative had a high binding affinity with 67 Ga at deferoxamine introduced to the terminal sugar ring of digoxin. The 67 Ga labeled digoxin derivative showed enough in vitro binding affinity and selectivity to anti-digoxin antibody as well as Na + , K + -ATPase. The 67 Ga labeled digoxin derivative is considered to be a potential metal-labeled bifunctional radiopharmaceutical for digoxin RIA as well as myocardial Na + , K + -ATPase imaging. (author)

  19. Neurodegeneration in D-bifunctional protein deficiency: diagnostic clues and natural history using serial magnetic resonance imaging

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Aneal [University of Calgary, Department of Medical Genetics and Pediatrics, Alberta Children' s Hospital, Calgary, AB (Canada); Wei, Xing-Chang [University of Calgary, Department of Radiology, Alberta Children' s Hospital, Calgary, AB (Canada); Snyder, Floyd F. [Alberta Children' s Hospital, Biochemical Genetics Laboratory, Calgary, AB (Canada); Mah, Jean K. [University of Calgary, Division of Neurology, Department of Pediatrics, Calgary, AB (Canada); Waterham, Hans; Wanders, Ronald J.A. [University of Amsterdam, Academic Medical Center, Lab Genetic Metabolic Diseases, Amsterdam (Netherlands)

    2010-12-15

    We report serial neurodegenerative changes on neuroimaging in a rare peroxisomal disease called D-bifunctional protein deficiency. The pattern of posterior to anterior demyelination with white matter disease resembles X-linked adrenoleukodystrophy. We feel this case is important to (1) highlight that D-bifunctional protein deficiency should be considered in cases where the neuroimaging resembles X-linked adrenoleukodystrophy, (2) to show different stages of progression to help identify this disease using neuroimaging in children, and (3) to show that neuroimaging suggesting a leukodystrophy can warrant peroxisomal beta-oxidation studies in skin fibroblasts even when plasma very long chain fatty acids are normal. (orig.)

  20. Synergistic extraction of Am(III) using HTTA and bi-functional (DHDECMP) and mono-functional (TBP) donors

    International Nuclear Information System (INIS)

    Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

    1999-01-01

    The equilibrium constant (log Ks) for the organic phase synergistic reaction for Am(III)-HTTA system with bi-functional neutral donor di-hexyl di-ethyl carbamoylmethyl phosphonate (DHDECMP) was found to be about two orders of magnitude higher than that of the mono-functional neutral donor (TBP) with comparable basicity values. This log Ks value along with a large positive entropy change with DHDECMP compared to that with TBP confirms that the neutral donors like DHDECMP behave as bi-functional, in sharp contrast to its mono-functional behaviour in Pu(VI). (author)

  1. Bifunctional silica nanospheres with 3-aminopropyl and phenyl groups. Synthesis approach and prospects of their applications

    Science.gov (United States)

    Kotsyuda, Sofiya S.; Tomina, Veronika V.; Zub, Yuriy L.; Furtat, Iryna M.; Lebed, Anastasia P.; Vaclavikova, Miroslava; Melnyk, Inna V.

    2017-10-01

    Spherical silica particles with bifunctional (tbnd Si(CH2)3NH2/tbnd SiC6H5) surface layers were synthesized by the Stöber method using ternary alkoxysilanes systems. The influence of the synthesis conditions, such as temperature and stirring time on the process of nanoparticles formation was studied. The presence of introduced functional groups was confirmed by FTIR. The composition of the surface layers examined by elemental analysis and acid-base titration was shown to be independent from the synthesis temperature. However, the size of the obtained particles depends on the synthesis temperature and, according to photon cross-correlation spectroscopy, can be varied from 50 to 846 nm. The variation of electric charges of N-functional groups was disclosed in obtained nanospheres and attributed to different surface location of these groups and their surrounding with other groups. The sorption of Cu(II) ions by functionalized silicas depends on the concentration of amino groups, which correlates with the isoelectric point values (determined to vary from 8.26 to 9.21). Bifunctional nanoparticles adsorb 99.0 mg/g of methylene blue, compared with 48.0 mg/g by silica sample with only amino groups. The nanospheres, both with and without adsorbed Cu2+, demonstrate reasonable antibacterial activity against S. aureus ATCC 25923, depending on particle concentration in water suspension.

  2. Synthesis of novel bifunctional chelators and their use in preparing monoclonal antibody conjugates for tumor targeting

    International Nuclear Information System (INIS)

    Westerberg, D.A.; Carney, P.L.; Rogers, P.E.; Kline, S.J.; Johnson, D.K.

    1989-01-01

    Bifunctional derivatives of the chelating agents ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, in which a p-isothiocyanatobenzyl moiety is attached at the methylene carbon atom of one carboxymethyl arm, was synthesized by reductive alkylation of the relevant polyamine with (p-nitrophenyl)pyruvic acid followed by carboxymethylation, reduction of the nitro group, and reaction with thiophosgene. The resulting isothiocyanate derivatives reacted with monoclonal antibody B72.3 to give antibody-chelator conjugates containing 3 mol of chelator per mole of immunoglobulin, without significant loss of immunological activity. Such conjugates, labeled with the radioisotopic metal indium-111, selectively bound a human colorectal carcinoma implanted in nude mice when given intravenously. Uptake into normal tissues was comparable to or lower than that reported for analogous conjugates with known bifunctional chelators. It is concluded that substitution with a protein reactive group at this position in polyaminopolycarboxylate chelators does not alter the chelating properties of these molecules to a sufficient extent to adversely affect biodistribution and thus provides a general method for the synthesis of such chelators

  3. Iminodiacetic acid as bifunctional linker for dimerization of cyclic RGD peptides

    International Nuclear Information System (INIS)

    Xu, Dong; Zhao, Zuo-Quan; Chen, Shu-Ting; Yang, Yong; Fang, Wei; Liu, Shuang

    2017-01-01

    Introduction: In this study, I2P-RGD 2 was used as the example to illustrate a novel approach for dimerization of cyclic RGD peptides. The main objective of this study was to explore the impact of bifunctional linkers (glutamic acid vs. iminodiacetic acid) on tumor-targeting capability and excretion kinetics of the 99m Tc-labeled dimeric cyclic RGD peptides. Methods: HYNIC-I2P-RGD 2 was prepared by reacting I2P-RGD 2 with HYNIC-OSu in the presence of diisopropylethylamine, and was evaluated for its α v β 3 binding affinity against 125 I-echistatin bound to U87MG glioma cells. 99m Tc-I2P-RGD 2 was prepared with high specific activity (~185 GBq/μmol). The athymic nude mice bearing U87MG glioma xenografts were used to evaluate its biodistribution properties and image quality in comparison with those of 99m Tc-3P-RGD 2 . Results: The IC 50 value for HYNIC-I2P-RGD 2 was determined to be 39 ± 6 nM, which was very close to that (IC 50 = 33 ± 5 nM) of HYNIC-3P-RGD 2 . Replacing glutamic acid with iminodiacetic acid had little impact on α v β 3 binding affinity of cyclic RGD peptides. 99m Tc-I2P-RGD 2 and 99m Tc-3P-RGD 2 shared similar tumor uptake values over the 2 h period, and its α v β 3 -specificity was demonstrated by a blocking experiment. The uptake of 99m Tc-I2P-RGD 2 was significantly lower than 99m Tc-3P-RGD 2 in the liver and kidneys. The U87MG glioma tumors were visualized by SPECT with excellent contrast using both 99m Tc-I2P-RGD 2 and 99m Tc-3P-RGD 2 . Conclusion: Iminodiacetic acid is an excellent bifunctional linker for dimerization of cyclic RGD peptides. Bifunctional linkers have significant impact on the excretion kinetics of 99m Tc radiotracers. Because of its lower liver uptake and better tumor/liver ratios, 99m Tc-I2P-RGD 2 may have advantages over 99m Tc-3P-RGD 2 for diagnosis of tumors in chest region. -- Graphical abstract: This report presents novel approach for dimerization of cyclic RGD peptides using iminodiacetic acid as a

  4. Complexation and biodistribution study of 111In complexes of bifunctional phosphinic acid analogues of H4DOTA

    Czech Academy of Sciences Publication Activity Database

    Forsterová, Michaela; Zimová, Jana; Petrík, M.; Lázníček, M.; Lázníčková, A.; Hermann, P.; Melichar, František

    2007-01-01

    Roč. 2, č. 337 (2007), s. 34-34 ISSN 1619-7070 R&D Projects: GA AV ČR 1QS100480501 Institutional research plan: CEZ:AV0Z10480505 Keywords : bifunctional H4DOTA ligands * phosphinic acid analogues, * complexation of 111In Subject RIV: FR - Pharmacology ; Medidal Chemistry

  5. Catalysis engineering of bifunctional solids for the one-step synthesis of liquid fuels from syngas : A review

    NARCIS (Netherlands)

    Sartipi, S.; Makkee, M.; Kapteijn, F.; Gascon, J.

    2014-01-01

    The combination of acidic zeolites and Fischer–Tropsch synthesis (FTS) catalysts for one-step production of liquid fuels from syngas is critically reviewed. Bifunctional systems are classified by the proximity between FTS and acid functionalities on three levels: reactor, catalyst particle, and

  6. The structure of Haemophilus influenzae prephenate dehydrogenase suggests unique features of bifunctional TyrA enzymes

    International Nuclear Information System (INIS)

    Chiu, Hsiu-Ju; Abdubek, Polat; Astakhova, Tamara; Axelrod, Herbert L.; Carlton, Dennis; Clayton, Thomas; Das, Debanu; Deller, Marc C.; Duan, Lian; Feuerhelm, Julie; Grant, Joanna C.; Grzechnik, Anna; Han, Gye Won; Jaroszewski, Lukasz; Jin, Kevin K.; Klock, Heath E.; Knuth, Mark W.; Kozbial, Piotr; Krishna, S. Sri; Kumar, Abhinav; Marciano, David; McMullan, Daniel; Miller, Mitchell D.; Morse, Andrew T.; Nigoghossian, Edward; Okach, Linda; Reyes, Ron; Tien, Henry J.; Trame, Christine B.; Bedem, Henry van den; Weekes, Dana; Xu, Qingping; Hodgson, Keith O.; Wooley, John; Elsliger, Marc-André; Deacon, Ashley M.; Godzik, Adam; Lesley, Scott A.; Wilson, Ian A.

    2010-01-01

    The crystal structure of the prephenate dehydrogenase component of the bifunctional H. influenzae TyrA reveals unique structural differences between bifunctional and monofunctional TyrA enzymes. Chorismate mutase/prephenate dehydrogenase from Haemophilus influenzae Rd KW20 is a bifunctional enzyme that catalyzes the rearrangement of chorismate to prephenate and the NAD(P) + -dependent oxidative decarboxylation of prephenate to 4-hydroxyphenylpyruvate in tyrosine biosynthesis. The crystal structure of the prephenate dehydrogenase component (HinfPDH) of the TyrA protein from H. influenzae Rd KW20 in complex with the inhibitor tyrosine and cofactor NAD + has been determined to 2.0 Å resolution. HinfPDH is a dimeric enzyme, with each monomer consisting of an N-terminal α/β dinucleotide-binding domain and a C-terminal α-helical dimerization domain. The structure reveals key active-site residues at the domain interface, including His200, Arg297 and Ser179 that are involved in catalysis and/or ligand binding and are highly conserved in TyrA proteins from all three kingdoms of life. Tyrosine is bound directly at the catalytic site, suggesting that it is a competitive inhibitor of HinfPDH. Comparisons with its structural homologues reveal important differences around the active site, including the absence of an α–β motif in HinfPDH that is present in other TyrA proteins, such as Synechocystis sp. arogenate dehydrogenase. Residues from this motif are involved in discrimination between NADP + and NAD + . The loop between β5 and β6 in the N-terminal domain is much shorter in HinfPDH and an extra helix is present at the C-terminus. Furthermore, HinfPDH adopts a more closed conformation compared with TyrA proteins that do not have tyrosine bound. This conformational change brings the substrate, cofactor and active-site residues into close proximity for catalysis. An ionic network consisting of Arg297 (a key residue for tyrosine binding), a water molecule, Asp206 (from

  7. (15)N NMR spectroscopy unambiguously establishes the coordination mode of the diimine linker 2-(2'-pyridyl)pyrimidine-4-carboxylic acid (cppH) in Ru(ii) complexes.

    Science.gov (United States)

    Battistin, Federica; Balducci, Gabriele; Demitri, Nicola; Iengo, Elisabetta; Milani, Barbara; Alessio, Enzo

    2015-09-21

    We investigated the reactivity of three Ru(ii) precursors -trans,cis,cis-[RuCl2(CO)2(dmso-O)2], cis,fac-[RuCl2(dmso-O)(dmso-S)3], and trans-[RuCl2(dmso-S)4] - towards the diimine linker 2-(2'-pyridyl)pyrimidine-4-carboxylic acid (cppH) or its parent compound 4-methyl-2-(2'-pyridyl)pyrimidine ligand (mpp), in which a methyl group replaces the carboxylic group on the pyrimidine ring. In principle, both cppH and mpp can originate linkage isomers, depending on how the pyrimidine ring binds to ruthenium through the nitrogen atom ortho (N(o)) or para (N(p)) to the group in position 4. The principal aim of this work was to establish a spectroscopic fingerprint for distinguishing the coordination mode of cppH/mpp also in the absence of an X-ray structural characterization. By virtue of the new complexes described here, together with the others previously reported by us, we successfully recorded {(1)H,(15)N}-HMBC NMR spectra at natural abundance of the (15)N isotope on a consistent number of fully characterized Ru(ii)-cppH/mpp compounds, most of them being stereoisomers and/or linkage isomers. Thus, we found that (15)N NMR chemical shifts unambiguously establish the binding mode of cppH and mpp - either through N(o) or N(p)- and can be conveniently applied also in the absence of the X-ray structure. In fact, coordination of cppH to Ru(ii) induces a marked upfield shift for the resonance of the N atoms directly bound to the metal, with coordination induced shifts (CIS) ranging from ca.-45 to -75 ppm, depending on the complex, whereas the unbound N atom resonates at a frequency similar to that of the free ligand. Similar results were found for the complexes of mpp. This work confirmed our previous finding that cppH has no binding preference, whereas mpp binds exclusively through N(p). Interestingly, the two cppH linkage isomers trans,cis-[RuCl2(CO)2(cppH-κN(p))] (5) and trans,cis-[RuCl2(CO)2(cppH-κN(o))] (6) were easily obtained in pure form by exploiting their different

  8. Magnetic adsorbent constructed from the loading of amino functionalized Fe{sub 3}O{sub 4} on coordination complex modified polyoxometalates nanoparticle and its tetracycline adsorption removal property study

    Energy Technology Data Exchange (ETDEWEB)

    Ou, Jinzhao; Mei, Mingliang; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

    2016-06-15

    A magnetic polyoxometalates based adsorbent has been synthesized successfully through the loading of amino functionalized Fe{sub 3}O{sub 4} (NH{sub 2}-Fe{sub 3}O{sub 4}) on nanoparticle of a coordination complex modified polyoxometalates (CC/POMNP). FTIR illustrate there exist intense hydrogen bonds between NH{sub 2}-Fe{sub 3}O{sub 4} and CC/POMNP, which keep the stability of this adsorbent. At room temperature, this adsorbent exhibits ferromagnetic character with saturation magnetization of 8.19 emu g{sup −1}, which provides prerequisite for fast magnetic separation. Water treatment experiment illustrates this POM based magnetic adsorbent exhibits high adsorption capacity on tetracycline. The adsorption process can be described well with Temkin model, which illustrates the interaction between adsorbent and tetracycline plays the dominated role in tetracycline removal. The rapid, high efficient tetracycline adsorption ability suggests this POM based magnetic adsorbent exhibits promising prospect in medical and agriculture waste water purification. A magnetic polyoxometalates based adsorbent, which exhibits excellent tetracycline adsorption removal property has been synthesized through the loading of NH{sub 2}-Fe{sub 3}O{sub 4} on coordination complex modified polyoxometalates - Graphical abstract: A magnetic polyoxometalates based adsorbent, which exhibits excellent tetracycline adsorption removal property has been synthesized through the loading of NH{sub 2}-Fe{sub 3}O{sub 4} on coordination complex modified polyoxometalate. Display Omitted - Highlights: • A POM based magnetic adsorbent was fabricated through the loading of NH{sub 2}-Fe{sub 3}O{sub 4} on POM nanoparticle. • This adsorbent possesses excellent tetracycline adsorption property. • Saturation magnetization value of this adsorbent is 8.19 emug−1, which is enough for magnetic separation.

  9. Growth and optical characterization of colloidal CdTe nanoparticles capped by a bifunctional molecule

    Energy Technology Data Exchange (ETDEWEB)

    Abd El-sadek, M.S., E-mail: el_sadek_99@email.co [Nanomaterial Laboratory, Physics Department, Faculty of Science, South Valley University, Qena-83523 (Egypt); Crystal Growth Centre, Anna University Chennai, Chennai-600025 (India); Moorthy Babu, S. [Crystal Growth Centre, Anna University Chennai, Chennai-600025 (India)

    2010-08-15

    Thiol-capped CdTe nanoparticles were synthesized in aqueous solution by wet chemical route. CdTe nanoparticles with bifunctional molecule mercaptoacetic acid as a stabilizer were synthesized at pH{approx}11.2 and using potassium tellurite as tellurium source. The effect of refluxing time on the preparation of these samples was measured using UV-vis absorption and photoluminescence analysis. By increasing the refluxing time the UV-vis absorption and photoluminescence results show that the band edge emission is redshifted. The synthesized thiol-capped CdTe were characterized with FT-IR, TEM and TG-DTA. The particle size was calculated by the effective mass approximation (EMA). The role of precursors, their composition, pH and reaction procedure on the development of nanoparticles are analyzed.

  10. Boehmite-An Efficient and Recyclable Acid-Base Bifunctional Catalyst for Aldol Condensation Reaction.

    Science.gov (United States)

    Reshma, P C Rajan; Vikneshvaran, Sekar; Velmathi, Sivan

    2018-06-01

    In this work boehmite was used as an acid-base bifunctional catalyst for aldol condensation reactions of aromatic aldehydes and ketones. The catalyst was prepared by simple sol-gel method using Al(NO3)3·9H2O and NH4OH as precursors. The catalyst has been characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), UV-visible spectroscopy (DRS), BET surface area analyses. Boehmite is successfully applied as catalyst for the condensation reaction between 4-nitrobenzaldehyde and acetone as a model substrate giving α, β-unsaturated ketones without any side product. The scope of the reaction is extended for various substituted aldehydes. A probable mechanism has been suggested to explain the cooperative behavior of the acidic and basic sites. The catalyst is environmentally friendly and easily recovered from the reaction mixture. Also the catalyst is reusable up to 3 catalytic cycles.

  11. Bi-functional biobased packing of the cassava starch, glycerol, licuri nanocellulose and red propolis.

    Directory of Open Access Journals (Sweden)

    Samantha Serra Costa

    Full Text Available The aim of this study was to characterize and determine the bi-functional efficacy of active packaging films produced with starch (4% and glycerol (1.0%, reinforced with cellulose nanocrystals (0-1% and activated with alcoholic extracts of red propolis (0.4 to 1.0%. The cellulose nanocrystals used in this study were extracted from licuri leaves. The films were characterized using moisture, water-activity analyses and water vapor-permeability tests and were tested regarding their total phenolic compounds and mechanical properties. The antimicrobial and antioxidant efficacy of the films were evaluated by monitoring the use of the active films for packaging cheese curds and butter, respectively. The cellulose nanocrystals increased the mechanical strength of the films and reduced the water permeability and water activity. The active film had an antimicrobial effect on coagulase-positive staphylococci in cheese curds and reduced the oxidation of butter during storage.

  12. Improving battery safety by early detection of internal shorting with a bifunctional separator

    Science.gov (United States)

    Wu, Hui; Zhuo, Denys; Kong, Desheng; Cui, Yi

    2014-10-01

    Lithium-based rechargeable batteries have been widely used in portable electronics and show great promise for emerging applications in transportation and wind-solar-grid energy storage, although their safety remains a practical concern. Failures in the form of fire and explosion can be initiated by internal short circuits associated with lithium dendrite formation during cycling. Here we report a new strategy for improving safety by designing a smart battery that allows internal battery health to be monitored in situ. Specifically, we achieve early detection of lithium dendrites inside batteries through a bifunctional separator, which offers a third sensing terminal in addition to the cathode and anode. The sensing terminal provides unique signals in the form of a pronounced voltage change, indicating imminent penetration of dendrites through the separator. This detection mechanism is highly sensitive, accurate and activated well in advance of shorting and can be applied to many types of batteries for improved safety.

  13. Basic evaluation of [sup 67]Ga labeled digoxin derivative as a metal-labeled bifunctional radiopharmaceutical

    Energy Technology Data Exchange (ETDEWEB)

    Fujibayashi, Yasuhisa; Konishi, Junji (Kyoto Univ. (Japan). Faculty of Medicine); Takemura, Yasutaka; Taniuchi, Hideyuki; Iijima, Naoko; Yokoyama, Akira

    1993-11-01

    To develop metal-labeled digoxin radiopharmaceuticals with affinity with anti-digoxin antibody as well as Na[sup +], K[sup +]-ATPase, a digoxin derivative conjugated with deferoxamine was synthesized. The derivative had a high binding affinity with [sup 67]Ga at deferoxamine introduced to the terminal sugar ring of digoxin. The [sup 67]Ga labeled digoxin derivative showed enough in vitro binding affinity and selectivity to anti-digoxin antibody as well as Na[sup +], K[sup +]-ATPase. The [sup 67]Ga labeled digoxin derivative is considered to be a potential metal-labeled bifunctional radiopharmaceutical for digoxin RIA as well as myocardial Na[sup +], K[sup +]-ATPase imaging. (author).

  14. First-Principles Study of Structure Property Relationships of Monolayer (Hydroxy)Oxide-Metal Bifunctional Electrocatalysts

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Kubal, Joseph; Greeley, Jeffrey Philip

    2015-01-01

    step towards accurate identification and prediction of a variety of oxide/electrode interfacial structure-properties relationships, but also provides the foundation for rational design and control of ‘targeted active phases’ at catalytic interfaces. The successful design of bifunctional......In the present study, on the basis of detailed density functional theory (DFT) calculations, and using Ni hydroxy(oxide) films on Pt(111) and Au(111) electrodes as model systems, we describe a detailed structural and electrocatalytic analysis of hydrogen evolution (HER) at three-phase boundaries...... under alkaline electrochemical conditions. We demonstrate that the structure and oxidation state of the films can be systematically tuned by changing the applied electrode potential and/or the nature of substrates. Structural features determined from the theoretical calculations provide a wealth...

  15. Polarization holograms in a bifunctional amorphous polymer exhibiting equal values of photoinduced linear and circular birefringences.

    Science.gov (United States)

    Provenzano, Clementina; Pagliusi, Pasquale; Cipparrone, Gabriella; Royes, Jorge; Piñol, Milagros; Oriol, Luis

    2014-10-09

    Light-controlled molecular alignment is a flexible and useful strategy introducing novelty in the fields of mechanics, self-organized structuring, mass transport, optics, and photonics and addressing the development of smart optical devices. Azobenzene-containing polymers are well-known photocontrollable materials with large and reversible photoinduced optical anisotropies. The vectorial holography applied to these materials enables peculiar optical devices whose properties strongly depend on the relative values of the photoinduced birefringences. Here is reported a polarization holographic recording based on the interference of two waves with orthogonal linear polarization on a bifunctional amorphous polymer that, exceptionally, exhibits equal values of linear and circular birefringence. The peculiar photoresponse of the material coupled with the holographic technique demonstrates an optical device capable of decomposing the light into a set of orthogonally polarized linear components. The holographic structures are theoretically described by the Jones matrices method and experimentally investigated.

  16. Development of tartaric esters as bifunctional additives of methanol-gasoline.

    Science.gov (United States)

    Zhang, Jie; Yang, Changchun; Tang, Ying; Zhou, Rui; Wang, Xiaoli; Xu, Lianghong

    2014-01-01

    Methanol has become an alternative fuel for gasoline, which is facing a rapidly rising world demand with a limited oil supply. Methanol-gasoline has been used in China, but phase stability and vapor lock still need to be resolved in methanol-gasoline applications. In this paper, a series of tartaric esters were synthesized and used as phase stabilizers and saturation vapor pressure depressors for methanol-gasoline. The results showed that the phase stabilities of tartaric esters for methanol-gasoline depend on the length of the alkoxy group. Several tartaric esters were found to be effective in various gasoline-methanol blends, and the tartaric esters display high capacity to depress the saturation vapor pressure of methanol-gasoline. According to the results, it can be concluded that the tartaric esters have great potential to be bifunctional gasoline-methanol additives.

  17. Novel 3-nitrotriazole-based amides and carbinols as bifunctional anti-Chagasic agents

    Science.gov (United States)

    Papadopoulou, Maria V.; Bloomer, William D.; Lepesheva, Galina I.; Rosenzweig, Howard S.; Kaiser, Marcel; Aguilera-Venegas, Benjamín; Wilkinson, Shane R.; Chatelain, Eric; Ioset, Jean-Robert

    2015-01-01

    3-Nitro-1H-1,2,4-triazole-based amides with a linear, rigid core and 3-nitrotriazole-based fluconazole analogs were synthesized as dual functioning antitrypanosomal agents. Such compounds are excellent substrates for type I nitroreductase (NTR) located in the mitochondrion of trypanosomatids and, at the same time, act as inhibitors of the sterol 14α-demethylase (T. cruzi CYP51) enzyme. Because combination treatments against parasites are often superior to monotherapy, we believe that this emerging class of bifunctional compounds may introduce a new generation of antitrypanosomal drugs. In the present work, the synthesis and in vitro and in vivo evaluation of such compounds is discussed. PMID:25580906

  18. On the molecular basis of D-bifunctional protein deficiency type III.

    Directory of Open Access Journals (Sweden)

    Maija L Mehtälä

    Full Text Available Molecular basis of D-bifunctional protein (D-BP deficiency was studied with wild type and five disease-causing variants of 3R-hydroxyacyl-CoA dehydrogenase fragment of the human MFE-2 (multifunctional enzyme type 2 protein. Complementation analysis in vivo in yeast and in vitro enzyme kinetic and stability determinants as well as in silico stability and structural fluctuation calculations were correlated with clinical data of known patients. Despite variations not affecting the catalytic residues, enzyme kinetic performance (K(m, V(max and k(cat of the recombinant protein variants were compromised to a varying extent and this can be judged as the direct molecular cause for D-BP deficiency. Protein stability plays an additional role in producing non-functionality of MFE-2 in case structural variations affect cofactor or substrate binding sites. Structure-function considerations of the variant proteins matched well with the available data of the patients.

  19. Defective DNA cross-link removal in Chinese hamster cell mutants hypersensitive to bifunctional alkylating agents

    International Nuclear Information System (INIS)

    Hoy, C.A.; Thompson, L.H.; Mooney, C.L.; Salazar, E.P.

    1985-01-01

    DNA repair-deficient mutants from five genetic complementation groups isolated previously from Chinese hamster cells were assayed for survival after exposure to the bifunctional alkylating agents mitomycin C or diepoxybutane. Groups 1, 3, and 5 exhibited 1.6- to 3-fold hypersensitivity compared to the wild-type cells, whereas Groups 2 and 4 exhibited extraordinary hypersensitivity. Mutants from Groups 1 and 2 were exposed to 22 other bifunctional alkylating agents in a rapid assay that compared cytotoxicity of the mutants to the wild-type parental strain, AA8. With all but two of the compounds, the Group 2 mutant (UV4) was 15- to 60-fold more sensitive than AA8 or the Group 1 mutant (UV5). UV4 showed only 6-fold hypersensitivity to quinacrine mustard. Alkaline elution measurements showed that this compound produced few DNA interstrand cross-links but numerous strand breaks. Therefore, the extreme hypersensitivity of mutants from Groups 2 and 4 appeared specific for compounds the main cytotoxic lesions of which were DNA cross-links. Mutant UV5 was only 1- to 4-fold hypersensitive to all the compounds. Although the initial number of cross-links was similar for the three cell lines, the efficiency of removal of cross-links was lowest in UV4 and intermediate in UV5. These results suggest that the different levels of sensitivity are specifically related to different efficiencies of DNA cross-link removal. The phenotype of hypersensitivity to both UV radiation and cross-link damage exhibited by the mutants in Groups 2 and 4 appears to differ from those of the known human DNA repair syndromes

  20. Arabidopsis RIBA Proteins: Two out of Three Isoforms Have Lost Their Bifunctional Activity in Riboflavin Biosynthesis

    Science.gov (United States)

    Hiltunen, Hanna-Maija; Illarionov, Boris; Hedtke, Boris; Fischer, Markus; Grimm, Bernhard

    2012-01-01

    Riboflavin serves as a precursor for flavocoenzymes (FMN and FAD) and is essential for all living organisms. The two committed enzymatic steps of riboflavin biosynthesis are performed in plants by bifunctional RIBA enzymes comprised of GTP cyclohydrolase II (GCHII) and 3,4-dihydroxy-2-butanone-4-phosphate synthase (DHBPS). Angiosperms share a small RIBA gene family consisting of three members. A reduction of AtRIBA1 expression in the Arabidopsis rfd1mutant and in RIBA1 antisense lines is not complemented by the simultaneously expressed isoforms AtRIBA2 and AtRIBA3. The intensity of the bleaching leaf phenotype of RIBA1 deficient plants correlates with the inactivation of AtRIBA1 expression, while no significant effects on the mRNA abundance of AtRIBA2 and AtRIBA3 were observed. We examined reasons why both isoforms fail to sufficiently compensate for a lack of RIBA1 expression. All three RIBA isoforms are shown to be translocated into chloroplasts as GFP fusion proteins. Interestingly, both AtRIBA2 and AtRIBA3 have amino acid exchanges in conserved peptides domains that have been found to be essential for the two enzymatic functions. In vitro activity assays of GCHII and DHBPS with all of the three purified recombinant AtRIBA proteins and complementation of E. coli ribA and ribB mutants lacking DHBPS and GCHII expression, respectively, confirmed the loss of bifunctionality for AtRIBA2 and AtRIBA3. Phylogenetic analyses imply that the monofunctional, bipartite RIBA3 proteins, which have lost DHBPS activity, evolved early in tracheophyte evolution. PMID:23203051

  1. Gently reduced graphene oxide incorporated into cobalt oxalate rods as bifunctional oxygen electrocatalyst

    International Nuclear Information System (INIS)

    Phihusut, Doungkamon; Ocon, Joey D.; Jeong, Beomgyun; Kim, Jin Won; Lee, Jae Kwang; Lee, Jaeyoung

    2014-01-01

    Graphical abstract: - Abstract: Water-oxygen electrochemistry is at the heart of key renewable energy technologies (fuel cells, electrolyzers, and metal-air batteries) due to the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Although much effort has been devoted to the development of improved bifunctional electrocatalysts, an inexpensive, highly active oxygen electrocatalyst, however, remains to be a challenge. In this paper, we present a facile and robust method to create gently reduced graphene oxide incorporated into cobalt oxalate microstructures (CoC 2 O 4 /gRGO) and demonstrate its excellent and stable electrocatalytic activity in both OER and ORR, arising from the inherent properties of the components and their physicochemical interaction. Our synthesis technique also explores a single pot method to partially reduce graphene oxide and form CoC 2 O 4 structures while maintaining the solution processability of reduced graphene oxide. While the OER activity of CoC 2 O 4 /gRGO is exclusively due to CoC 2 O 4 , which transformed into OER-active Co species, the combination with gRGO significantly improves OER stability. On the other hand, CoC 2 O 4 /gRGO exhibits synergistic effect towards ORR, via a quasi-four-electron pathway, leading to a slightly higher ORR limiting current than Pt/C. Remarkably, gRGO offers dual functionality, contributing to ORR activity via the N-functional groups and also enhancing OER stability through the gRGO coating around CoC 2 O 4 structures. Our results suggest a new class of metal-carbon composite that has the potential to be alternative bifunctional catalysts for regenerative fuel cells and metal-air batteries

  2. AmpH, a bifunctional DD-endopeptidase and DD-carboxypeptidase of Escherichia coli.

    Science.gov (United States)

    González-Leiza, Silvia M; de Pedro, Miguel A; Ayala, Juan A

    2011-12-01

    In Escherichia coli, low-molecular-mass penicillin-binding proteins (LMM PBPs) are important for correct cell morphogenesis. These enzymes display DD-carboxypeptidase and/or dd-endopeptidase activities associated with maturation and remodeling of peptidoglycan (PG). AmpH has been classified as an AmpH-type class C LMM PBP, a group closely related to AmpC β-lactamases. AmpH has been associated with PG recycling, although its enzymatic activity remained uncharacterized until now. Construction and purification of His-tagged AmpH from E. coli permitted a detailed study of its enzymatic properties. The N-terminal export signal of AmpH is processed, but the protein remains membrane associated. The PBP nature of AmpH was demonstrated by its ability to bind the β-lactams Bocillin FL (a fluorescent penicillin) and cefmetazole. In vitro assays with AmpH and specific muropeptides demonstrated that AmpH is a bifunctional DD-endopeptidase and DD-carboxypeptidase. Indeed, the enzyme cleaved the cross-linked dimers tetrapentapeptide (D45) and tetratetrapeptide (D44) with efficiencies (k(cat)/K(m)) of 1,200 M(-1) s(-1) and 670 M(-1) s(-1), respectively, and removed the terminal D-alanine from muropeptides with a C-terminal D-Ala-D-Ala dipeptide. Both DD-peptidase activities were inhibited by 40 μM cefmetazole. AmpH also displayed a weak β-lactamase activity for nitrocefin of 1.4 × 10(-3) nmol/μg protein/min, 1/1,000 the rate obtained for AmpC under the same conditions. AmpH was also active on purified sacculi, exhibiting the bifunctional character that was seen with pure muropeptides. The wide substrate spectrum of the DD-peptidase activities associated with AmpH supports a role for this protein in PG remodeling or recycling.

  3. Preparation of Ga-67 labeled monoclonal antibodies using deferoxamine as a bifunctional chelating agent

    International Nuclear Information System (INIS)

    Endo, K.; Furukawa, T.; Ohmomo, Y.

    1984-01-01

    Ga-67 labeled monoclonal IgG or F(ab')/sub 2/ fragments against α-fetoprotein and β-subunit of human choriogonadotropin (HCG), were prepared using Deferoxamine (DFO) as a bifunctional chelating agent. DFO, a well-known iron chelating agent, was conjugated with monoclonal antibodies (Ab) by a glutaraldehyde two step method and the effect of conjugation on the Ab activities was examined by RIA and Scatchard plot analysis. In both monoclonal Ab preparations, the conjugation reaction was favored as the pH increased. However, Ab-binding activities decreased as the molecular ratios of DFO to Ab increased. Preserved Ab activities were observed when Ab contained DFO per Ab molecule less than 2.1. At a ratio of over 3.3 DFO molecules per Ab, the maximal binding capacity rather than the affinity constant decreased. The inter-molecular cross linkage seemed to be responsible for the deactivation of binding activities. The obtained DFO-Ab conjugates, were then easily labeled with high efficiency and reproducibility and Ga-67 DFO-Ab complexes were highly stable both in vitro and in vivo. Thus, biodistribution of Ga-67 labeled F(ab')/sub 2/ fragments of monoclonal Ab to HCG β-subunit was attempted in nude mice transplanted with HCG-producing human teratocarcinoma. Tumor could be visualized, in spite of relatively high background imaging of liver, kidney and spleen. The use of DFO as a bifunctional chelating agent provided good evidence for its applicability to labeling monoclonal Ab with almost full retention of Ab activities. Further, availability of Ga-68 will make Ga-68 DFO-monoclonal Ab a very useful tool for positron tomography imaging of various tumors

  4. A Ru(II) complex with 2-(4-(methylsulfonyl)phenyl)-1H-imidazo[4,5- f][1,10]phenanthroline: Synthesis, characterization, and acid-base and DNA-binding properties

    Science.gov (United States)

    Gao, Jie; Wang, Zhi-Ping; Yuan, Cui-Li; Jia, Hai-Shun; Wang, Ke-Zhi

    2011-09-01

    A new Ru(II) complex of [Ru(bpy) 2(Hmspip)]Cl 2 {in which bpy = 2,2'-bipyridine, Hmspip = 2-(4-(methylsulfonyl)phenyl)-1 H-imidazo[4,5- f][1,10]phenanthroline} have been synthesized and characterized. The ground- and excited-state acid-base properties of [Ru(bpy) 2(Hmspip)]Cl 2 and its parent complex of [Ru(bpy) 2(Hpip)]Cl 2 {Hpip = 2-phenyl-1H-imidazo[4,5- f][1,10]phenanthroline} have been studied by UV-visible (UV-vis) and emission spectrophotometric pH titrations. [Ru(bpy) 2(Hmspip)]Cl 2 acts as a calf thymus DNA intercalators with a binding constant of 4.0 × 10 5 M -1 in buffered 50 mM NaCl, as evidenced by UV-vis and luminescence titrations, steady-state emission quenching by [Fe(CN) 6] 4-, DNA competitive binding with ethidium bromide, reverse salt titrations and viscosity measurements.

  5. Dynamics of tropomyosin in muscle fibers as monitored by saturation transfer EPR of bi-functional probe.

    Directory of Open Access Journals (Sweden)

    Roni F Rayes

    Full Text Available The dynamics of four regions of tropomyosin was assessed using saturation transfer electron paramagnetic resonance in the muscle fiber. In order to fully immobilize the spin probe on the surface of tropomyosin, a bi-functional spin label was attached to i,i+4 positions via cysteine mutagenesis. The dynamics of bi-functionally labeled tropomyosin mutants decreased by three orders of magnitude when reconstituted into "ghost muscle fibers". The rates of motion varied along the length of tropomyosin with the C-terminus position 268/272 being one order of magnitude slower then N-terminal domain or the center of the molecule. Introduction of troponin decreases the dynamics of all four sites in the muscle fiber, but there was no significant effect upon addition of calcium or myosin subfragment-1.

  6. Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

    Science.gov (United States)

    Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

    2018-01-01

    Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Functionalization of nanoparticle titanium dioxide with different bifunctional organic molecules and trimers of transition compounds for obtaining new materials

    International Nuclear Information System (INIS)

    Rivera Martinez, Maria Cinthya

    2012-01-01

    Functionalization of titanium dioxide in nanoporous anatase phase is investigated for obtaining new nanomaterials. Functionalizations were performed using two heating methods: the conventional of refluxing heating method and microwave irradiation with bifunctional organic molecules is used to study how to anchor molecules and the change in the wettability of the material. Besides, reactions with organic molecules were performed as the derived from nanoproxene. The growth layer by layer is performed using the bifunctional molecules previous for the immobilization of cobalt trimers. Functionalized molecules were characterized by infrared spectroscopy, X-ray diffraction, contact angle, scanning electron microscopy, x-ray elemental analysis, plasma atomic emission spectroscopy coupled inductively, x-ray photoelectron spectroscopy and thermogravimetric analysis. This type of functionalizations on nanoporous titanium dioxide could potentially improve optical sensitivity and activity of this nanomaterial in the visible region. (author) [es

  8. Rational design of micro-RNA-like bifunctional siRNAs targeting HIV and the HIV coreceptor CCR5.

    Science.gov (United States)

    Ehsani, Ali; Saetrom, Pål; Zhang, Jane; Alluin, Jessica; Li, Haitang; Snøve, Ola; Aagaard, Lars; Rossi, John J

    2010-04-01

    Small-interfering RNAs (siRNAs) and micro-RNAs (miRNAs) are distinguished by their modes of action. SiRNAs serve as guides for sequence-specific cleavage of complementary mRNAs and the targets can be in coding or noncoding regions of the target transcripts. MiRNAs inhibit translation via partially complementary base-pairing to 3' untranslated regions (UTRs) and are generally ineffective when targeting coding regions of a transcript. In this study, we deliberately designed siRNAs that simultaneously direct cleavage and translational suppression of HIV RNAs, or cleavage of the mRNA encoding the HIV coreceptor CCR5 and suppression of translation of HIV. These bifunctional siRNAs trigger inhibition of HIV infection and replication in cell culture. The design principles have wide applications throughout the genome, as about 90% of genes harbor sites that make the design of bifunctional siRNAs possible.

  9. Post-modified acid-base bifunctional MIL-101(Cr) for one-pot deacetalization-Knoevenagel reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Manman [Tianjin University, School of Science (China); Yan, Xilong; Li, Yang; Chen, Ligong, E-mail: lgchen@tju.edu.cn [Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) (China)

    2017-04-15

    A novel and convenient approach for the construction of the bifunctional MIL-101 material bearing sulfonic acid and amino groups was established via the post-synthetic modification. This material possesses high BET surface area (1446 m{sup 2}/g) and large pore volume (0.77 cm{sup 3}/g). Significantly, this material could serve as a bifunctional heterogeneous catalyst and was initially employed for one-pot deacetalization-Knoevenagel reaction, exhibiting excellent catalytic performance (yield 99.74%). More importantly, it can be easily recovered and reused at least three times. Finally, our proposed catalytic mechanism indicated that amino and the sulfonic acid groups played a synergistic effect on this one-pot deacetalization-Knoevenagel reaction.

  10. Crystallization and preliminary X-ray analysis of a bifunctional catalase-phenol oxidase from Scytalidium thermophilum

    International Nuclear Information System (INIS)

    Sutay Kocabas, Didem; Pearson, Arwen R.; Phillips, Simon E. V.; Bakir, Ufuk; Ogel, Zumrut B.; McPherson, Michael J.; Trinh, Chi H.

    2009-01-01

    The bifunctional enzyme catalase-phenol oxidase from S. thermophilum was crystallized by the hanging-drop vapour-diffusion method in space group P2 1 and diffraction data were collected to 2.8 Å resolution. Catalase-phenol oxidase from Scytalidium thermophilum is a bifunctional enzyme: its major activity is the catalase-mediated decomposition of hydrogen peroxide, but it also catalyzes phenol oxidation. To understand the structural basis of this dual functionality, the enzyme, which has been shown to be a tetramer in solution, has been purified by anion-exchange and gel-filtration chromatography and has been crystallized using the hanging-drop vapour-diffusion technique. Streak-seeding was used to obtain larger crystals suitable for X-ray analysis. Diffraction data were collected to 2.8 Å resolution at the Daresbury Synchrotron Radiation Source. The crystals belonged to space group P2 1 and contained one tetramer per asymmetric unit

  11. Self-organization of Au–CdSe hybrid nanoflowers at different length scales via bi-functional diamine linkers

    Energy Technology Data Exchange (ETDEWEB)

    AbouZeid, Khaled Mohamed [Virginia Commonwealth University, Department of Chemistry (United States); Mohamed, Mona Bakr [Cairo University, National Institute of Laser Enhanced Science (NILES) (Egypt); El-Shall, M. Samy, E-mail: mselshal@vcu.edu [Virginia Commonwealth University, Department of Chemistry (United States)

    2016-01-15

    This work introduces a series of molecular bridging bi-functional linkers to produce laterally self-assembled nanostructures of the Au–CdSe nanoflowers on different length scales ranging from 10 nm to 100 microns. Assembly of Au nanocrystals within amorphous CdSe rods is found in the early stages of the growth of the Au–CdSe nanoflowers. The Au–CdSe nanoflowers are formed through a one-pot low temperature (150 °C) process where CdSe clusters are adsorbed on the surface of the Au cores, and they then start to form multiple arms and branches resulting in flower-shaped hybrid nanostructures. More complex assembly at a micron length scale can be achieved by means of bi-functional capping agents with appropriate alkyl chain lengths, such as 1,12-diaminododecane.

  12. Purification, crystallization and preliminary X-ray crystallographic analysis of rice bifunctional α-amylase/subtilisin inhibitor from Oryza sativa

    International Nuclear Information System (INIS)

    Lin, Yi-Hung; Peng, Wen-Yan; Huang, Yen-Chieh; Guan, Hong-Hsiang; Hsieh, Ying-Cheng; Liu, Ming-Yih; Chang, Tschining; Chen, Chun-Jung

    2006-01-01

    The crystallization of rice α-amylase/subtilisin bifunctional inhibitor is reported. Rice bifunctional α-amylase/subtilisin inhibitor (RASI) can inhibit both α-amylase from larvae of the red flour beetle (Tribolium castaneum) and subtilisin from Bacillus subtilis. The synthesis of RASI is up-regulated during the late milky stage in developing seeds. The 8.9 kDa molecular-weight RASI from rice has been crystallized using the hanging-drop vapour-diffusion method. According to 1.81 Å resolution X-ray diffraction data from rice RASI crystals, the crystal belongs to space group P2 1 2 1 2, with unit-cell parameters a = 79.99, b = 62.95, c = 66.70 Å. Preliminary analysis indicates two RASI molecules in an asymmetric unit with a solvent content of 44%

  13. Construction of Bifunctional Co/H-ZSM-5 Catalysts for the Hydrodeoxygenation of Stearic Acid to Diesel-range Alkanes.

    Science.gov (United States)

    Wu, Guangjun; Zhang, Nan; Dai, Weili; Guan, Naijia; Li, Landong

    2018-04-27

    Bifunctional Co/H-ZSM-5 zeolites were prepared by surface organometallic chemistry grafting route, namely by the stoichiometric reaction between cobaltocene and the Brønsted acid sites in zeolites, and applied to the model reaction of stearic acid catalytic hydrodeoxygenation. Cobalt species existed in the form of isolated Co2+ ions at exchange positions after grafting, transformed to CoO species on the surface of zeolite and stabilized inside zeolite channels upon calcination in air, and finally reduced to metallic cobalt species of homogeneous clusters of ca. 1.5 nm by hydrogen. During this process, the Brønsted acid sites of H-ZSM-5 zeolites could be preserved with acid strength slightly reduced. The as-prepared bifunctional catalyst exhibited a ~16 times higher activity in stearic acid hydrodeoxygenation (2.11 gSAgcat-1h-1) than the reference catalyst (0.13 gSAgcat-1h-1) prepared by solid-state ion exchange, and a high C18/C17 ratio of ~24 was achieved as well. The remarkable hydrodeoxygenation performance of bifunctional Co/H-ZSM-5 could be explained from the effective synergy between the uniformed metallic cobalt clusters and the Brønsted acid sites in H-ZSM-5 zeolite. The simplified reaction network and kinetics of stearic acid hydrodeoxygenation catalyzed by the as-prepared bifunctional Co/H-ZSM-5 zeolites were also investigated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. ZIF-67 incorporated with carbon derived from pomelo peels: A highly efficient bifunctional catalyst for oxygen reduction/evolution reactions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Yin, Feng-Xiang; Chen, Biao-Hua; He, Xiao-Bo; Lv, Peng-Liang; Ye, Cai-Yun; Liu, Di-Jia

    2017-05-01

    Developing carbon catalyst materials using natural, abundant and renewable resources as precursors plays an increasingly important role in clean energy generation and environmental protection. In this work, N-doped pomelo-peel-derived carbon (NPC) materials were prepared using a widely available food waste-pomelo peels and melamine. The synthetic NPC exhibits well-defined porosities and a highly doped-N content (e.g. 6.38 at% for NPC-2), therefore affords excellent oxygen reduction reaction (ORR) catalytic activities in alkaline electrolytes. NPC was further integrated with ZIF-67 to form ZIF-67@NPC hybrids through solvothermal reactions. The hybrid catalysts show substantially enhanced ORR catalytic activities comparable to that of commercial 20 wa Pt/C. Furthermore, the catalysts also exhibit excellent oxygen evolution reaction (OER) catalytic activities. Among all prepared ZIF-67@NPC hybrids, the optimal composition with ZIF-67 to NPC ratio of 2:1 exhibits the best ORR and OER bifunctional catalytic performance and the smallest Delta E (E-OER@10 mA cm(-2)-E-ORR@-1 mA cm(-2)) value of 0.79 V. The catalyst also demonstrated desirable 4-electron transfer pathways and superior catalytic stabilities. The Co-N-4 in ZIF-67, electrochemical active surface area, and the strong interactions between ZIF-67 and NPC are attributed as the main contributors to the bifunctional catalytic activities. These factors act synergistically, resulting in substantially enhanced bifunctional catalytic activities and stabilities; consequently, this hybrid catalyst is among the best of the reported bifunctional electrocatalysts and is promising for use in metal-air batteries and fuel cells. (C) 2016 Elsevier B.V. All rights reserved.

  15. L-Threonine-derived novel bifunctional phosphine-sulfonamide catalyst-promoted enantioselective aza-morita-Baylis-Hillman reaction

    KAUST Repository

    Zhong, Fangrui

    2011-03-18

    A series of novel bifunctional phosphine-sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita-Baylis-Hillman (MBH) reactions. l-Threonine-derived phosphine-sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities. © 2011 American Chemical Society.

  16. Catalysis engineering of bifunctional solids for the one-step synthesis of liquid fuels from syngas: A review

    OpenAIRE

    Sartipi, S.; Makkee, M.; Kapteijn, F.; Gascon, J.

    2014-01-01

    The combination of acidic zeolites and Fischer–Tropsch synthesis (FTS) catalysts for one-step production of liquid fuels from syngas is critically reviewed. Bifunctional systems are classified by the proximity between FTS and acid functionalities on three levels: reactor, catalyst particle, and active phase. A thorough analysis of the published literature on this topic reveals that efficiency in the production of liquid fuels correlates well with the proximity of FTS and acid sites. Moreover,...

  17. Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

    Science.gov (United States)

    Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

    2018-01-01

    A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

  18. Electrodeposited nano-scale islands of ruthenium oxide as a bifunctional electrocatalyst for simultaneous catalytic oxidation of hydrazine and hydroxylamine

    Energy Technology Data Exchange (ETDEWEB)

    Zare, Hamid R., E-mail: hrzare@yazduni.ac.ir [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Nanotechnology Research Center, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of); Hashemi, S. Hossein; Benvidi, Ali [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)

    2010-06-04

    For the first time, an electrodeposited nano-scale islands of ruthenium oxide (ruthenium oxide nanoparticles), as an excellent bifunctional electrocatalyst, was successfully used for hydrazine and hydroxylamine electrocatalytic oxidation. The results show that, at the present bifunctional modified electrode, two different redox couples of ruthenium oxides serve as electrocatalysts for simultaneous electrocatalytic oxidation of hydrazine and hydroxylamine. At the modified electrode surface, the peaks of differential pulse voltammetry (DPV) for hydrazine and hydroxylamine oxidation were clearly separated from each other when they co-exited in solution. Thus, it was possible to simultaneously determine hydrazine and hydroxylamine in the samples at a ruthenium oxide nanoparticles modified glassy carbon electrode (RuON-GCE). Linear calibration curves were obtained for 2.0-268.3 {mu}M and 268.3-417.3 {mu}M of hydrazine and for 4.0-33.8 {mu}M and 33.8-78.3 {mu}M of hydroxylamine at the modified electrode surface using an amperometric method. The amperometric method also exhibited the detection limits of 0.15 {mu}M and 0.45 {mu}M for hydrazine and hydroxylamine respectively. RuON-GCE was satisfactorily used for determination of spiked hydrazine in two water samples. Moreover, the studied bifunctional modified electrode exhibited high sensitivity, good repeatability, wide linear range and long-term stability.

  19. Synthesis of deuterium-labeled analogs of the lipid hydroperoxide-derived bifunctional electrophile 4-oxo-2(E)-nonenal.

    Science.gov (United States)

    Arora, Jasbir S; Oe, Tomoyuki; Blair, Ian A

    2011-05-15

    Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2( E )-nonenal and 4-oxo-2( E )-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α , β -unsaturated aldehyde that can react in multiple ways and with glutathione, proteins and DNA. Heavy isotope-labeled analogs of ONE are not readily available for conducting mechanistic studies or for use as internal standards in mass spectrometry (MS)-based assays. An efficient onestep cost-effective method has been developed for the preparation of C-9 deuterium-labeled ONE. In addition, a method for specific deuterium labeling of ONE at C-2, C-3 or both C-2 and C-3 has been developed. This latter method involved the selective reduction of an intermediate alkyne either by lithium aluminum hydride or lithium aluminum deuteride and quenching with water or deuterium oxide. The availability of these heavy isotope analogs will be useful as internal standards for quantitative studies employing MS and for conducting mechanistic studies of complex interactions between ONE and DNA bases as well as between ONE and proximal amino acid residues in peptides and proteins.

  20. A fundamental trade-off in covalent switching and its circumvention by enzyme bifunctionality in glucose homeostasis.

    Science.gov (United States)

    Dasgupta, Tathagata; Croll, David H; Owen, Jeremy A; Vander Heiden, Matthew G; Locasale, Jason W; Alon, Uri; Cantley, Lewis C; Gunawardena, Jeremy

    2014-05-09

    Covalent modification provides a mechanism for modulating molecular state and regulating physiology. A cycle of competing enzymes that add and remove a single modification can act as a molecular switch between "on" and "off" and has been widely studied as a core motif in systems biology. Here, we exploit the recently developed "linear framework" for time scale separation to determine the general principles of such switches. These methods are not limited to Michaelis-Menten assumptions, and our conclusions hold for enzymes whose mechanisms may be arbitrarily complicated. We show that switching efficiency improves with increasing irreversibility of the enzymes and that the on/off transition occurs when the ratio of enzyme levels reaches a value that depends only on the rate constants. Fluctuations in enzyme levels, which habitually occur due to cellular heterogeneity, can cause flipping back and forth between on and off, leading to incoherent mosaic behavior in tissues, that worsens as switching becomes sharper. This trade-off can be circumvented if enzyme levels are correlated. In particular, if the competing catalytic domains are on the same protein but do not influence each other, the resulting bifunctional enzyme can switch sharply while remaining coherent. In the mammalian liver, the switch between glycolysis and gluconeogenesis is regulated by the bifunctional 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase (PFK-2/FBPase-2). We suggest that bifunctionality of PFK-2/FBPase-2 complements the metabolic zonation of the liver by ensuring coherent switching in response to insulin and glucagon.

  1. The Mycobacterium tuberculosis Rv2540c DNA sequence encodes a bifunctional chorismate synthase

    Directory of Open Access Journals (Sweden)

    Santos Diógenes S

    2008-04-01

    Full Text Available Abstract Background The emergence of multi- and extensively-drug resistant Mycobacterium tuberculosis strains has created an urgent need for new agents to treat tuberculosis (TB. The enzymes of shikimate pathway are attractive targets to the development of antitubercular agents because it is essential for M. tuberculosis and is absent from humans. Chorismate synthase (CS is the seventh enzyme of this route and catalyzes the NADH- and FMN-dependent synthesis of chorismate, a precursor of aromatic amino acids, naphthoquinones, menaquinones, and mycobactins. Although the M. tuberculosis Rv2540c (aroF sequence has been annotated to encode a chorismate synthase, there has been no report on its correct assignment and functional characterization of its protein product. Results In the present work, we describe DNA amplification of aroF-encoded CS from M. tuberculosis (MtCS, molecular cloning, protein expression, and purification to homogeneity. N-terminal amino acid sequencing, mass spectrometry and gel filtration chromatography were employed to determine identity, subunit molecular weight and oligomeric state in solution of homogeneous recombinant MtCS. The bifunctionality of MtCS was determined by measurements of both chorismate synthase and NADH:FMN oxidoreductase activities. The flavin reductase activity was characterized, showing the existence of a complex between FMNox and MtCS. FMNox and NADH equilibrium binding was measured. Primary deuterium, solvent and multiple kinetic isotope effects are described and suggest distinct steps for hydride and proton transfers, with the former being more rate-limiting. Conclusion This is the first report showing that a bacterial CS is bifunctional. Primary deuterium kinetic isotope effects show that C4-proS hydrogen is being transferred during the reduction of FMNox by NADH and that hydride transfer contributes significantly to the rate-limiting step of FMN reduction reaction. Solvent kinetic isotope effects and

  2. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst

    Science.gov (United States)

    Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

    2017-10-01

    Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because of the extreme inertness of CO2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

  3. Bifunctional Anti-Non-Amyloid Component α-Synuclein Nanobodies Are Protective In Situ.

    Directory of Open Access Journals (Sweden)

    David C Butler

    Full Text Available Misfolding, abnormal accumulation, and secretion of α-Synuclein (α-Syn are closely associated with synucleinopathies, including Parkinson's disease (PD. VH14 is a human single domain intrabody selected against the non-amyloid component (NAC hydrophobic interaction region of α-Syn, which is critical for initial aggregation. Using neuronal cell lines, we show that as a bifunctional nanobody fused to a proteasome targeting signal, VH14PEST can counteract heterologous proteostatic effects of mutant α-Syn on mutant huntingtin Exon1 and protect against α-Syn toxicity using propidium iodide or Annexin V readouts. We compared this anti-NAC candidate to NbSyn87, which binds to the C-terminus of α-Syn. NbSyn87PEST degrades α-Syn as well or better than VH14PEST. However, while both candidates reduced toxicity, VH14PEST appears more effective in both proteostatic stress and toxicity assays. These results show that the approach of reducing intracellular monomeric targets with novel antibody engineering technology should allow in vivo modulation of proteostatic pathologies.

  4. Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

    Science.gov (United States)

    Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

    2017-02-01

    Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

  5. Hypoxia targeted bifunctional suicide gene expression enhances radiotherapy in vitro and in vivo

    International Nuclear Information System (INIS)

    Sun, Xiaorong; Xing, Ligang; Deng, Xuelong; Hsiao, Hung Tsung; Manami, Akiko; Koutcher, Jason A.; Clifton Ling, C.; Li, Gloria C.

    2012-01-01

    Purpose: To investigate whether hypoxia targeted bifunctional suicide gene expression-cytosine deaminase (CD) and uracil phosphoribosyltransferase (UPRT) with 5-FC treatments can enhance radiotherapy. Materials and methods: Stable transfectants of R3327-AT cells were established which express a triple-fusion-gene: CD, UPRT and monomoric DsRed (mDsRed) controlled by a hypoxia inducible promoter. Hypoxia-induced expression/function of CDUPRTmDsRed was verified by western blot, flow cytometry, fluorescent microscopy, and cytotoxicity assay of 5-FU and 5-FC. Tumor-bearing mice were treated with 5-FC and local radiation. Tumor volume was monitored and compared with those treated with 5-FC or radiation alone. In addition, the CDUPRTmDsRed distribution in hypoxic regions of tumor sections was visualized with fluorescent microscopy. Results: Hypoxic induction of CDUPRTmDsRed protein correlated with increased sensitivity to 5-FC and 5-FU. Significant radiosensitization effects were detected after 5-FC treatments under hypoxic conditions. In the tumor xenografts, the distribution of CDUPRTmDsRed expression visualized with fluorescence microscopy was co-localized with the hypoxia marker pimonidazole positive staining cells. Furthermore, administration of 5-FC to mice in combination with local irradiation resulted in significant tumor regression, as in comparison with 5-FC or radiation treatments alone. Conclusions: Our data suggest that the hypoxia-inducible CDUPRT/5-FC gene therapy strategy has the ability to specifically target hypoxic cancer cells and significantly improve the tumor control in combination with radiotherapy.

  6. Bifunctional Rhodamine Probes of Myosin Regulatory Light Chain Orientation in Relaxed Skeletal Muscle Fibers

    Science.gov (United States)

    Brack, Andrew S.; Brandmeier, Birgit D.; Ferguson, Roisean E.; Criddle, Susan; Dale, Robert E.; Irving, Malcolm

    2004-01-01

    The orientation of the regulatory light chain (RLC) region of the myosin heads in relaxed skinned fibers from rabbit psoas muscle was investigated by polarized fluorescence from bifunctional rhodamine (BR) probes cross-linking pairs of cysteine residues introduced into the RLC. Pure 1:1 BR-RLC complexes were exchanged into single muscle fibers in EDTA rigor solution for 30 min at 30°C; ∼60% of the native RLC was removed and stoichiometrically replaced by BR-RLC, and >85% of the BR-RLC was located in the sarcomeric A-bands. The second- and fourth-rank order parameters of the orientation distributions of BR dipoles linking RLC cysteine pairs 100-108, 100-113, 108-113, and 104-115 were calculated from polarized fluorescence intensities, and used to determine the smoothest RLC orientation distribution—the maximum entropy distribution—consistent with the polarized fluorescence data. Maximum entropy distributions in relaxed muscle were relatively broad. At the peak of the distribution, the “lever” axis, linking Cys707 and Lys843 of the myosin heavy chain, was at 70–80° to the fiber axis, and the “hook” helix (Pro830–Lys843) was almost coplanar with the fiber and lever axes. The temperature and ionic strength of the relaxing solution had small but reproducible effects on the orientation of the RLC region. PMID:15041671

  7. Toward Protein Structure In Situ: Comparison of Two Bifunctional Rhodamine Adducts of Troponin C

    Science.gov (United States)

    Julien, Olivier; Sun, Yin-Biao; Knowles, Andrea C.; Brandmeier, Birgit D.; Dale, Robert E.; Trentham, David R.; Corrie, John E. T.; Sykes, Brian D.; Irving, Malcolm

    2007-01-01

    As part of a program to develop methods for determining protein structure in situ, sTnC was labeled with a bifunctional rhodamine (BR or BSR), cross-linking residues 56 and 63 of its C-helix. NMR spectroscopy of the N-terminal domain of BSR-labeled sTnC in complex with Ca2+ and the troponin I switch peptide (residues 115–131) showed that BSR labeling does not significantly affect the secondary structure of the protein or its dynamics in solution. BR-labeling was previously shown to have no effect on the solution structure of this complex. Isometric force generation in isolated demembranated fibers from rabbit psoas muscle into which BR- or BSR-labeled sTnC had been exchanged showed reduced Ca2+-sensitivity, and this effect was larger with the BSR label. The orientation of rhodamine dipoles with respect to the fiber axis was determined by polarized fluorescence. The mean orientations of the BR and BSR dipoles were almost identical in relaxed muscle, suggesting that both probes accurately report the orientation of the C-helix to which they are attached. The BSR dipole had smaller orientational dispersion, consistent with less flexible linkers between the rhodamine dipole and cysteine-reactive groups. PMID:17483167

  8. A self-cleaning Li-S battery enabled by a bifunctional redox mediator

    Science.gov (United States)

    Ren, Y. X.; Zhao, T. S.; Liu, M.; Zeng, Y. K.; Jiang, H. R.

    2017-09-01

    The polysulfide shuttle effect and lithium dendrite growth in lithium-sulfur (Li-S) batteries can repeatedly breach the anodic solid electrolyte interphase (SEI) over cycling. As a result, irreversible short-chain sulfide side products (Li2Sx, x = 1, 2) keep depositing on the Li anode, leading to the active material loss, increasing the Li+ transport resistance, and thereby reducing the cycle life. In this work, indium iodide (InI3) is investigated as a bifunctional electrolyte additive for Li-S batteries to protect the Li anode and decompose the side products spontaneously. On the one hand, Indium (In) is electrodeposited onto the Li anode prior to Li plating during the initial charging process, forming a chemically and mechanically stable SEI to prevent the Li anode from reacting with soluble polysulfide species to form Li2Sx (x = 1, 2) side products. On the other hand, by adequately overcharging the battery, the triiodide/iodide redox mediator is capable of chemically transforming side products deposited on the Li anode and separator into soluble polysulfides, which can be recycled by the cathode. It is shown that the battery with the InI3 additive exhibits a prolonged cycle life, and is capable of retrieving its capacity by a facile overcharging process.

  9. Bifunctional separator as a polysulfide mediator for highly stable Li-S batteries

    KAUST Repository

    Abbas, Syed Ali

    2016-05-24

    The shuttling process involving lithium polysulfides is one of the major factors responsible for the degradation in capacity of lithium–sulfur batteries (LSBs). Herein, we demonstrate a novel and simple strategy—using a bifunctional separator, prepared by spraying poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) on pristine separator—to obtain long-cycle LSBs. The negatively charged SO3– groups present in PSS act as an electrostatic shield for soluble lithium polysulfides through mutual coulombic repulsion, whereas PEDOT provides chemical interactions with insoluble polysulfides (Li2S, Li2S2). The dual shielding effect can provide an efficient protection from the shuttling phenomenon by confining lithium polysulfides to the cathode side of the battery. Moreover, coating with PEDOT:PSS transforms the surface of the separator from hydrophobic to hydrophilic, thereby improving the electrochemical performance. We observed an ultralow decay of 0.0364% per cycle when we ran the battery for 1000 cycles at 0.25 C—far superior to that of the pristine separator and one of the lowest recorded values reported at a low current density. We examined the versatility of our separator by preparing a flexible battery that functioned well under various stress conditions; it displayed flawless performance. Accordingly, this economical and simple strategy appears to be an ideal platform for commercialization of LSBs.

  10. The Design of New HIV-IN Tethered Bifunctional Inhibitors using Multiple Microdomain Targeted Docking.

    Science.gov (United States)

    Ciubotaru, Mihai; Musat, Mihaela Georgiana; Surleac, Marius; Ionita, Elena; Petrescu, Andrei Jose; Abele, Edgars; Abele, Ramona

    2018-04-05

    Currently used antiretroviral HIV therapy drugs exclusively target critical groups in the enzymes essential for the viral life cycle. Increased mutagenesis of their genes, changes these viral enzymes which once mutated can evade therapeutic targeting, effects which confer drug resistance. To circumvent this, our review addresses a strategy to design and derive HIV-Integrase (HIV-IN) inhibitors which simultaneously target two IN functional domains, rendering it inactive even if the enzyme accumulates many mutations. First we review the enzymatic role of IN to insert the copied viral DNA into a chromosome of the host T lymphocyte, highlighting its main functional and structural features to be subjected to inhibitory action. From a functional and structural perspective we present all classes of HIV-IN inhibitors with their most representative candidates. For each chosen compound we also explain its mechanism of IN inhibition. We use the recently resolved cryo EM IN tetramer intasome DNA complex [1] onto which we dock various reference IN inhibitory chemical scaffolds such as to target adjacent functional IN domains. Pairing compounds with complementary activity, which dock in the vicinity of a IN structural microdomain, we design bifunctional new drugs which may not only be more resilient to IN mutations but also may be more potent inhibitors than their original counterparts. In the end of our review we propose synthesis pathways to link such paired compounds with enhanced synergistic IN inhibitory effects. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  11. A bifunctional electrolyte additive for separator wetting and dendrite suppression in lithium metal batteries

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Hao; Xie, Yong; Xiang, Hongfa; Shi, Pengcheng; Liang, Xin; Xu, Wu

    2018-04-01

    Reformulation of electrolyte systems and improvement of separator wettability are vital to electrochemical performances of rechargeable lithium (Li) metal batteries, especially for suppressing Li dendrites. In this work we report a bifunctional electrolyte additive that improves separator wettability and suppresses Li dendrite growth in LMBs. A triblock polyether (Pluronic P123) was introduced as an additive into a commonly used carbonate-based electrolyte. It was found that addition of 0.2~1% (by weight) P123 into the electrolyte could effectively enhance the wettability of polyethylene separator. More importantly, the adsorption of P123 on Li metal surface can act as an artificial solid electrolyte interphase layer and contribute to suppress the growth of Li dendrites. A smooth and dendritic-free morphology can be achieved in the electrolyte with 0.2% P123. The Li||Li symmetric cells with the 0.2% P123 containing electrolyte exhibit a relatively stable cycling stability at high current densities of 1.0 and 3.0 mA cm-2.

  12. Highly stable acyclic bifunctional chelator for {sup 64}Cu PET imaging

    Energy Technology Data Exchange (ETDEWEB)

    Abada, S.; Lecointre, A.; Christine, C.; Charbonniere, L. [CNRS/UDS, EPCM, Strasbourg (France). Lab. d' Ingenierie Appliquee a l' Analyse; Dechamps-Olivier, I. [Univ. de Reims Champagne Ardenne, Reims (France). Group Chimie de Coordination; Platas-Iglesias, C. [Univ. da Coruna (Spain). Dept. de Quimica Fundamental; Elhabiri, M. [CNRS/UDS, EPCM, Strasbourg (France). Lab. de Physico-Chimie Bioinorganique

    2011-07-01

    Ligand L{sup 1}, based on a pyridine scaffold, functionalized by two bis(methane phosphonate)aminomethyl groups, was shown to display a very high affinity towards Cu(II) (log K{sub CuL}=22.7) and selectivity over Ni(II), Co(II), Zn(II) and Ga(III) ({delta} log K{sub ML}>4) as shown by the values of the stability constants obtained from potentiometric measurements. Insights into the coordination mode of the ligand around Cu(II) cation were obtained by UV-Vis absorption and EPR spectroscopies as well as density functional theory (DFT) calculations (B3LYP model) performed in aqueous solution. The results point to a pentacoordination pattern of the metal ion in the fully deprotonated [CuL{sup 1}]{sup 6-} species. Considering the beneficial thermodynamic parameters of this ligand, kinetic experiments were run to follow the formation of the copper(II) complexes, indicating a very rapid formation of the complex, appropriate for {sup 64}Cu complexation. As L{sup 1} represents a particularly interesting target within the frame of {sup 64}Cu PET imaging, a synthetic protocol was developed to introduce a labeling function on the pyridyl moiety of L{sup 1}, thereby affording L{sup 2}, a potential bifunctional chelator (BFC) for PET imaging.

  13. Bifunctional separator as a polysulfide mediator for highly stable Li-S batteries

    KAUST Repository

    Abbas, Syed Ali; Ibrahem, Mohammed Aziz; Hu, Lung-hao; Lin, Chia-Nan; Fang, Jason; Boopathi, Karunakara Moorthy; Wang, Pen-Cheng; Li, Lain-Jong; Chu, Chih Wei

    2016-01-01

    The shuttling process involving lithium polysulfides is one of the major factors responsible for the degradation in capacity of lithium–sulfur batteries (LSBs). Herein, we demonstrate a novel and simple strategy—using a bifunctional separator, prepared by spraying poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) on pristine separator—to obtain long-cycle LSBs. The negatively charged SO3– groups present in PSS act as an electrostatic shield for soluble lithium polysulfides through mutual coulombic repulsion, whereas PEDOT provides chemical interactions with insoluble polysulfides (Li2S, Li2S2). The dual shielding effect can provide an efficient protection from the shuttling phenomenon by confining lithium polysulfides to the cathode side of the battery. Moreover, coating with PEDOT:PSS transforms the surface of the separator from hydrophobic to hydrophilic, thereby improving the electrochemical performance. We observed an ultralow decay of 0.0364% per cycle when we ran the battery for 1000 cycles at 0.25 C—far superior to that of the pristine separator and one of the lowest recorded values reported at a low current density. We examined the versatility of our separator by preparing a flexible battery that functioned well under various stress conditions; it displayed flawless performance. Accordingly, this economical and simple strategy appears to be an ideal platform for commercialization of LSBs.

  14. Solution Structure of a Novel C2-Symmetrical Bifunctional Bicyclic Inhibitor Based on SFTI-1

    International Nuclear Information System (INIS)

    Jaulent, Agnes M.; Brauer, Arnd B. E.; Matthews, Stephen J.; Leatherbarrow, Robin J.

    2005-01-01

    A novel bifunctional bicyclic inhibitor has been created that combines features both from the Bowman-Birk inhibitor (BBI) proteins, which have two distinct inhibitory sites, and from sunflower trypsin inhibitor-1 (SFTI-1), which has a compact bicyclic structure. The inhibitor was designed by fusing together a pair of reactive loops based on a sequence derived from SFTI-1 to create a backbone-cyclized disulfide-bridged 16-mer peptide. This peptide has two symmetrically spaced trypsin binding sites. Its synthesis and biological activity have been reported in a previous communication [Jaulent and Leatherbarrow, 2004, PEDS 17, 681]. In the present study we have examined the three-dimensional structure of the molecule. We find that the new inhibitor, which has a symmetrical 8-mer half-cystine CTKSIPP'I' motif repeated through a C 2 symmetry axis also shows a complete symmetry in its three-dimensional structure. Each of the two loops adopts the expected canonical conformation common to all BBIs as well as SFTI-1. We also find that the inhibitor displays a strong and unique structural identity, with a notable lack of minor conformational isomers that characterise most reactive site loop mimics examined to date as well as SFTI-1. This suggests that the presence of the additional cyclic loop acts to restrict conformational mobility and that the deliberate introduction of cyclic symmetry may offer a general route to locking the conformation of β-hairpin structures

  15. Flexible control of cellular encapsulation, permeability, and release in a droplet-templated bifunctional copolymer scaffold.

    Science.gov (United States)

    Chen, Qiushui; Chen, Dong; Wu, Jing; Lin, Jin-Ming

    2016-11-01

    Designing cell-compatible, bio-degradable, and stimuli-responsive hydrogels is very important for biomedical applications in cellular delivery and micro-scale tissue engineering. Here, we report achieving flexible control of cellular microencapsulation, permeability, and release by rationally designing a diblock copolymer, alginate-conjugated poly(N-isopropylacrylamide) (Alg-co-PNiPAM). We use the microfluidic technique to fabricate the bifunctional copolymers into thousands of mono-disperse droplet-templated hydrogel microparticles for controlled encapsulation and triggered release of mammalian cells. In particular, the grafting PNiPAM groups in the synthetic cell-laden microgels produce lots of nano-aggregates into hydrogel networks at elevated temperature, thereafter enhancing the permeability of microparticle scaffolds. Importantly, the hydrogel scaffolds are readily fabricated via on-chip quick gelation by triggered release of Ca 2+ from the Ca-EDTA complex; it is also quite exciting that very mild release of microencapsulated cells is achieved via controlled degradation of hydrogel scaffolds through a simple strategy of competitive affinity of Ca 2+ from the Ca-Alginate complex. This finding suggests that we are able to control cellular encapsulation and release through ion-induced gelation and degradation of the hydrogel scaffolds. Subsequently, we demonstrate a high viability of microencapsulated cells in the microgel scaffolds.

  16. Designing calcium phosphate-based bifunctional nanocapsules with bone-targeting properties

    Energy Technology Data Exchange (ETDEWEB)

    Khung, Yit-Lung; Bastari, Kelsen; Cho, Xing Ling; Yee, Wu Aik; Loo, Say Chye Joachim, E-mail: joachimloo@ntu.edu.sg [Nanyang Technological University, School of Materials Science and Engineering (Singapore)

    2012-06-15

    Using sodium dodecyl sulphate micelles as template, hollow-cored calcium phosphate nanocapsules were produced. The surfaces of the nanocapsule were subsequently silanised by a polyethylene glycol (PEG)-based silane with an N-hydroxysuccinimide ester end groups which permits for further attachment with bisphosphonates (BP). Characterisations of these nanocapsules were investigated using Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy, Fourier Transform Infra-Red Spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Dynamic Light Scattering. To further validate the bone-targeting potential, dentine discs were incubated with these functionalised nanocapsules. FESEM analysis showed that these surface-modified nanocapsules would bind strongly to dentine surfaces compared to non-functionalised nanocapsules. We envisage that respective components would give this construct a bifunctional attribute, whereby (1) the shell of the calcium phosphate nanocapsule would serve as biocompatible coating aiding in gradual osteoconduction, while (2) surface BP moieties, acting as targeting ligands, would provide the bone-targeting potential of these calcium phosphate nanocapsules.

  17. Designing calcium phosphate-based bifunctional nanocapsules with bone-targeting properties

    International Nuclear Information System (INIS)

    Khung, Yit-Lung; Bastari, Kelsen; Cho, Xing Ling; Yee, Wu Aik; Loo, Say Chye Joachim

    2012-01-01

    Using sodium dodecyl sulphate micelles as template, hollow-cored calcium phosphate nanocapsules were produced. The surfaces of the nanocapsule were subsequently silanised by a polyethylene glycol (PEG)-based silane with an N-hydroxysuccinimide ester end groups which permits for further attachment with bisphosphonates (BP). Characterisations of these nanocapsules were investigated using Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy, Fourier Transform Infra-Red Spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Dynamic Light Scattering. To further validate the bone-targeting potential, dentine discs were incubated with these functionalised nanocapsules. FESEM analysis showed that these surface-modified nanocapsules would bind strongly to dentine surfaces compared to non-functionalised nanocapsules. We envisage that respective components would give this construct a bifunctional attribute, whereby (1) the shell of the calcium phosphate nanocapsule would serve as biocompatible coating aiding in gradual osteoconduction, while (2) surface BP moieties, acting as targeting ligands, would provide the bone-targeting potential of these calcium phosphate nanocapsules.

  18. "Click" chemistry mildly stabilizes bifunctional gold nanoparticles for sensing and catalysis.

    Science.gov (United States)

    Li, Na; Zhao, Pengxiang; Liu, Na; Echeverria, María; Moya, Sergio; Salmon, Lionel; Ruiz, Jaime; Astruc, Didier

    2014-07-01

    A large family of bifunctional 1,2,3-triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox-robust metal complex, or a β-cyclodextrin unit) has been synthesized by facile "click" chemistry and mildly coordinated to nanogold particles, thus providing stable water-soluble gold nanoparticles (AuNPs) in the size range 3.0-11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence "turn-on" assay, and the catalytic activity of the smallest triazole-AuNPs (core of 3.0 nm) is excellent for the reduction of 4-nitrophenol in water. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. A High Molar Extinction Coefficient Ru(II Complex Functionalized with cis-Dithiocyanato-bis-(9-anthracenyl-10-(2-methyl-2-butenoic acid-1,10-phenanthroline: Potential Sensitizer for Stable Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2014-01-01

    Full Text Available New heteroleptic ruthenium(II complex was formulated as [Ru(L12(NCS2], where L1 = 9-anthracenyl-10-(2-methyl-2-butenoic acid-1,10-phenanthroline was synthesized and its photophysical properties were studied and compared to previously reported analogue complex containing no anthracene moiety [Ru(L22(NCS2], L2 = (2-methyl-2-butenoic acid-1,10-phenanthroline. The two complexes though exhibit very strong molar extinction coefficient values; however, [Ru(L12(NCS2] shows better characteristic broad and intense metal-to-ligand charge transfer (MLCT absorption band and higher molar absorptivity coefficient at (λmax=522 nm, ε=6.60×104 M−1 cm−1 than that of [Ru(L22(NCS2] complex, (λmax=446 nm, ε=4.82×104 M−1 cm−1. At room temperature, long wavelength emissions with strong intensity ratio centered at 660 nm were recorded for [Ru(L12(NCS2] complex with a bathochromic shift (λem=700 nm for [Ru(L22(NCS2] complex. It was shown that the luminescence wavelength characteristic of the complexes may be a function relating to the increasing length of π-conjugation and/or molecular weight. A preliminary cyclic voltammetry of [Ru(L12(NCS2] complex also exhibits good electroredox activity with oxidation potential of about 1.04 V, significantly better than other Ru(II polypyridine complexes containing bidentate ligands.

  20. Synthesis and Photophysical and Electrochemical Properties of Functionalized Mono-, Bis-, and Trisanthracenyl Bridged Ru(II Bis(2,2′:6′,2″-terpyridine Charge Transfer Complexes

    Directory of Open Access Journals (Sweden)

    Adewale O. Adeloye

    2014-01-01

    Full Text Available With the aim of developing new molecular devices having long-range electron transfer in artificial systems and as photosensitizers, a series of homoleptic ruthenium(II bisterpyridine complexes bearing one to three anthracenyl units sandwiched between terpyridine and 2-methyl-2-butenoic acid group are synthesized and characterized. The complexes formulated as bis-4′-(9-monoanthracenyl-10-(2-methyl-2-butenoic acid terpyridyl ruthenium(II bis(hexafluorophosphate (RBT1, bis-4′-(9-dianthracenyl-10-(2-methyl-2-butenoic acid terpyridyl ruthenium(II bis(hexafluorophosphate (RBT2, and bis-4′-(9-trianthracenyl-10-(2-methyl-2-butenoic acid terpyridyl ruthenium(II bis(hexafluorophosphate (RBT3 were characterized by elemental analysis, FT-IR, UV-Vis, photoluminescence, 1H and 13C NMR spectroscopy, and electrochemical techniques by elemental analysis, FT-IR, UV-Vis, photoluminescence, 1H and 13C NMR spectroscopy, and electrochemical techniques. The cyclic voltammograms (CVs of (RBT1, (RBT2, and (RBT3 display reversible one-electron oxidation processes at E1/2 = 1.13 V, 0.71 V, and 0.99 V, respectively (versus Ag/AgCl. Based on a general linear correlation between increase in the length of π-conjugation bond and the molar extinction coefficients, the Ru(II bisterpyridyl complexes show characteristic broad and intense metal-to-ligand charge transfer (MLCT band absorption transitions between 480–600 nm, ε=9.45×103 M−1 cm−1, and appreciable photoluminescence spanning the visible region.

  1. DFT Simulation of Structural and Optical Properties of 9-Aminoacridine Half-Sandwich Ru(II), Rh(III), and Ir(III) Antitumoral Complexes and Their Interaction with DNA.

    Science.gov (United States)

    Cerón-Carrasco, José Pedro; Ruiz, José; Vicente, Consuelo; de Haro, Concepción; Bautista, Delia; Zúñiga, José; Requena, Alberto

    2017-08-08

    In this work, we use DFT-based methods to simulate the chemical structures, optical properties, and interaction with DNA of a recently synthesized chelated C^N 9-aminoacridine arene Ru(II) anticancer agent and two new closely related Rh(III) and Ir(III) complexes using DFT-based methods. Four chemical models and a number of theoretical approaches, which representatively include the PBE0, B97D, ωB97X, ωB97X-D, M06, and M06-L density functionals and the LANL2DZ, def2-SVP, and def2-TZVP basis sets, are tested. The best overall accuracy/cost performance for the optimization process is reached at the ωB97X-D/def2-SVP and M06/def2-SVP levels of theory. Inclusion of explicit solvent molecules (CHCl 3 ) further refines the geometry, while taking into account the crystal network gives no significant improvements of the computed bond distances and angles. The analysis of the excited states reveals that the M06 level matches better the experimental absorption spectra, compared to ωB97X-D. The use of the M06/def2-SVP approach is therefore a well-balanced method to study theoretically the bioactivity of this type of antitumoral complexes, so we couple this TD-DFT approach to molecular dynamics simulations in order to assess their reactivity with DNA. The reported results demonstrate that these drugs could be used to inject electrons into DNA, which might broaden their applications in photoactivated chemotherapy and as new materials for DNA-based electrochemical nanodevices.

  2. Solvent extraction of uranium(VI), plutonium(VI) and americium(III) with HTTA/HPMBP using mono- and bi-functional neutral donors. Synergism and thermodynamics

    International Nuclear Information System (INIS)

    Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

    2000-01-01

    Synergistic extraction of hexavalent uranium and plutonium as well as trivalent americium was studied in HNO 3 with thenoyl, trifluoro-acetone (HTTA)/1-phenyl, 3-methyl, 4-benzoyl pyrazolone-5 (HPMBP) in combination with neutral donors viz. DPSO, TBP, TOPO (mono-functional) and DBDECMP, DHDECMP, CMPO (bi-functional) with wide basicity range using benzene as diluent. A linear correlation was observed when the equilibrium constant log Ks for the organic phase synergistic reaction of both U(VI) and Pu(VI) with either of the chelating agents HTTA or HPMBP was plotted vs. the basicity (log Kh) of the donor (both mono- and bi-functional) indicating bi-functional donors also behave as mono-functional. This was supported by the thermodynamic data (ΔG 0 , ΔH 0 , ΔS 0 ) obtained for these systems. The organic phase adduct formation reactions were identified for the above systems from the thermodynamic data. In the Am(III) HTTA system log K s values of bi-functional donors were found to be very high and deviate from the linear plot (log K s vs. log K h ) obtained for mono-functional donors, indicating that they function as bi-functional for the Am(III)/HTTA) system studied. This was supported by high +ve ΔS 0 values obtained for this system. (author)

  3. Gadolinium and fluorescent bi-functionally labeling and in vitro MRI of rat bone marrow mesenchymal stem cells

    International Nuclear Information System (INIS)

    Shen Jun; Zhou Cuiping; Cheng Li'na; Duan Xiaohui; Liang Biling; Fu Yue; Bi Xiaobin; Liu Yu; Deng Yubin

    2008-01-01

    Objective: To determine the feasibility of magnetically labeling and tracking mesenchymal stem cells (MSCs) in vitro by using a gadolinium and fluorescent bi-functionally transfection agent of polyethylenimine. Methods: A gadolinium bifunctional transfection reagent complex was obtained after the linear polyethylenimine derivative (JetPEI-FluoR) was incubated with Gd-DTPA. Mesenchymal stem cells isolated from the bone marrows of SD rats were cultured and expanded. The mesenchymal stem cells were incubated with the bi-functional labeling agents. After labeling, the MSCs were examined with fluoroscope and electron microscope and the biological characters were detected including trypan blue exclusion test, MTT, and apoptosis detection. On a 1.5 T MR system, the labeled MSCs were examined with spin echo T 1 WI and T 2 WI and T 1 measurement with mixed sequence. After labeling, the cells were cultured and undergone routine passage. Prior MR examinations were repeated for each passage of labeled cells. All data was statistically prolessed with SPSS for Windows. Results: Of 5 x 10 5 MSCs incubated with the bi-functional agents, 4.25 x 10 5 MSCs were successfully labeled, the percentage of labeled MSCs was 85% fluoroscopically. The high density electron particles of gadolinium observed electron microscopically existed around cellular apparatuses, especially around Golgi apparatus. In trypan blue exclusion test, the exclusion rate of labeled MSCs with incubation duration of 3,6,12,24 h was (96.55±2.90)%, (94.17± 2.56)%, (97.16±3.12)% and (94.23±2.67)%, respectively. The corresponding exclusion rate of unlabeled MSCs was (95.86±2.67)%, (92.04±2.21)%, (93.38±3.64)% and (92.12±2.53)%, respectively. There was no statistical difference of trypan blue exclusion rate between labeled cells and control unlabeled cells within 24 hours of incubation (F=4.523, P>0.05). In the proliferation test, the optical absorption value of labeled MSC with 2.5, 5.0, 10.0, 20.0, 30.0 and 40

  4. Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

    Science.gov (United States)

    Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

    2017-08-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Bifunctional Au@TiO_2 core–shell nanoparticle films for clean water generation by photocatalysis and solar evaporation

    International Nuclear Information System (INIS)

    Huang, Jian; He, Yurong; Wang, Li; Huang, Yimin; Jiang, Baocheng

    2017-01-01

    Highlights: • Au@TiO_2 core-shell nanoparticles were prepared in this study. • Bifunctional films for photocatalysis and solar evaporation were designed. • The evaporation and photodegradation with core-shell structures were investigated. - Abstract: With water scarcity becoming an increasingly critical issue for modern society, solar seawater desalination represents a promising approach to mitigating water shortage. In addition, solar seawater desalination shows great potential for mitigating the energy crisis due to its high photo-thermal conversion efficiency. However, the increasing contamination of seawater makes it difficult to generate clean water through simple desalination processes. In this work, clean water is generated by a newly designed bifunctional Au@TiO_2 core-shell nanoparticle film with a high photo-thermal conversion efficiency that is capable of photocatalysis and solar evaporation for seawater desalination. Bifunctional films of Au@TiO_2 core-shell nanoparticles with good stability were prepared. It was found that the formation of the core-shell structures played a key role in promoting the photo-thermal conversion efficiency and the evaporation of seawater, while the photocatalytic function demonstrated herein could contribute to the purification of polluted seawater. Furthermore, the film structure can serve to concentrate the NPs for the photo-reaction, as well as heat for water evaporation, improving both the photo-reaction efficiency and photo-thermal conversion efficiency. This efficient approach to solar seawater desalination, which combines evaporation with the photodegradation of pollutants, could help to address the dual issues of water scarcity and water pollution.

  6. Bifunctional Agents for MRI, PET and Fluorescence Imaging and Study of Nanoparticles Formed from Water Oxidation Catalysts /

    OpenAIRE

    Abadjian, Marie-Caline Z.

    2014-01-01

    The work is divided into four parts : (1) MRI contrast agents are designed to enhance T₁ relaxivity by coupling them to dendrimers, the precise structure of which can be controlled through synthesis. Cyclen is used as a starting scaffold for the synthesis of bifunctional Gd-DOTA and Gd- DOTMA analogues. One unique side chain on the macrocycle contains an azide moiety that can be clicked to an alkyne- containing core, making a first-generation dendrimer with the potential to improve MRI effici...

  7. The sunburn cell in hairless mouse epidermis: quantitative studies with UV-A radiation and mono- and bifunctional psoralens

    International Nuclear Information System (INIS)

    Young, A.R.; Magnus, I.A.

    1982-01-01

    The production of the sunburn cell by UV-A radiation and topical psoralens in hairless mouse epidermis has been studied. It has been shown that the appearance of this cell is dependent on the dose of both UV-A radiation and of the psoralen. The time-course with 8-methoxypsoralen has peak sunburn cell numbers at 28 hr postirradiation. A comparison of 2 bifunctional (8-methoxypsoralen and 5-methoxypsoralen) and 2 monofunctional (angelicin and 3-carbethoxypsoralen) psoralens showed the former are more potent. This suggests that DNA crosslink lesions may play a rle in sunburn cell production

  8. Enantioselective Alkylation of 2-Oxindoles Catalyzed by a Bifunctional Phase-Transfer Catalyst: Synthesis of (-)-Debromoflustramine B.

    Science.gov (United States)

    Craig, Ryan; Sorrentino, Emiliano; Connon, Stephen J

    2018-03-26

    A new bifunctional phase-transfer catalyst that employs hydrogen bonding as a control element was developed to promote efficient enantioselective S N 2 reactions for the construction all-carbon quaternary stereocenters in high yield and excellent enantioselectivity (up to 97 % ee) utilizing the alkylation of a malleable oxindole substrate. The utility of the methodology was demonstrated through a concise and highly enantioselective synthesis of (-)-debromoflustramine B. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Ascorbic acid as a bifunctional hydrogen bond donor for the synthesis of cyclic carbonates from CO2 under ambient conditions

    KAUST Repository

    Arayachukiat, Sunatda

    2017-07-14

    Readily available ascorbic acid was discovered as an environmentally benign hydrogen bond donor (HBD) for the synthe-sis of cyclic organic carbonates from CO2 and epoxides in the presence of nucleophilic co-catalysts. The ascorbic acid/TBAI (TBAI: tetrabutylammonium iodide) binary system could be applied for the cycloaddition of CO2 to various epoxides under ambient or mild conditions. DFT calculations and catalysis experiments revealed an intriguing bifunctional mechanism in the step of CO2 insertion involving different hydroxyl moieties (enediol, ethyldiol) of the ascorbic acid scaffold.

  10. Ascorbic acid as a bifunctional hydrogen bond donor for the synthesis of cyclic carbonates from CO2 under ambient conditions

    KAUST Repository

    Arayachukiat, Sunatda; Kongtes, Chutima; Barthel, Alexander; Vummaleti, Sai V. C.; Poater, Albert; Wannakao, Sippakorn; Cavallo, Luigi; D'Elia, Valerio

    2017-01-01

    Readily available ascorbic acid was discovered as an environmentally benign hydrogen bond donor (HBD) for the synthe-sis of cyclic organic carbonates from CO2 and epoxides in the presence of nucleophilic co-catalysts. The ascorbic acid/TBAI (TBAI: tetrabutylammonium iodide) binary system could be applied for the cycloaddition of CO2 to various epoxides under ambient or mild conditions. DFT calculations and catalysis experiments revealed an intriguing bifunctional mechanism in the step of CO2 insertion involving different hydroxyl moieties (enediol, ethyldiol) of the ascorbic acid scaffold.

  11. NAD-Dependent DNA-Binding Activity of the Bifunctional NadR Regulator of Salmonella typhimurium

    OpenAIRE

    Penfound, Thomas; Foster, John W.

    1999-01-01

    NadR is a 45-kDa bifunctional regulator protein. In vivo genetic studies indicate that NadR represses three genes involved in the biosynthesis of NAD. It also participates with an integral membrane protein (PnuC) in the import of nicotinamide mononucleotide, an NAD precursor. NadR was overexpressed and purified as a His-tagged fusion in order to study its DNA-binding properties. The protein bound to DNA fragments containing NAD box consensus sequences. NAD proved to be the relevant in vivo co...

  12. Recent Advances in Dynamic Kinetic Resolution by Chiral Bifunctional (Thio)urea- and Squaramide-Based Organocatalysts.

    Science.gov (United States)

    Li, Pan; Hu, Xinquan; Dong, Xiu-Qin; Zhang, Xumu

    2016-10-14

    The organocatalysis-based dynamic kinetic resolution (DKR) process has proved to be a powerful strategy for the construction of chiral compounds. In this feature review, we summarized recent progress on the DKR process, which was promoted by chiral bifunctional (thio)urea and squaramide catalysis via hydrogen-bonding interactions between substrates and catalysts. A wide range of asymmetric reactions involving DKR, such as asymmetric alcoholysis of azlactones, asymmetric Michael-Michael cascade reaction, and enantioselective selenocyclization, are reviewed and demonstrate the efficiency of this strategy. The (thio)urea and squaramide catalysts with dual activation would be efficient for more unmet challenges in dynamic kinetic resolution.

  13. Novel bifunctional anthracycline and nitrosourea chemotherapy for human bladder cancer: analysis in a preclinical survival model.

    Science.gov (United States)

    Glaves, D; Murray, M K; Raghavan, D

    1996-08-01

    A hybrid drug [N-2-chloroethylnitrosoureidodaunorubicin (AD312)] that combines structural and functional features of both anthracyclines and nitrosoureas was evaluated in a preclinical survival model of human bladder cancer. To measure the therapeutic activity of AD312, UCRU-BL13 transitional cell carcinoma cells were grown as xenografts in nude mice, and tumor growth rates were compared after i.v. administration of the drug at three dose levels. AD312 treatment at 45 and 60 mg/kg achieved 7-10-fold inhibition of tumor growth and increased host survival by 156 and 249%, respectively. Doses of 60 mg/kg showed optimal therapeutic efficacy, with sustained tumor growth inhibition, an over 2-fold increase in life span, and 40% of mice tumor free ("cured") at 120 days. Tumors were unresponsive to maximum tolerated doses of doxorubicin, a standard anthracycline used as a single agent and in combination therapies for bladder cancer. 1,3-Bis-[2-chloroethyl]-1-nitrosourea was used as a control for the apparently enhanced response of human tumors in murine hosts to nitrosoureas. 1, 3-Bis-[2-chloroethyl]-1-nitrosourea administered in three injections of 20 mg/kg did not cure mice but temporarily inhibited tumor growth by 70% and prolonged survival by 55%; its activity in this model suggests that it may be included in the repertoire of alkylating agents currently used for treatment of bladder cancers. AD312 showed increased antitumor activity with less toxicity than doxorubicin, and its bifunctional properties provide the opportunity for simultaneous treatment of individual cancer cells with two cytotoxic modalities as well as treatment of heterogeneous populations typical of bladder cancers. This novel cytotoxic drug cured doxorubicin-refractory disease and should be investigated for the clinical management of bladder cancer.

  14. Modification of bifunctional epoxy resin using CO{sub 2} fixation process and nanoclay

    Energy Technology Data Exchange (ETDEWEB)

    Khoshkish, Morteza; Bouhendi, Hosein, E-mail: H.boohendi@ippi.ac.ir; Vafayan, Mehdi

    2014-10-15

    A bifunctional epoxy resin was modified by using a CO{sub 2} fixation solution process in the presence of tetra n-butyl ammonium bromide (TBAB) as catalyst and the modified treated resin was treated by cloisite 30B as nano additive. The Unmodified epoxy resin (UME), CO{sub 2} fixated modified epoxy resin (CFME), and CFME/clay nano composite (CFMEN), were cured by diethylenetriamine (DETA). A cycloaliphatic compound as a reactive diluent was used to control the viscosity of high viscose CFME. The exfoliation of organoclay in UME and CFME was investigated by X-ray diffraction and activation energy was computed using the advanced integral isoconversional method. The activation energy dependency demonstrated that the mechanism of UME curing did not change in the presence of nanoclay. In contrast, the CO{sub 2} fixation results showed a significant change in the activation energy dependency. The Thermal stability parameters include the initial degradation temperature (IDT), the temperature at the maximum rate of weight loss (T{sub max}), and the decomposition activation energy (E{sub d}) were determined by thermal gravimetry analysis. Dynamic mechanical thermal analysis measurements showed that the presence of organoclay in CFME increases the T{sub g} of nano composite in contrast to UME. The fracture roughness of UME, CFME and CFNE were determined by scanning electron microscope. The exfoliated UME/1%clay nanocomposite was confirmed by TEM image. - Highlights: • A new epoxy resin was synthesized using CO{sub 2} fixation reaction. • The synthesized epoxy resin was modified by an organo nano-clay. • CO{sub 2} fixation noticeably changed the curing mechanism. • CO{sub 2} fixation reaction consumes CO{sub 2} which is a harmful greenhouse gas.

  15. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

    Science.gov (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

    2017-05-22

    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Spectrophotometric method for determination of bifunctional macrocyclic ligands in macrocyclic ligand-protein conjugates

    International Nuclear Information System (INIS)

    Dadachova, E.; Chappell, L.L.; Brechbiel, M.W.

    1999-01-01

    A simple spectrophotometric assay for determination of bifunctional polyazacarboxylate-macrocyclic ligands of different sizes that are conjugated to proteins has been developed for: 12-membered macrocycle DOTA (2-[4-nitrobenzyl]-1, 4, 7, 10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid) and analogs, the 15-membered PEPA macrocycle (2-[4-nitrobenzyl]-1,4,7,10,13-pentaazacyclopentadecane-N,N',N'',N''',N'''' -pentaacetic acid), and the large 18-membered macrocycle HEHA (1,4,7,10,13,16-hexaazacyclooctadecane-N,N',N'',N''',N''''-hexaacetic acid). The method is based on titration of the blue-colored 1:1 Pb(II)-Arsenazo III (AAIII) complex with the polyazacarboxylate macrocyclic ligand in the concentration range of 0-2.5 μM, wherein color change occurring upon transchelation of the Pb(II) from the AAIII to the polyazamacrocyclic ligand is monitored at 656 nm. The assay is performed at ambient temperature within 20 min without any interfering interaction between the protein and Pb(II)-AA(III) complex. Thus, this method also provides a ligand-to-protein ratio (L/P ratio) that reflects the effective number of ligands per protein molecule available to radiolabeling. The method is not suitable for 14-membered TETA macrocycle (2-[4-nitrobenzyl]-1, 4, 8, 11-tetraazacyclotetradecane N,N',N'',N'''-tetraacetic acid) because of low stability constant of Pb(II)-TETA complex. The method is rapid, simple and may be customized for other polyazacarboxylate macrocyclic ligands

  17. Enhancing Cooperativity in Bifunctional Acid–Pd Catalysts with Carboxylic Acid-Functionalized Organic Monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Coan, Patrick D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Ellis, Lucas D. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Griffin, Michael B. [National Bioenergy Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States; Schwartz, Daniel K. [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States; Medlin, J. Will [Department of Chemical and Biological Engineering, University of Colorado—Boulder, Boulder, Colorado 80309, United States

    2018-03-01

    Cooperative catalysts containing a combination of noble metal hydrogenation sites and Bronsted acid sites are critical for many reactions, including the deoxygenation (DO) of biomass-derived oxygenates in the upgrading of pyrolysis oil. One route toward the design of cooperative catalysts is to tether two different catalytically active functions so that they are in close proximity while avoiding undesirable interactions that can block active sites. Here, we deposited carboxylic acid (CA)-functionalized organophosphonate monolayers onto Al2O3-supported Pd nanoparticle catalysts to prepare bifunctional catalysts containing both Bronsted acid and metal sites. Modification with phosphonic acids (PAs) improved activity and selectivity for gas-phase DO reactions, but the degree of improvement was highly sensitive to both the presence and positioning of the CA group, suggesting a significant contribution from both the PA and CA sites. Short spacer lengths of 1-2 methylene groups between the phosphonate head and CA tail were found to yield the best DO rates and selectivities, whereas longer chains performed similarly to self-assembled monolayers having alkyl tails. Results from a combination of density functional theory and Fourier transform infrared spectroscopy suggested that the enhanced catalyst performance on the optimally positioned CAs was due to the generation of strong acid sites on the Al2O3 support adjacent to the metal. Furthermore, the high activity of these sites was found to result from a hydrogen-bonded cyclic structure involving cooperativity between the phosphonate head group and CA tail function. More broadly, these results indicate that functional groups tethered to supports via organic ligands can influence catalytic chemistry on metal nanoparticles.

  18. Facile preparation of Ag-Cu bifunctional electrocatalysts for zinc-air batteries

    International Nuclear Information System (INIS)

    Jin, Yachao; Chen, Fuyi

    2015-01-01

    Highlights: • Ag-Cu dendrites are observed for the first time to exhibit high catalytic activity for oxygen reduction reaction. • Ag-Cu dendrites are directly synthesized through galvanic displacement on the current collector layer made of Ni foams. • A bifunctional air cathode is fabricated using Ag-Cu dendrites as a carbon-free, binder-free catalyst layer. • Both the primary and rechargeable zinc–air batteries fabricated by Ag-Cu catalysts exhibit excellent performance. - ABSTRACT: An inexpensive, facile galvanic displacement reaction for the direct growth of silver–copper (Ag-Cu) catalysts on nickel foams is developed for the first time. The resulting Ag-Cu catalysts exhibit dendritic morphologies. Ag and Cu atoms are in their metallic state while the presence of CuO and Cu 2 O are limited on the surface of catalyst. The catalysts demonstrate high catalytic activity for oxygen reduction reaction (ORR) in alkaline solution, as evaluated by both linear scanning voltammetry and rotating disk electrode polarization measurements. The ORR catalysed by Ag-Cu catalyst in alkaline solution proceeds through a four-electron pathway. An air cathode is fabricated using Ag-Cu catalyst as a carbon-free, binder-free catalyst layer. Using this Ag-Cu catalyst based air cathode, both the primary and rechargeable zinc-air batteries show excellent battery performance. The specific capacity of the primary zinc-air battery is 572 mAh g −1 . Especially, the rechargeable zinc-air battery shows high round-trip efficiency, appealing stability at a long charge-discharge cycle period

  19. Modification of bifunctional epoxy resin using CO2 fixation process and nanoclay

    International Nuclear Information System (INIS)

    Khoshkish, Morteza; Bouhendi, Hosein; Vafayan, Mehdi

    2014-01-01

    A bifunctional epoxy resin was modified by using a CO 2 fixation solution process in the presence of tetra n-butyl ammonium bromide (TBAB) as catalyst and the modified treated resin was treated by cloisite 30B as nano additive. The Unmodified epoxy resin (UME), CO 2 fixated modified epoxy resin (CFME), and CFME/clay nano composite (CFMEN), were cured by diethylenetriamine (DETA). A cycloaliphatic compound as a reactive diluent was used to control the viscosity of high viscose CFME. The exfoliation of organoclay in UME and CFME was investigated by X-ray diffraction and activation energy was computed using the advanced integral isoconversional method. The activation energy dependency demonstrated that the mechanism of UME curing did not change in the presence of nanoclay. In contrast, the CO 2 fixation results showed a significant change in the activation energy dependency. The Thermal stability parameters include the initial degradation temperature (IDT), the temperature at the maximum rate of weight loss (T max ), and the decomposition activation energy (E d ) were determined by thermal gravimetry analysis. Dynamic mechanical thermal analysis measurements showed that the presence of organoclay in CFME increases the T g of nano composite in contrast to UME. The fracture roughness of UME, CFME and CFNE were determined by scanning electron microscope. The exfoliated UME/1%clay nanocomposite was confirmed by TEM image. - Highlights: • A new epoxy resin was synthesized using CO 2 fixation reaction. • The synthesized epoxy resin was modified by an organo nano-clay. • CO 2 fixation noticeably changed the curing mechanism. • CO 2 fixation reaction consumes CO 2 which is a harmful greenhouse gas

  20. Synthesis and Characterization of Bifunctional Organic-Glasses Based on Diphenylhydrazone and Barbituric Acid Derivative for Photorefractive Application

    Energy Technology Data Exchange (ETDEWEB)

    Park, Ki Hong [KIST, Seoul (Korea, Republic of); Lee, Sang Ho; Choi, Chil Sung; Kim, Nak Joong [Hanyang University, Seoul (Korea, Republic of); Choi, Dong Hoon [Kyunghee University, Youngin (Korea, Republic of)

    2003-12-15

    A series of amorphous molecules that possess both photoconductive and electro-optic properties was synthesized in order to investigate photorefractive properties of bifunctional organic-glasses. Diethylaminobenzaldehyde- diphenylhydrazone was covalently attached to 5-(4-diethylamino-benzylidene)-1,3-dimethylpyrimidine- 2,4,6-trione through a flexible alkyl chain (3, 4, 5, 6 and 10 carbons) containing two ether linkages. The longer linkage not only lowered the glass transition temperature (Tg) of the molecules, but also allowed faster orientation of the chromophore. To examine the photorefractive properties, a 50 μm-thick film was prepared from the mixture of a bifunctional molecule, butyl benzyl phthalate, and C{sup 60}. The photoconductivity of this composite was as high as 8.01 x 10{sup -12} S/cm at 60 V/μm, and the maximum diffraction efficiency (ηmax) of 50 μm-thick film was about 5% at 80 V/μm.

  1. Preparation of highly hydrophobic cotton fabrics by modification with bifunctional silsesquioxanes in the sol-gel process

    Energy Technology Data Exchange (ETDEWEB)

    Przybylak, Marcin, E-mail: marcin.przybylak@ppnt.poznan.pl [Poznań Science and Technology Park, Adam Mickiewicz University Foundation, Rubież 46, 61-612 Poznań (Poland); Maciejewski, Hieronim, E-mail: maciejm@amu.edu.pl [Poznań Science and Technology Park, Adam Mickiewicz University Foundation, Rubież 46, 61-612 Poznań (Poland); Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, 61-614 Poznań (Poland); Dutkiewicz, Agnieszka, E-mail: agdut@interia.pl [Poznań Science and Technology Park, Adam Mickiewicz University Foundation, Rubież 46, 61-612 Poznań (Poland)

    2016-11-30

    Highlights: • Fabric hydrophobization process using bifunctional silsesquioxanes was studied. • Superhydrophobic fabric was produced using fluorofunctional silsesquioxanes. • Surface of modified fabrics was analyzed using different techniques. - Abstract: The surface modification of cotton fabrics was carried out using two types of bifunctional fluorinated silsesquioxanes with different ratios of functional groups. The modification was performed either by one- or two-step process. Two methods, the sol-gel and the dip coating method were used in different configurations. The heat treatment and the washing process were applied after modification. The wettability of cotton fabric was evaluated by measuring water contact angles (WCA). Changes in the surface morphology were examined by scanning electron microscopy (SEM, SEM-LFD) and atomic force microscopy (AFM). Moreover, the modified fabrics were subjected to analysis of elemental composition of the applied coatings using SEM-EDS techniques. Highly hydrophobic textiles were obtained in all cases studied and one of the modifications resulted in imparting superhydrophobic properties. Most of impregnated textiles remained hydrophobic even after multiple washing process which shows that the studied modification is durable.

  2. A novel bifunctional Ni-doped TiO2 inverse opal with enhanced SERS performance and excellent photocatalytic activity

    Science.gov (United States)

    Li, Xuehong; Wu, Yun; Shen, Yuhua; Sun, Yan; Yang, Ying; Xie, Anjian

    2018-01-01

    Three-dimensional inverse opal photonic microarray (IOPM) structure exhibits good qualities in structural regularity and interconnectivity, such as high specific surface area, large pore volume, uniform pore size, and ordered periodic construction. Here, a novel nickel-doped titanium dioxide IOPM (Ni-TiO2 IOPM) was fabricated for the first time as a bifunctional material for the applications of surface-enhanced Raman scattering (SERS) substrate and photocatalyst. The Ni doping could change the defect concentration of the substrate to enhance the SERS effect, and could increase the light absorption of the substrate in visible region. The synergistic effect of Ni doping and the periodically ordered porous structure enhanced both SERS sensitivity and photocatalytic activity. As a SERS substrate, the Ni-TiO2 IOPM exhibited highly sensitive detection capability for 4-mercaptobenzoic acid (4-MBA) at a concentration as low as 1 × 10-11 M. Under simulated sunlight, about 95% of the methylene blue (MB) was degraded within 90 min when Ni-TiO2 IOPM was used as the photocatalytst. The Ni-TiO2 IOPM prepared in this work may be a promising bifunctional SERS substrate candidate for organic sewage detection and environment protection. In addition, the fabrication strategy can be extended to synthesize other nanomaterials with orderly and porous structure.

  3. Bifunctional cis-Abienol Synthase from Abies balsamea Discovered by Transcriptome Sequencing and Its Implications for Diterpenoid Fragrance Production*

    Science.gov (United States)

    Zerbe, Philipp; Chiang, Angela; Yuen, Macaire; Hamberger, Björn; Hamberger, Britta; Draper, Jason A.; Britton, Robert; Bohlmann, Jörg

    2012-01-01

    The labdanoid diterpene alcohol cis-abienol is a major component of the aromatic oleoresin of balsam fir (Abies balsamea) and serves as a valuable bioproduct material for the fragrance industry. Using high-throughput 454 transcriptome sequencing and metabolite profiling of balsam fir bark tissue, we identified candidate diterpene synthase sequences for full-length cDNA cloning and functional characterization. We discovered a bifunctional class I/II cis-abienol synthase (AbCAS), along with the paralogous levopimaradiene/abietadiene synthase and isopimaradiene synthase, all of which are members of the gymnosperm-specific TPS-d subfamily. The AbCAS-catalyzed formation of cis-abienol proceeds via cyclization and hydroxylation at carbon C-8 of a postulated carbocation intermediate in the class II active site, followed by cleavage of the diphosphate group and termination of the reaction sequence without further cyclization in the class I active site. This reaction mechanism is distinct from that of synthases of the isopimaradiene- or levopimaradiene/abietadiene synthase type, which employ deprotonation reactions in the class II active site and secondary cyclizations in the class I active site, leading to tricyclic diterpenes. Comparative homology modeling suggested the active site residues Asp-348, Leu-617, Phe-696, and Gly-723 as potentially important for the specificity of AbCAS. As a class I/II bifunctional enzyme, AbCAS is a promising target for metabolic engineering of cis-abienol production. PMID:22337889

  4. Robust Control of PEP Formation Rate in the Carbon Fixation Pathway of C4 Plants by a Bi-functional Enzyme

    Directory of Open Access Journals (Sweden)

    Hart Yuval

    2011-10-01

    Full Text Available Abstract Background C4 plants such as corn and sugarcane assimilate atmospheric CO2 into biomass by means of the C4 carbon fixation pathway. We asked how PEP formation rate, a key step in the carbon fixation pathway, might work at a precise rate, regulated by light, despite fluctuations in substrate and enzyme levels constituting and regulating this process. Results We present a putative mechanism for robustness in C4 carbon fixation, involving a key enzyme in the pathway, pyruvate orthophosphate dikinase (PPDK, which is regulated by a bifunctional enzyme, Regulatory Protein (RP. The robust mechanism is based on avidity of the bifunctional enzyme RP to its multimeric substrate PPDK, and on a product-inhibition feedback loop that couples the system output to the activity of the bifunctional regulator. The model provides an explanation for several unusual biochemical characteristics of the system and predicts that the system's output, phosphoenolpyruvate (PEP formation rate, is insensitive to fluctuations in enzyme levels (PPDK and RP, substrate levels (ATP and pyruvate and the catalytic rate of PPDK, while remaining sensitive to the system's input (light levels. Conclusions The presented PPDK mechanism is a new way to achieve robustness using product inhibition as a feedback loop on a bifunctional regulatory enzyme. This mechanism exhibits robustness to protein and metabolite levels as well as to catalytic rate changes. At the same time, the output of the system remains tuned to input levels.

  5. Effects of thiourea and ammonium bicarbonate on the formation and stability of bifunctional cisplatin-DNA adducts : consequences for the accurate quantification of adducts in (cellular) DNA

    NARCIS (Netherlands)

    Fichtinger-Schepman, A.M.J.; Dijk-Knijnenburg, H.C.M. van; Dijt, F.J.; Velde-Visser, S.D. van der; Berends, F.; Baan, R.A.

    1995-01-01

    Cisplatin reacts with DNA by forming mainly bifunctional adducts via reactive monofunctional intermediates. When freshly platinated DNA was postincubated with thiourea (10 mM, at 23 or 37°C) for periods of up to 24 h, followed by determination of mono- and diadducts, a rapid initial decrease was

  6. Insights Into the Bifunctional Aphidicolan-16-ß-ol Synthase Through Rapid Biomolecular Modeling Approaches.

    Science.gov (United States)

    Hirte, Max; Meese, Nicolas; Mertz, Michael; Fuchs, Monika; Brück, Thomas B

    2018-01-01

    Diterpene synthases catalyze complex, multi-step C-C coupling reactions thereby converting the universal, aliphatic precursor geranylgeranyl diphosphate into diverse olefinic macrocylces that form the basis for the structural diversity of the diterpene natural product family. Since catalytically relevant crystal structures of diterpene synthases are scarce, homology based biomolecular modeling techniques offer an alternative route to study the enzyme's reaction mechanism. However, precise identification of catalytically relevant amino acids is challenging since these models require careful preparation and refinement techniques prior to substrate docking studies. Targeted amino acid substitutions in this protein class can initiate premature quenching of the carbocation centered reaction cascade. The structural characterization of those alternative cyclization products allows for elucidation of the cyclization reaction cascade and provides a new source for complex macrocyclic synthons. In this study, new insights into structure and function of the fungal, bifunctional Aphidicolan-16-ß-ol synthase were achieved using a simplified biomolecular modeling strategy. The applied refinement methodologies could rapidly generate a reliable protein-ligand complex, which provides for an accurate in silico identification of catalytically relevant amino acids. Guided by our modeling data, ACS mutations lead to the identification of the catalytically relevant ACS amino acid network I626, T657, Y658, A786, F789, and Y923. Moreover, the ACS amino acid substitutions Y658L and D661A resulted in a premature termination of the cyclization reaction cascade en-route from syn-copalyl diphosphate to Aphidicolan-16-ß-ol. Both ACS mutants generated the diterpene macrocycle syn-copalol and a minor, non-hydroxylated labdane related diterpene, respectively. Our biomolecular modeling and mutational studies suggest that the ACS substrate cyclization occurs in a spatially restricted location of

  7. Insights Into the Bifunctional Aphidicolan-16-ß-ol Synthase Through Rapid Biomolecular Modeling Approaches

    Directory of Open Access Journals (Sweden)

    Max Hirte

    2018-04-01

    Full Text Available Diterpene synthases catalyze complex, multi-step C-C coupling reactions thereby converting the universal, aliphatic precursor geranylgeranyl diphosphate into diverse olefinic macrocylces that form the basis for the structural diversity of the diterpene natural product family. Since catalytically relevant crystal structures of diterpene synthases are scarce, homology based biomolecular modeling techniques offer an alternative route to study the enzyme's reaction mechanism. However, precise identification of catalytically relevant amino acids is challenging since these models require careful preparation and refinement techniques prior to substrate docking studies. Targeted amino acid substitutions in this protein class can initiate premature quenching of the carbocation centered reaction cascade. The structural characterization of those alternative cyclization products allows for elucidation of the cyclization reaction cascade and provides a new source for complex macrocyclic synthons. In this study, new insights into structure and function of the fungal, bifunctional Aphidicolan-16-ß-ol synthase were achieved using a simplified biomolecular modeling strategy. The applied refinement methodologies could rapidly generate a reliable protein-ligand complex, which provides for an accurate in silico identification of catalytically relevant amino acids. Guided by our modeling data, ACS mutations lead to the identification of the catalytically relevant ACS amino acid network I626, T657, Y658, A786, F789, and Y923. Moreover, the ACS amino acid substitutions Y658L and D661A resulted in a premature termination of the cyclization reaction cascade en-route from syn-copalyl diphosphate to Aphidicolan-16-ß-ol. Both ACS mutants generated the diterpene macrocycle syn-copalol and a minor, non-hydroxylated labdane related diterpene, respectively. Our biomolecular modeling and mutational studies suggest that the ACS substrate cyclization occurs in a spatially

  8. Insights into the bifunctional Aphidicolan-16-ß-ol synthase through rapid biomolecular modelling approaches

    Science.gov (United States)

    Hirte, Max; Meese, Nicolas; Mertz, Michael; Fuchs, Monika; Brück, Thomas B.

    2018-04-01

    Diterpene synthases catalyze complex, multi-step C-C coupling reactions thereby converting the universal, aliphatic precursor geranylgeranyl diphosphate into diverse olefinic macrocylces that form the basis for the structural diversity of the diterpene natural product family. Since catalytically relevant crystal structures of diterpene synthases are scarce, homology based biomolecular modelling techniques offer an alternative route to study the enzyme’s reaction mechanism. However, precise identification of catalytically relevant amino acids is challenging since these models require careful preparation and refinement techniques prior to substrate docking studies. Targeted amino acid substitutions in this protein class can initiate premature quenching of the carbocation centered reaction cascade. The structural characterization of those alternative cyclization products allows for elucidation of the cyclization reaction cascade and provides a new source for complex macrocyclic synthons. In this study, new insights into structure and function of the fungal, bifunctional Aphidicolan-16-ß-ol synthase were achieved using a simplified biomolecular modelling strategy. The applied refinement methodologies could rapidly generate a reliable protein-ligand complex, which provides for an accurate in silico identification of catalytically relevant amino acids. Guided by our modelling data, ACS mutations lead to the identification of the catalytically relevant ACS amino acid network I626, T657, Y658, A786, F789 and Y923. Moreover, the ACS amino acid substitutions Y658L and D661A resulted in a premature termination of the cyclization reaction cascade en-route from syn-copalyl diphosphate to Aphidicolan-16-ß-ol. Both ACS mutants generated the diterpene macrocycle syn-copalol and a minor, non-hydroxylated labdane related diterpene, respectively. Our biomolecular modelling and mutational studies suggest that the ACS substrate cyclization occurs in a spatially restricted location

  9. Parameter design and experimental study of a bifunctional isolator for optical payload protection and stabilization

    Science.gov (United States)

    Wang, Guang-yuan; Guan, Xin; Cao, Dong-jing; Tang, Shao-fan; Chen, Xiang; Liang, Lu; Zheng, Gang-tie

    2017-11-01

    With the raise of resolution, optical payloads are becoming increasingly sensitive to satellite jitter. An approach where the entire spacecraft is pointed with great accuracy requires sophisticated and expensive bus design. In an effort to lower the overall cost of space missions that require highly stable line-of-sight pointing, a method of separating the bus and the payload with low frequency isolators is proposed. This isolation system can block the transmission of disturbance and allow relatively large bus motion. However, if the isolator is linear then there is a trade-off between isolation and static deflection as the launch and the on-orbit stage have difference requirements on the isolation frequency. Otherwise, an extra locking system should be appended to protect the payload before getting into orbit, as the STABLE isolation system[1] and the MIM isolation system[2] did. To overcome this limitation, an alternative approach is to design a nonlinear isolator with high-static stiffness during launch and low dynamic stiffness on orbit. Several specially designed nonlinear isolators have achieved low dynamic stiffness with large static load capacity. Virgin[3] considered a structure made from a highly deformed elastic element to achieve a softening spring. Platus[4] exploited the buckling of beams under axial load in a specific configuration to achieve a negative stiffness in combination with a positive stiffness, and hence low-dynamic stiffness. Others have achieved the same by connecting linear springs with positive stiffness in parallel with elements of negative stiffness[5] [7]. In the present study, a bifunctional isolator has been developed for optical payloads. The isolator have good performance both during launch and on orbit because of its specially designed nonlinear stiffness and damping. The isolator works in a linear part with low stiffness and small damping ratio under the micro-vibration and microgravity on orbit. The transmissibility

  10. Acid/base bifunctional carbonaceous nanomaterial with large surface area: Preparation, characterization, and adsorption properties for cationic and anionic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Li, Kai; Ma, Chun–Fang; Ling, Yuan; Li, Meng [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Gao, Qiang, E-mail: gaoqiang@cug.edu.cn [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Engineering Research Center of Nano-Geo Materials of Ministry of Education, China University of Geosciences, Wuhan 430074 (China); Luo, Wen–Jun, E-mail: heartnohome@yahoo.com.cn [Department of Chemistry, Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China)

    2015-07-15

    Nanostructured carbonaceous materials are extremely important in the nano field, yet developing simple, mild, and “green” methods that can make such materials possess large surface area and rich functional groups on their surfaces still remains a considerable challenge. Herein, a one-pot and environment-friendly method, i.e., thermal treatment (180 °C; 18 h) of water mixed with glucose and chitosan (CTS), has been proposed. The resultant carbonaceous nanomaterials were characterized by field emitting scanning electron microscope, N{sub 2} adsorption/desorption, Fourier transform infrared spectroscope, X-ray photoelectron spectroscopy, and zeta-potential analysis. It was found that, in contrast to the conventional hydrothermally carbonized product from pure glucose, with low surface area (9.3 m{sup 2} g{sup −1}) and pore volume (0.016 cm{sup 3} g{sup −1}), the CTS-added carbonaceous products showed satisfactory textural parameters (surface area and pore volume up to 254 m{sup 2} g{sup −1} and 0.701 cm{sup 3} g{sup −1}, respectively). Moreover, it was also interestingly found that these CTS-added carbonaceous products possessed both acidic (–COOH) and basic (–NH{sub 2}) groups on their surfaces. Taking the advantages of large surface area and –COOH/–NH{sub 2} bifunctional surface, the carbonaceous nanomaterials exhibited excellent performance for adsorptions of cationic compound (i.e., methylene blue) at pH 10 and anionic compound (i.e., acid red 18) at pH 2, respectively. This work not only provides a simple and green route to prepare acid/base bifunctional carbonaceous nanomaterials with large surface area but also well demonstrates their potential for application in adsorption. - Highlights: • A simple and green method was proposed to prepare carbon nanomaterials. • The carbon product showed acid/base bifunctional surface with large surface area. • The carbon material could efficiently adsorb both cationic and anionic compounds.

  11. Facile synthesis of flower like FePt@ZnO core–shell structure and its bifunctional properties

    Energy Technology Data Exchange (ETDEWEB)

    Majeed, Jerina [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Jayakumar, O.D., E-mail: ddjaya@barc.gov.in [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Mandal, B.P. [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Salunke, H.G. [Technical Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India); Naik, R. [Department of Physics, Wayne State University, Detroit, MI 48202 (United States); Tyagi, A.K., E-mail: aktyagi@barc.gov.in [Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085 (India)

    2014-06-01

    Graphical abstract: Flower shaped FePt and ZnO coated FePt with core–shell nanostructures are synthesized by a facile solvothermal procedure. Shell thickness of ZnO over FePt core was tuned by varying FePt concentration with respect to ZnO. Hybrid structure with lower FePt concentration exhibited bifunctionality such as near room temperature ferromagnetism and photoluminescence. Pristine FePt crystallize in the fct (L1{sub 0}) phase whereas it converts into fcc phase in presence of ZnO. - Highlights: • FePt@ZnO hybrid core–shell particles, with unique flower shape morphology have been prepared by solvothermal method. • Phase transition of fct-FePt to fcc-FePt has been found in presence of ZnO nanoparticles. • Plausible mechanism for growth of flowershaped nanoparticle is in accordance with energy minimization principle. • The core shell structure (FePt@ZnO) exhibits bi-functional properties. - Abstract: Flower shaped FePt and ZnO coated FePt (FePt@ZnO) core–shell nanostructures are synthesized by a facile solvothermal procedure. Two different compositions (molar ratio) of FePt and ZnO (FePt:ZnO = 1:3 and FePt:ZnO = 1:6) core–shells with different thicknesses of ZnO shells were synthesized. Hybrid FePt@ZnO core–shell flower structure with lower FePt concentration (FePt:ZnO = 1:6) exhibited bifunctionality including near room temperature ferromagnetism and photoluminescence at ambient conditions. X-ray diffraction patterns of pristine FePt showed partially ordered face centred tetragonal (fct) L1{sub 0} phase whereas ZnO coated FePt (FePt@ZnO) nanostructures showed hexagonal ZnO and disordered phase of FePt with fcc structure. The phase transition of fct FePt to fcc phase occurring in presence of ZnO is further confirmed by transmission electron microscopy and magnetic measurement studies. The formation of the nanoflowers was possibly due to growth along the [0 1 1] or [0 0 1] direction, keeping the core nearly spherical in accordance with the

  12. Development of bifunctional microencapsulated phase change materials with crystalline titanium dioxide shell for latent-heat storage and photocatalytic effectiveness

    International Nuclear Information System (INIS)

    Chai, Luxiao; Wang, Xiaodong; Wu, Dezhen

    2015-01-01

    Highlights: • We designed and synthesized a sort of bifunctional PCMs-based microcapsules. • These microcapsules have an n-eicosane core and a crystalline TiO 2 shell. • Such a crystalline TiO 2 shell exhibited a good photocatalytic activity. • The microcapsules showed good performance in energy storage and sterilization. - Abstract: A sort of novel bifunctional microencapsulated phase change material (PCM) was designed by encapsulating n-eicosane into a crystalline titanium dioxide (TiO 2 ) shell and, then, was successfully synthesized through in-situ polycondensation in the sol–gel process using tetrabutyl titanate as a titania precursor. The resultant microcapsule samples were characterized by Fourier-transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to determine their chemical compositions and structures. Furthermore, the crystallinity of the TiO 2 shell was verified by powder X-ray diffraction patterns. It was confirmed that the fluorinions could induce the phase transition from the amorphous TiO 2 to the brookite-form crystals during the sol–gel process, thus resulting in a crystalline TiO 2 shell for the microencapsulated n-eicosane. The scanning and transmission electron microscopy investigations indicated that all of the resultant microcapsules presented a perfect spherical shape with a uniform particle size of 1.5–2 μm, and they also exhibited a well-defined core–shell structure as well as a smooth and compact shell. The crystalline TiO 2 shell made the resultant microcapsules a photocatalytic activity, and therefore, these microcapsules demonstrated a good photocatalytic effect for the chemical degradation and an antimicrobial function for some of the Gram-negative bacteria. Most of all, all of the microencapsulated n-eicosane samples indicated good phase-change performance and high thermal reliability for latent-heat storage and release, and moreover, they achieved a high

  13. Imine derivatives of lathonones. Part I -- Reactions of neodymium (III) isopropoxide with monofunctional bidendtate and bifunctional tridentate aldimines and ketamines

    International Nuclear Information System (INIS)

    Mital, S.P.; Singh, R.V.; Tandon, J.P.

    1980-01-01

    Nd(OPrsup(i))sub(2) (SB) and Nd(Oprsup(i))(SB)sub(2) [where SBH represents the molecule of monofunctional bidentate aldimine] type of derivatives have been synthesised by 1:1 and 1:2 molar reactions of neodymium isopropoxide with the aldimines having the donor system NOH and formed by the condensation of salicylaldehyde with alkylamines. However, bifunctional tridentate Schiff bases (LH) 2 have been found to yield Nd(OPrsup(i)) (L) and Nd 2 (L) 3 type of complexes in 1:1 and 2:3 molar ratio respectively. The isopropoxy groups of the 1:1 complexes have been found to undergo replacement reactions with excess of t-butanol and the resulting complexes are hydrolytically stable. All the newly synthesized complexes have been characterized on the basis of elemental analyses, molecular weight determinations, conductance measurements and infrared and proton magnetic resonance spectral studies. (auth.)

  14. Acid–Base Bifunctional Hf Nanohybrids Enable High Selectivity in the Catalytic Conversion of Ethyl Levulinate to γ-Valerolactone

    Directory of Open Access Journals (Sweden)

    Weibo Wu

    2018-06-01

    Full Text Available The catalytic upgrading of bio-based platform molecules is a promising approach for biomass valorization. However, most solid catalysts are not thermally or chemically stable, and are difficult to prepare. In this study, a stable organic phosphonate–hafnium solid catalyst (PPOA–Hf was synthesized, and acid–base bifunctional sites were found to play a cooperative role in the cascade transfer hydrogenation and cyclization of ethyl levulinate (EL to γ-valerolactone (GVL. Under relatively mild reaction conditions of 160 °C for 6 h, EL was completely converted to GVL with a good yield of 85%. The apparent activation energy was calculated to be 53 kJ/mol, which was lower than other solid catalysts for the same reaction. In addition, the PPOA-Hf solid catalyst did not significantly decrease its activity after five recycles, and no evident leaching of Hf was observed, indicating its high stability and potential practical application.

  15. Potent antitumor bifunctional DNA alkylating agents, synthesis and biological activities of 3a-aza-cyclopenta[a]indenes.

    Science.gov (United States)

    Kakadiya, Rajesh; Dong, Huajin; Lee, Pei-Chih; Kapuriya, Naval; Zhang, Xiuguo; Chou, Ting-Chao; Lee, Te-Chang; Kapuriya, Kalpana; Shah, Anamik; Su, Tsann-Long

    2009-08-01

    A series of bifunctional DNA interstrand cross-linking agents, bis(hydroxymethyl)- and bis(carbamates)-8H-3a-azacyclopenta[a]indene-1-yl derivatives were synthesized for antitumor evaluation. The preliminary antitumor studies revealed that these agents exhibited potent cytotoxicity in vitro and antitumor therapeutic efficacy against human tumor xenografts in vivo. Furthermore, these derivatives have little or no cross-resistance to either Taxol or Vinblastine. Remarkably, complete tumor remission in nude mice bearing human breast carcinoma MX-1 xenograft by 13a,b and 14g,h and significant suppression against prostate adenocarcinoma PC3 xenograft by 13b were achieved at the maximum tolerable dose with relatively low toxicity. In addition, these agents induce DNA interstrand cross-linking and substantial G2/M phase arrest in human non-small lung carcinoma H1299 cells. The current studies suggested that these agents are promising candidates for preclinical studies.

  16. Application of bifunctional Saccharomyces cerevisiae to remove lead(II) and cadmium(II) in aqueous solution

    International Nuclear Information System (INIS)

    Zhang Yunsong; Liu Weiguo; Zhang Li; Wang Meng; Zhao Maojun

    2011-01-01

    A magnetic adsorbent, EDTAD-functionalized Saccharomyces cerevisiae, has been synthesized to behave as an adsorbent for heavy metal ions by adjusting the pH value of the aqueous solution to make carboxyl and amino groups protonic or non-protonic. The bifunctional Saccharomyces cerevisiae (EMS) were used to remove lead(II) and cadmium(II) in solution in a batch system. The results showed that the adsorption capacity of the EMS for the heavy metal ions increased with increasing solution pH, and the maximum adsorption capacity (88.16 mg/g for Pb 2+ , 40.72 mg/g for Cd 2+ ) at 10 deg. C was found to occur at pH 5.5 and 6.0, respectively. The adsorption process followed the Langmuir isotherm model. The regeneration experiments revealed that the EMS could be successfully reused.

  17. Nb-Based Zeolites: Efficient bi-Functional Catalysts for the One-Pot Synthesis of Succinic Acid from Glucose

    Directory of Open Access Journals (Sweden)

    Magdi El Fergani

    2017-12-01

    Full Text Available The one-pot production of succinic acid from glucose was investigated in pure hot water as solvent using Nb (0.02 and 0.05 moles%-Beta zeolites obtained by a post-synthesis methodology. Structurally, they are comprised of residual framework Al-acid sites, extra-framework isolated Nb (V and Nb2O5 pore-encapsulated clusters. The Nb-modified Beta-zeolites acted as bi-functional catalysts in which glucose is dehydrated to levulinic acid (LA which, further, suffers an oxidation process to succinic acid (SA. After the optimization of the reaction conditions, that is, at 180 °C, 18 bar O2, and 12 h reaction time, the oxidation of glucose occurred with a selectivity to succinic acid as high as 84% for a total conversion.

  18. Recovery of plutonium from nitric acid containing oxalate and fluoride by a macroporous bifunctional phosphinic acid resin (MPBPA)

    International Nuclear Information System (INIS)

    Venugopal Chetty, K.; Godbole, A.G.; Swarup, R.; Vaidya, V.N.; Venugopal, V.; Vasudeva Rao, P.R.

    2006-01-01

    The sorption of Pu from nitric acid solutions containing oxalate/fluoride was studied using an indigenously available macroporous bifunctional phosphinic acid (MPBPA) resin. Batch experiments were carried out to obtain the distribution data of Pu(IV) with a view to optimize conditions for its recovery from nitric acid waste solutions containing oxalate or fluoride ions. The measurements showed high distribution ratio (D) values even in the presence of strong complexing ions, like oxalate and fluoride, indicating the possibility of recovery of Pu from these types of waste solution. Column studies were carried out using this resin to recover Pu from the oxalate supernatant waste solution, which showed that up to 99% of Pu could be adsorbed on the resin. Elution of Pu loaded on the resin was studied using different eluting agents. (author)

  19. The synthesis of new oxazoline-containing bifunctional catalysts and their application in the addition of diethylzinc to aldehydes.

    Science.gov (United States)

    Coeffard, Vincent; Müller-Bunz, Helge; Guiry, Patrick J

    2009-04-21

    The straightforward preparation of new modular oxazoline-containing bifunctional catalysts is reported employing a microwave-assisted Buchwald-Hartwig aryl amination as the key step. Covalent attachment of 2-(o-aminophenyl)oxazolines and pyridine derivatives generated in good-to-high yields a series of ligands in two or three steps in which each part was altered independently to tune the activity and the selectivity of the corresponding catalysts. These catalysts prepared in situ were subsequently applied in the asymmetric addition of diethylzinc to various aldehydes, producing the corresponding alcohols with enantioselectivities of up to 68%. A transition state model, based on relevant X-ray crystal structures, has also been proposed to explain the observed stereoselectivities.

  20. Graphene-cobaltite-Pd hybrid materials for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells.

    Science.gov (United States)

    Sharma, Chandra Shekhar; Awasthi, Rahul; Singh, Ravindra Nath; Sinha, Akhoury Sudhir Kumar

    2013-12-14

    Hybrid materials comprising of Pd, MCo2O4 (where M = Mn, Co or Ni) and graphene have been prepared for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells. Structural and electrochemical characterizations were carried out using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, chronoamperometry and cyclic, CO stripping, and linear sweep voltammetries. The study revealed that all the three hybrid materials are active for both methanol oxidation (MOR) and oxygen reduction (ORR) reactions in 1 M KOH. However, the Pd-MnCo2O4/GNS hybrid electrode exhibited the greatest MOR and ORR activities. This active hybrid electrode has also outstanding stability under both MOR and ORR conditions, while Pt- and other Pd-based catalysts undergo degradation under similar experimental conditions. The Pd-MnCo2O4/GNS hybrid catalyst exhibited superior ORR activity and stability compared to even Pt in alkaline solutions.

  1. Cloning and characterization of Escherichia coli DUF299: a bifunctional ADP-dependent kinase - Pi-dependent pyrophosphorylase from bacteria

    Directory of Open Access Journals (Sweden)

    Burnell Jim N

    2010-01-01

    Full Text Available Abstract Background Phosphoenolpyruvate synthetase (PEPS; EC 2.7.9.2 catalyzes the synthesis of phosphoenolpyruvate from pyruvate in Escherichia coli when cells are grown on a three carbon source. It also catalyses the anabolic conversion of pyruvate to phosphoenolpyruvate in gluconeogenesis. A bioinformatics search conducted following the successful cloning and expression of maize leaf pyruvate, orthophosphate dikinase regulatory protein (PDRP revealed the presence of PDRP homologs in more than 300 bacterial species; the PDRP homolog was identified as DUF299. Results This paper describes the cloning and expression of both PEPS and DUF299 from E. coli and establishes that E. coli DUF299 catalyzes both the ADP-dependent inactivation and the Pi-dependent activation of PEPS. Conclusion This paper represents the first report of a bifunctional regulatory enzyme catalysing an ADP-dependent phosphorylation and a Pi-dependent pyrophosphorylation reaction in bacteria.

  2. Application of bifunctional Saccharomyces cerevisiae to remove lead(II) and cadmium(II) in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Yunsong [Department of Chemistry, College of Life and Science, Sichuan Agricultural University, Yaan 625014 (China); Liu Weiguo [Agronomy College, Sichuan Agricultural University, Wenjiang 611130 (China); Zhang Li; Wang Meng [Department of Chemistry, College of Life and Science, Sichuan Agricultural University, Yaan 625014 (China); Zhao Maojun, E-mail: yaanyunsong@yahoo.com.cn [Department of Chemistry, College of Life and Science, Sichuan Agricultural University, Yaan 625014 (China)

    2011-09-15

    A magnetic adsorbent, EDTAD-functionalized Saccharomyces cerevisiae, has been synthesized to behave as an adsorbent for heavy metal ions by adjusting the pH value of the aqueous solution to make carboxyl and amino groups protonic or non-protonic. The bifunctional Saccharomyces cerevisiae (EMS) were used to remove lead(II) and cadmium(II) in solution in a batch system. The results showed that the adsorption capacity of the EMS for the heavy metal ions increased with increasing solution pH, and the maximum adsorption capacity (88.16 mg/g for Pb{sup 2+}, 40.72 mg/g for Cd{sup 2+}) at 10 deg. C was found to occur at pH 5.5 and 6.0, respectively. The adsorption process followed the Langmuir isotherm model. The regeneration experiments revealed that the EMS could be successfully reused.

  3. Combination of Bifunctional Alkylating Agent and Arsenic Trioxide Synergistically Suppresses the Growth of Drug-Resistant Tumor Cells

    Directory of Open Access Journals (Sweden)

    Pei-Chih Lee

    2010-05-01

    Full Text Available Drug resistance is a crucial factor in the failure of cancer chemotherapy. In this study, we explored the effect of combining alkylating agents and arsenic trioxide (ATO on the suppression of tumor cells with inherited or acquired resistance to therapeutic agents. Our results showed that combining ATO and a synthetic derivative of 3a-aza-cyclopenta[a]indenes (BO-1012, a bifunctional alkylating agent causing DNA interstrand cross-links, was more effective in killing human cancer cell lines (H460, H1299, and PC3 than combining ATO and melphalan or thiotepa. We further demonstrated that the combination treatment of H460 cells with BO-1012 and ATO resulted in severe G2/M arrest and apoptosis. In a xenograft mouse model, the combination treatment with BO-1012 and ATO synergistically reduced tumor volumes in nude mice inoculated with H460 cells. Similarly, the combination of BO-1012 and ATO effectively reduced the growth of cisplatin-resistant NTUB1/P human bladder carcinoma cells. Furthermore, the repair of BO-1012-induced DNA interstrand cross-links was significantly inhibited by ATO, and consequently, γH2AX was remarkably increased and formed nuclear foci in H460 cells treated with this drug combination. In addition, Rad51 was activated by translocating and forming foci in nuclei on treatment with BO-1012, whereas its activation was significantly suppressed by ATO. We further revealed that ATO might mediate through the suppression of AKT activity to inactivate Rad51. Taken together, the present study reveals that a combination of bifunctional alkylating agents and ATO may be a rational strategy for treating cancers with inherited or acquired drug resistance.

  4. Structure of the phosphotransferase domain of the bifunctional aminoglycoside-resistance enzyme AAC(6')-Ie-APH(2'')-Ia.

    Science.gov (United States)

    Smith, Clyde A; Toth, Marta; Bhattacharya, Monolekha; Frase, Hilary; Vakulenko, Sergei B

    2014-06-01

    The bifunctional acetyltransferase(6')-Ie-phosphotransferase(2'')-Ia [AAC(6')-Ie-APH(2'')-Ia] is the most important aminoglycoside-resistance enzyme in Gram-positive bacteria, conferring resistance to almost all known aminoglycoside antibiotics in clinical use. Owing to its importance, this enzyme has been the focus of intensive research since its isolation in the mid-1980s but, despite much effort, structural details of AAC(6')-Ie-APH(2'')-Ia have remained elusive. The structure of the Mg2GDP complex of the APH(2'')-Ia domain of the bifunctional enzyme has now been determined at 2.3 Å resolution. The structure of APH(2'')-Ia is reminiscent of the structures of other aminoglycoside phosphotransferases, having a two-domain architecture with the nucleotide-binding site located at the junction of the two domains. Unlike the previously characterized APH(2'')-IIa and APH(2'')-IVa enzymes, which are capable of utilizing both ATP and GTP as the phosphate donors, APH(2'')-Ia uses GTP exclusively in the phosphorylation of the aminoglycoside antibiotics, and in this regard closely resembles the GTP-dependent APH(2'')-IIIa enzyme. In APH(2'')-Ia this GTP selectivity is governed by the presence of a `gatekeeper' residue, Tyr100, the side chain of which projects into the active site and effectively blocks access to the adenine-binding template. Mutation of this tyrosine residue to a less bulky phenylalanine provides better access for ATP to the NTP-binding template and converts APH(2'')-Ia into a dual-specificity enzyme.

  5. A paclitaxel prodrug with bifunctional folate and albumin binding moieties for both passive and active targeted cancer therapy.

    Science.gov (United States)

    Shan, Lingling; Zhuo, Xin; Zhang, Fuwu; Dai, Yunlu; Zhu, Guizhi; Yung, Bryant C; Fan, Wenpei; Zhai, Kefeng; Jacobson, Orit; Kiesewetter, Dale O; Ma, Ying; Gao, Guizhen; Chen, Xiaoyuan

    2018-01-01

    Folate receptor (FR) has proven to be a valuable target for chemotherapy using folic acid (FA) conjugates. However, FA-conjugated chemotherapeutics still have low therapeutic efficacy accompanied with side effects, resulting from complications such as short circulation half-life, limited tumor delivery, as well as high kidney accumulation. Herein, we present a novel FA-conjugated paclitaxel (PTX) prodrug which was additionally conjugated with an Evans blue (EB) derivative for albumin binding. The resulting bifunctional prodrug prolonged blood circulation, enhanced tumor accumulation, and consequently improved tumor therapeutic efficacy. Methods: Fmoc-Cys(Trt)-OH was coupled onto PTX at the 7'-OH position for further synthesis of ester prodrug FA-PTX-EB. The targeting ability was investigated using confocal microscopy and flow cytometry. The pharmacokinetics of this bifunctional compound was also studied. Meanwhile, cell viability was evaluated in normal cells and three cancer cell lines by MTT assay. In vivo therapeutic effect was tested on FR-α overexpressing MDA-MB-231 tumor model. Results: Compared with free PTX, the FA-PTX, PTX-EB and FA-PTX-EB prodrugs increased circulation half-life in mice from 2.19 to 3.82, 4.41, and 7.51 h, respectively. Pharmacokinetics studies showed that the FA-PTX-EB delivered more PTX to tumors than FA-PTX and free PTX. In vitro and in vivo studies demonstrated that FA-EB-conjugated PTX induced potent antitumor activity. Conclusion: FA-PTX-EB showed prolonged blood circulation, enhanced drug accumulation in tumors, higher therapeutic index, and lower side effects than either free PTX or monofunctional FA-PTX and EB-PTX. The results support the potential of using EB for the development of long-acting therapeutics.

  6. Study of application properties of novel trisazo hetero bi-functional reactive dyes based on j-acid derivatives for cotton

    International Nuclear Information System (INIS)

    Mokhtari, Javad; Akbarzadeh, A; Phillips, D A S; Taylor, J A

    2009-01-01

    Three novel trisazo hetero bi-functional reactive dyes based on J-acid derivatives were prepared using the diazonium salt of [4-(4-sulphophenylazo-)-2,5-dimethylazobenzene-2-sulphonic acid] and a hetero bi-functional coupling component, derived from 1-hydroxy-6-aminonapthalene-3-sulphonic acid (J-acid), 1-hydroxy-6- methylaminonapthalene-3-sulphonic acid (methyl J-acid), and 1-hydroxy-6-aminonaphthalene-3,5-disulphonic acid (sulpho J-acid). On balance, the dye derived from sulpho J-acid displayed the most attractive set of technical properties, building up and fixing more efficiently than those derived from J-acid and methyl J-acid. In addition, the sulpho J-acid based dye offered better migration and, therefore, level dyeing and ease of wash off. (author)

  7. Therapeutic potential of a non-steroidal bifunctional anti-inflammatory and anti-cholinergic agent against skin injury induced by sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Yoke-Chen; Wang, James D.; Hahn, Rita A.; Gordon, Marion K.; Joseph, Laurie B. [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States); Heck, Diane E. [Department of Environmental Science, New York Medical College, Valhalla, NY (United States); Heindel, Ned D. [Department of Chemistry, Lehigh University, Bethlehem, PA (United States); Young, Sherri C. [Department of Chemistry, Muhlenberg College, Allentown, PA (United States); Sinko, Patrick J. [Department of Pharmaceutics, Rutgers University, Piscataway, NJ (United States); Casillas, Robert P. [MRIGlobal, Kansas City, MO (United States); Laskin, Jeffrey D. [Environmental and Occupational Medicine, Robert Wood Johnson Medical School, Rutgers University, Piscataway, NJ (United States); Laskin, Debra L. [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States); Gerecke, Donald R., E-mail: gerecke@eohsi.rutgers.edu [Department of Pharmacology and Toxicology, Rutgers University, Piscataway, NJ (United States)

    2014-10-15

    Sulfur mustard (bis(2-chloroethyl) sulfide, SM) is a highly reactive bifunctional alkylating agent inducing edema, inflammation, and the formation of fluid-filled blisters in the skin. Medical countermeasures against SM-induced cutaneous injury have yet to be established. In the present studies, we tested a novel, bifunctional anti-inflammatory prodrug (NDH 4338) designed to target cyclooxygenase 2 (COX2), an enzyme that generates inflammatory eicosanoids, and acetylcholinesterase, an enzyme mediating activation of cholinergic inflammatory pathways in a model of SM-induced skin injury. Adult SKH-1 hairless male mice were exposed to SM using a dorsal skin vapor cup model. NDH 4338 was applied topically to the skin 24, 48, and 72 h post-SM exposure. After 96 h, SM was found to induce skin injury characterized by edema, epidermal hyperplasia, loss of the differentiation marker, keratin 10 (K10), upregulation of the skin wound marker keratin 6 (K6), disruption of the basement membrane anchoring protein laminin 322, and increased expression of epidermal COX2. NDH 4338 post-treatment reduced SM-induced dermal edema and enhanced skin re-epithelialization. This was associated with a reduction in COX2 expression, increased K10 expression in the suprabasal epidermis, and reduced expression of K6. NDH 4338 also restored basement membrane integrity, as evidenced by continuous expression of laminin 332 at the dermal–epidermal junction. Taken together, these data indicate that a bifunctional anti-inflammatory prodrug stimulates repair of SM induced skin injury and may be useful as a medical countermeasure. - Highlights: • Bifunctional anti-inflammatory prodrug (NDH4338) tested on SM exposed mouse skin • The prodrug NDH4338 was designed to target COX2 and acetylcholinesterase. • The application of NDH4338 improved cutaneous wound repair after SM induced injury. • NDH4338 treatment demonstrated a reduction in COX2 expression on SM injured skin. • Changes of skin repair

  8. All-optical OR/NOR Bi-functional logic gate by using cross-gain modulation in semiconductor optical amplifiers

    International Nuclear Information System (INIS)

    Choi, Kyoung Sun; Byun, Young Tae; Lee, Seok; Jhon, Young Min

    2010-01-01

    An OR/NOR bi-functional all-optical logic gate has been experimentally demonstrated at 10 Gbit/s by using cross-gain modulation (XGM) in only 2 semiconductor optical amplifiers (SOAs). One SOA was used for NOR operation and the other SOA was used for inversion to obtain OR operation. Numerical simulation has also been performed, which coincided well with the experimental results.

  9. Radioiodination of protein using 2,3,5,6-tetrafluorophenyl 3-(nido-carboranyl) propionate (TCP) as a potential bi-functional linker: Synthesis and biodistribution in mice

    International Nuclear Information System (INIS)

    Lin Rushan; Liu Ning; Yang Yuanyou; Li Bing; Liao Jiali; Jin Jiannan

    2009-01-01

    2,3,5,6-Tetrafluorophenyl 3-(nido-carboranyl) propionate (TCP), as a new potential bi-functional linker for radiohalogenation of proteins or peptides, was synthesized. With this bi-functional linker, the first attempt to conjugate bovine serum albumin (BSA) with 125 I was made and the biodistribution of the conjugated BSA ( 125 I-TCP-BSA) was investigated in NIH strain mice. By the use of TCP as the linker, BSA was conjugated with 125 I in a labeling yield of 58-75% and with radiochemical purity of 99.8% after purification by Sephadex TM G-50. Even after being kept at room temperature for 72 h, the radiochemical purity of 125 I-TCP-BSA was still more than 98%, much higher than that of the directly 125 I-labeled BSA ( 125 I-BSA). Meanwhile, biodistribution experiments in mice indicated that the uptake of 125 I with 125 I-TCP-BSA into thyroid was obviously less than that with 125 I-BSA post-injection. All the results implied that the 125 I-conjugated BSA ( 125 I-TCP-BSA) was considerably stable in vivo as well as in vitro, and TCP was regarded as a promising bi-functional linker for radiohalogenation of proteins

  10. Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

    Science.gov (United States)

    Shinde, Sambhaji S; Lee, Chi Ho; Yu, Jin-Young; Kim, Dong-Hyung; Lee, Sang Uck; Lee, Jung-Ho

    2018-01-23

    The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C 2 N aerogels (S-C 2 NA) as bifunctional catalysts for Zn-air and Li-O 2 batteries. The S-C 2 NA exhibited ultrahigh surface area (∼1943 m 2 g -1 ) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO 2 ) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C 2 NA air cathodes exhibit superb energy densities (958 and 862 Wh kg -1 ), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO 2 catalysts, respectively. Notably, Li-O 2 batteries with S-C 2 NA demonstrated an outstanding specific capacity of ∼648.7 mA h g -1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

  11. Novel Electrospun Dual-Layered Composite Nanofibrous Membrane Endowed with Electricity-Magnetism Bifunctionality at One Layer and Photoluminescence at the Other Layer.

    Science.gov (United States)

    Wang, Zijiao; Ma, Qianli; Dong, Xiangting; Li, Dan; Xi, Xue; Yu, Wensheng; Wang, Jinxian; Liu, Guixia

    2016-10-05

    Dual-layered composite nanofibrous membrane equipped with electrical conduction, magnetism and photoluminescence trifunctionality is constructed via electrospinning. The composite membrane consists of a polyaniline (PANI)/Fe 3 O 4 nanoparticles (NPs)/polyacrylonitrile (PAN) tuned electrical-magnetic bifunctional nanofibrous layer at one side and a Eu(TTA) 3 (TPPO) 2 /polyvinylpyrrolidone (PVP) photoluminescent nanofibrous layer at the other side, and the two layers are tightly combined face-to-face together into the novel dual-layered composite membrane with trifunctionality. The electric conductivity and magnetism of electrical-magnetic bifunctionality can be respectively tunable via modulating the respective PANI and Fe 3 O 4 NPs contents, and the highest electric conductivity approaches the order of 1 × 10 -2 S cm -1 . Predominant red emission at 615 nm can be obviously observed in the photoluminescent layer under 366 nm excitation. Moreover, the luminescent intensity of photoluminescent layer is almost unaffected by the electrical-magnetic bifunctional layer because of the fact that the photoluminescent materials have been successfully isolated from dark-colored PANI and Fe 3 O 4 NPs. The novel dual-layered composite nanofibrous membrane with trifunctionality has potentials in many fields. Furthermore, the design philosophy and fabrication method for the dual-layered multifunctional membrane provide a new and facile strategy toward other membranes with multifunctionality.

  12. CaCu3Ti4O12: A Bifunctional Perovskite Electrocatalyst for Oxygen Evolution and Reduction Reaction in Alkaline Medium

    International Nuclear Information System (INIS)

    Kushwaha, H.S.; Halder, Aditi; Thomas, P.; Vaish, Rahul

    2017-01-01

    Highlights: •A cost effective double perovskite CaCu 3 Ti 4 O 12 have been synthesized using oxalate precursor method. •CCTO electrocatalyst exhibit enhanced bifunctional electrocatalytic activities. •CCTO electrocatalyst have lower overpotential and higher mass activity as compared to noble metal oxide and well-known perovskite catalysts. •Electrochemical impedance spectroscopy investigations of oxygen reactions on perovskite surfaces. -- Abstract: Perovskite oxides are prominent materials as the bifunctional electrocatalysts for both oxygen reduction/evolution reactions (ORR/OER) for the electrochemical energy conversion and storage using regenerative fuel cells and rechargeable metal-air batteries. In this work, a quadruple perovskite CaCu 3 Ti 4 O 12 has been synthesized oxalate precursor route. X-ray diffraction pattern shows phase purity of the synthesized electrocatalyst. The synthesized CCTO electrocatalyst have crystallite size of 26 nm. Electrochemical investigations reveal that CCTO exhibit efficient catalytic activity. More interestingly, an extremely high OER activity is observed for CCTO electrocatalysts which is found superior than similar class of perovskites. Additionally, CCTO shows efficient ORR activity with an onset potential of 0.83 V which is better than that of Pt/C catalyst (≈0.94 V). These results demonstrate the significant potential of CCTO perovskite as a bifunctional electrode material for alkaline fuel cells and metal-air batteries.

  13. NiCo2S4 nanowires array as an efficient bifunctional electrocatalyst for full water splitting with superior activity

    Science.gov (United States)

    Liu, Danni; Lu, Qun; Luo, Yonglan; Sun, Xuping; Asiri, Abdullah M.

    2015-09-01

    The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm-2 at an overpotential of 305 mV for hydrogen evolution and 100 mA cm-2 at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm-2 water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability.The present communication reports the topotactic conversion of NiCo2O4 nanowires array on carbon cloth (NiCo2O4 NA/CC) into NiCo2S4 NA/CC, which is used as an efficient bifunctional electrocatalyst for water splitting with good durability and superior activity in 1.0 M KOH. This NiCo2S4 NA/CC electrode produces 100 mA cm-2 at an overpotential of 305 mV for hydrogen evolution and 100 mA cm-2 at an overpotential of 340 mV for oxygen evolution. To afford a 10 mA cm-2 water-splitting current, the alkaline water electrolyzer made from NiCo2S4 NA/CC needs a cell voltage of 1.68 V, which is 300 mV less than that for NiCo2O4 NA/CC, and has good stability. Electronic supplementary information (ESI) available: Experimental section and ESI Figures. See DOI: 10.1039/c5nr04064g

  14. Synthesis of 4-([{sup 18}F]fluoromethyl)-2-chlorophenylisothiocyanate: a novel bifunctional {sup 18}F-labelling agent

    Energy Technology Data Exchange (ETDEWEB)

    Wuest, F.; Mueller, M.; Bergmann, R. [Inst. fuer Bioanorganische und Radiopharmazeutische Chemie, FZ-Rossendorf e.V., Dresden (Germany)

    2004-07-01

    The one-step radiosynthesis of 4-([{sup 18}F]fluoromethyl)-2-chlorophenylisothiocyanate {sup 18}F-7 as a novel bifunctional {sup 18}F-labelling agent is described. Optimised reaction conditions in a remotely controlled synthesis module gave isothiocyanate {sup 18}F-7 in radiochemical yields of 45% (decay-corrected) within 40 min and high radiochemical purity of > 95% after solid-phase-extraction. Coupling of compound {sup 18}F-7 with the primary amine benzylamine as a model reaction afforded the corresponding ((4-[{sup 18}F]fluoromethyl)-2-chloro-phenyl)-benzyl thiourea {sup 18}F-8 in a high radiochemical yield of > 90%. Stability studies of thiourea {sup 18}F-8 in terms of radiodefluorination showed appreciable buffer stability at pH 7.4, whereas significant radiodefluorination was observed when {sup 18}F-8 was incubated in buffers at pH 3.6 and pH 9.4. Preliminary dynamic PET studies with thiourea {sup 18}F-8 in male Wistar rats showed high bone accumulation, indicative of high in vivo radiodefluorination. (orig.)

  15. Phenyl and ionic liquid based bifunctional periodic mesoporous organosilica supported copper: An efficient nanocatalyst for clean production of polyhydroquinolines.

    Science.gov (United States)

    Elhamifar, Dawood; Ardeshirfard, Hakimeh

    2017-11-01

    A novel phenyl and ionic liquid based bifunctional periodic mesoporous organosilica supported copper (Cu@BPMO-Ph-IL) is prepared, characterized and its catalytic application is developed in the clean production of polyhydroquinolines. The Cu@BPMO-Ph-IL was prepared via chemical grafting of ionic liquid groups onto phenyl-based PMO followed by treatment with copper acetate. This nanocatalyst was characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs), thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD), nitrogen-sorption and energy dispersive X-ray (EDX) analyses. This was successfully applied in the one-pot Hantzsch condensation of aldehydes, ammonium acetate, alkylacetoacetates and dimedone to prepare a set of different derivatives of polyhydroquinolines in high yields and selectivity. The catalyst was effectively recovered and reused several times without important decrease in efficiency. The recovered catalyst was also characterized with TEM analysis to study its stability and durability under applied conditions. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Novel Bifunctional Quinolonyl Diketo Acid Derivatives as HIV-1 Integrase Inhibitors: Design, Synthesis, Biological Activities and Mechanism of Action

    Science.gov (United States)

    Di Santo, Roberto; Costi, Roberta; Roux, Alessandra; Artico, Marino; Lavecchia, Antonio; Marinelli, Luciana; Novellino, Ettore; Palmisano, Lucia; Andreotti, Mauro; Amici, Roberta; Galluzzo, Clementina Maria; Nencioni, Lucia; Palamara, Anna Teresa; Pommier, Yves; Marchand, Christophe

    2008-01-01

    The virally encoded integrase protein is an essential enzyme in the life cycle of the HIV-1 virus and represents an attractive and validated target in the development of therapeutics against HIV infection. Drugs that selectively inhibit this enzyme, when used in combination with inhibitors of reverse transcriptase and protease, are believed to be highly effective in suppressing the viral replication. Among the HIV-1 integrase inhibitors, the β-diketo acids (DKAs) represent a major lead for anti-HIV-1drug development. In this study, novel bifunctional quinolonyl diketo acid derivatives were designed, synthesized and tested for their inhibitory ability against HIV-1 integrase. The compounds are potent inhibitors of integrase activity. Particularly, derivative 8 is a potent IN inhibitor for both steps of the reaction (3′-processing and strand transfer) and exhibits both high antiviral activity against HIV-1 infected cells and low cytotoxicity. Molecular modeling studies provide a plausible mechanism of action, which is consistent with ligand SARs and enzyme photo-crosslinking experiments. PMID:16539381

  17. Catalytic Upgrading of 5-Hydroxymethylfurfural to Drop-in Biofuels by Solid Base and Bifunctional Metal-Acid Catalysts.

    Science.gov (United States)

    Bohre, Ashish; Saha, Basudeb; Abu-Omar, Mahdi M

    2015-12-07

    Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop-in biofuels. Herein, we report a two-step process for upgrading 5-hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3 )x ), which gave 92 % C9 -aldol product with high selectivity at nearly 100 % HMF conversion. The as-synthesised Zr(CO3 )x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3 )x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite-β catalyst in ethanol, which showed quantitative conversion of the aldol product to n-nonane and 1-ethoxynonane with 40 and 56 % selectivity, respectively. 1-Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Voltammetric determination of In3+ based on the bifunctionality of a multi-walled carbon nanotubes-nafion modified electrode.

    Science.gov (United States)

    Li, Junhua; Zhang, Fuxing; Wang, Jianqiu; Xu, Zhifeng; Zeng, Rongying

    2009-05-01

    Due to the strong cation-exchange ability of Nafion and the excellent properties of multi-walled carbon nanotubes (MWCNTs), a highly sensitive and mercury-free method of determining trace levels of In(3+) has been established based on the bifunctionality of a MWCNTs/Nafion modified glassy carbon electrode (GCE). The MWCNTs/Nafion modified GCE detects In(3+) in a 0.01 M HAc-NaAc buffer solution at pH 5.0 using anodic stripping voltammetry (ASV). The experimental results suggest that a sensitive anodic stripping peak appears at -0.58 V on anodic stripping voltammograms, which can be used as an analytical signal for the determination of In(3+). A good linear relationship between the stripping peak currents and the In(3+) concentration is obtained, covering the concentration range from 5.0 x 10(-10) to 2.0 x 10(-7) M, with a correlation coefficient of 0.999; the detection limit is 1.0 x 10(-11) M. This proposed method has been applied to detect In(3+) as a new way.

  19. Voltammetric determination of Cd{sup 2+} based on the bifunctionality of single-walled carbon nanotubes-Nafion film

    Energy Technology Data Exchange (ETDEWEB)

    Sun Dong [Department of Pharmacy, Wenzhou Medical College, Wenzhou 325000 (China) and Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074 (China)]. E-mail: sun_dong11@163.com; Xie Xiafeng [Department of Pharmacy, Wenzhou Medical College, Wenzhou 325000 (China); Cai Yuepiao [Department of Pharmacy, Wenzhou Medical College, Wenzhou 325000 (China); Zhang Huajie [Department of Pharmacy, Wenzhou Medical College, Wenzhou 325000 (China); Wu Kangbing [Department of Chemistry, Huazhong University of Science and Technology, Wuhan 430074 (China)

    2007-01-02

    In the presence of Nafion, single-walled carbon nanotubes (SWNTs) were easily dispersed into ethanol, resulting in a homogeneous SWNTs/Nafion suspension. After evaporating ethanol, a SWNTs/Nafion film with bifunctionality was constructed onto glassy carbon electrode (GCE) surface. Attributing to the strong cation-exchange ability of Nafion and excellent properties of SWNTs, the SWNTs/Nafion film-coated GCE remarkably enhances the sensitivity of determination of Cd{sup 2+}. Based on this, an electrochemical method was developed for the determination of trace levels of Cd{sup 2+} by anodic stripping voltammetry (ASV). In pH 5.0 NaAc-HAc buffer, Cd{sup 2+} was firstly exchanged and adsorbed onto SWNTs/Nafion film surface, and then reduce at -1.10 V. During the positive potential sweep, reduced cadmium was oxidized, and a well-defined stripping peak appeared at -0.84 V, which can be used as analytical signal for Cd{sup 2+}. The linear range is found to be from 4.0 x 10{sup -8} to 4.0 x 10{sup -6} mol L{sup -1}, and the lowest detectable concentration is estimated to be 4.0 x 10{sup -9} mol L{sup -1}. Finally, this method was successfully employed to detect Cd{sup 2+} in water samples.

  20. Two-Step Hydrothermal Synthesis of Bifunctional Hematite-Silver Heterodimer Nanoparticles for Potential Antibacterial and Anticancer Applications

    Science.gov (United States)

    Trang, Vu Thi; Tam, Le Thi; Phan, Vu Ngoc; Van Quy, Nguyen; Huy, Tran Quang; Le, Anh-Tuan

    2017-06-01

    In recent years, the development of composite nanostructures containing noble metal and magnetic nanocrystals has attracted much interest because they offer a promising avenue for multifunctional applications in nanomedicine and pharmacotherapy. In this work, we present a facile two-step hydrothermal approach for the synthesis of bifunctional heterodimer nanoparticles (HDNPs) composed of hematite nanocubes (α-Fe2O3 NCs) and silver nanoparticles (Ag-NPs). The formation and magnetic property of α-Fe2O3-Ag HDNPs was analyzed by transmission electron microscopy, x-ray diffraction and vibrating sample magnetometer. Interestingly, the hydrothermal-synthesized α-Fe2O3-Ag HDNPs were found to display significant antibacterial activity against three types of infectious bacteria. The cytotoxicity of α-Fe2O3-Ag nanocomposite against lung cancer A549 cell line was investigated and compared with that of pure α-Fe2O3 NCs and Ag-NPs. The obtained results reveal that the α-Fe2O3-Ag nanocomposite exhibited higher anticancer performance than that of pure Ag-NPs, whereas pure α-Fe2O3 NCs were not cytotoxic to the tested cells. The inhibitory concentration (IC50) of the α-Fe2O3-Ag nanocomposite was found at 20.94 μg/mL. With the aforementioned properties, α-Fe2O3-Ag HDNPs showed a high potential as a multifunctional material for advanced biomedicine and nanotherapy applications.

  1. Fusions between green fluorescent protein and beta-glucuronidase as sensitive and vital bifunctional reporters in plants.

    Science.gov (United States)

    Quaedvlieg, N E; Schlaman, H R; Admiraal, P C; Wijting, S E; Stougaard, J; Spaink, H P

    1998-11-01

    By fusing the genes encoding green fluorescent protein (GFP) and beta-glucuronidase (GUS) we have created a set of bifunctional reporter constructs which are optimized for use in transient and stable expression studies in plants. This approach makes it possible to combine the advantage of GUS, its high sensitivity in histochemical staining, with the advantages of GFP as a vital marker. The fusion proteins were functional in transient expression studies in tobacco using either DNA bombardment or potato virus X as a vector, and in stably transformed Arabidopsis thaliana and Lotus japonicus plants. The results show that high level of expression does not interfere with efficient stable transformation in A. thaliana and L. japonicus. Using confocal laser scanning microscopy we show that the fusion constructs are very suitable for promoter expression studies in all organs of living plants, including root nodules. The use of these reporter constructs in the model legume L. japonicus offers exciting new possibilities for the study of the root nodulation process.

  2. Dissolution of pre-existing platelet thrombus by synergistic administration of low concentrations of bifunctional antibodies against β3 integrin.

    Directory of Open Access Journals (Sweden)

    Suying Dang

    Full Text Available Most antithrombotic approaches target prevention rather than the more clinically relevant issue of resolution of an existing thrombus. In this study, we describe a novel and effective therapeutic strategy for ex vivo clearance of pre-existing platelet thrombus by the combination of two bifunctional platelet GPIIIa49-66 ligands that target different parts of the arterial thrombus. We produced an additional GPIIIa49-66 agent (named APAC, which homes to activated platelets. Like our previously described SLK (which targets newly deposited fibrin strands surrounding the platelet thrombus, APAC destroys platelet aggregates ex vivo in an identical fashion with 85% destruction of platelet aggregates at 2 hours. The combined application of APAC and SLK demonstrated a ~2 fold greater platelet thrombus dissolution than either agent alone at a low concentration (0.025 µM. Platelet-rich clot lysis experiments demonstrated the time required for 50% platelet-rich fibrin clot lysis (T(50% by APAC (95 ± 6.1 min or SLK (145 ± 7.1 min was much longer than that by combined APAC + SLK (65 ± 7.6 min at the final concentration of 0.025 µM (APAC + SLK vs APAC, p<0.05; APAC + SLK vs SLK, p<0.01. Thus these low concentrations of a combination of both agents are likely to be more effective and less toxic when used therapeutically in vivo.

  3. Voltammetric determination of Cd2+ based on the bifunctionality of single-walled carbon nanotubes-Nafion film

    International Nuclear Information System (INIS)

    Sun Dong; Xie Xiafeng; Cai Yuepiao; Zhang Huajie; Wu Kangbing

    2007-01-01

    In the presence of Nafion, single-walled carbon nanotubes (SWNTs) were easily dispersed into ethanol, resulting in a homogeneous SWNTs/Nafion suspension. After evaporating ethanol, a SWNTs/Nafion film with bifunctionality was constructed onto glassy carbon electrode (GCE) surface. Attributing to the strong cation-exchange ability of Nafion and excellent properties of SWNTs, the SWNTs/Nafion film-coated GCE remarkably enhances the sensitivity of determination of Cd 2+ . Based on this, an electrochemical method was developed for the determination of trace levels of Cd 2+ by anodic stripping voltammetry (ASV). In pH 5.0 NaAc-HAc buffer, Cd 2+ was firstly exchanged and adsorbed onto SWNTs/Nafion film surface, and then reduce at -1.10 V. During the positive potential sweep, reduced cadmium was oxidized, and a well-defined stripping peak appeared at -0.84 V, which can be used as analytical signal for Cd 2+ . The linear range is found to be from 4.0 x 10 -8 to 4.0 x 10 -6 mol L -1 , and the lowest detectable concentration is estimated to be 4.0 x 10 -9 mol L -1 . Finally, this method was successfully employed to detect Cd 2+ in water samples

  4. Rational geometrical engineering of palladium sulfide multi-arm nanostructures as a superior bi-functional electrocatalyst.

    Science.gov (United States)

    Nandan, R; Nanda, K K

    2017-08-31

    Geometrical tunability offers sharp edges and an open-armed structure accompanied with a high electrochemical active surface area to ensure the efficient and effective utilization of materials by exposing the electrochemical active sites for facile accessibility of reactant species. Herein, we report a one-step, single-pot, surfactant-free, electroless, and economic route to synthesize palladium sulfide nanostructures with different geometries at mild temperatures and their catalytic properties towards the oxygen reduction reaction (ORR) and methanol electro-oxidation (MOR). For ORR, the positive on-set, half wave potentials, smaller Tafel slope, high electrochemical active surface area, large roughness factor, and better cyclic stability of the proposed nanostructures as compared to those of the commercial state-of-the-art Pt-C/PdS catalysts suggest their superiority in an alkaline medium. In addition, high mass activity (J f ∼ 715 mA mg -1 ), in comparison with that of the commercial state-of-the-art Pt-C/PdS catalysts (J f ∼ 138/41 mA mg -1 , respectively), and high J f /J b (1.52) along with the superior operational stability of the multi-arm palladium sulfide nanostructures towards MOR advocates the bi-functional behavior of the catalyst and its potential as a promising Pt-free anode/cathode electrocatalyst in fuel cells.

  5. Crumpled rGO-supported Pt-Ir bifunctional catalyst prepared by spray pyrolysis for unitized regenerative fuel cells

    Science.gov (United States)

    Kim, In Gyeom; Nah, In Wook; Oh, In-Hwan; Park, Sehkyu

    2017-10-01

    Three-dimensional (3D) crumpled reduced graphene oxide supported Pt-Ir alloys that served as bifunctional oxygen catalysts for use in untized regenerative fuel cells were synthesized by a facile spray pyrolysis method. Pt-Ir catalysts supported on rGO (Pt-Ir/rGOs) were physically characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) to observe change in composition by heat treatment, alloying, and morphological transition of the catalysts. Their catalytic activities and stabilities for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) conditions were electrochemically investigated using cyclic voltammetry (CV), linear sweep voltammetry (LSV), potential cycling and hold tests on the rotating disk electrode (RDE). Pt-Ir/rGO with no post heat-treatment (Pt-Ir/rGO_NP) showed a lower activity for ORR and OER although metal nanoparticles decorated on the support are relatively small. However, Pt-Ir/rGO showed remarkably enhanced activity following heat treatment, depending on temperature. Pt-Ir/rGO heat-treated at 600 °C after spray pyrolysis (Pt-Ir/rGO_P600) exhibited a higher activity and stability than a commercially available Pt/C catalyst kept under the ORR condition, and it also revealed a comparable OER activity and durability versus the commercial unsupported Ir catalyst.

  6. Local suppression of contact hypersensitivity in mice by a new bifunctional psoralen, 4,4',5'-trimethylazapsoralen, and UVA radiation.

    Science.gov (United States)

    Aubin, F; Dall'Acqua, F; Kripke, M L

    1991-07-01

    Although psoralens plus UVA radiation (320-400 nm) have been widely used for the treatment of dermatologic diseases, the toxic effects of these agents have led investigators to develop new photochemotherapeutic compounds. One such compound is 4,4',5'-trimethylazapsoralen (TMAP), a new bifunctional molecule. The purpose of this study was to examine the immunologic side effects of repeated treatment of C3H mice with TMAP plus UVA radiation. During this treatment, the number of ATPase+, la+, and Thy-1+ dendritic epidermal cells greatly decreased in the treated site, despite the lack of phototoxicity. The reduction in the number of detectable cutaneous immune cells was accompanied by a decrease in the induction of contact hypersensitivity to dinitrofluorobenzene applied to the treated skin, an impairment in the antigen-presenting activity of draining lymph node cells, and the presence of suppressor lymphoid cells in the spleen of unresponsive mice. Treatment with UVA radiation alone also reduced the number of ATPase+, Ia+, and Thy-1+ cells in the skin, but did not cause any detectable alterations in immune function. This implies that morphologic alterations in these cells do not necessarily indicate loss of function. Thus, although TMAP in combination with UVA radiation is not overtly phototoxic, it is highly immunosuppressive in mice.

  7. Bifunctional viscous nanovesicles co-loaded with resveratrol and gallic acid for skin protection against microbial and oxidative injuries.

    Science.gov (United States)

    Vitonyte, Justina; Manca, Maria Letizia; Caddeo, Carla; Valenti, Donatella; Peris, Josè Esteban; Usach, Iris; Nacher, Amparo; Matos, Maria; Gutiérrez, Gemma; Orrù, Germano; Fernàndez-Busquets, Xavier; Fadda, Anna Maria; Manconi, Maria

    2017-05-01

    Resveratrol and gallic acid were co-loaded in phospholipid vesicles aiming at protecting the skin from external injuries, such as oxidative stress and microbial infections. Liposomes were prepared using biocompatible phospholipids dispersed in water. To improve vesicle stability and applicability, the phospholipids and the phenols were dispersed in water/propylene glycol or water/glycerol, thus obtaining PEVs and glycerosomes, respectively. The vesicles were characterized by size, morphology, physical stability, and their therapeutic efficacy was investigated in vitro. The vesicles were spherical, unilamellar and small in size: liposomes and glycerosomes were around 70nm in diameter, while PEVs were larger (∼170nm). The presence of propylene glycol or glycerol increased the viscosity of the vesicle systems, positively affecting their stability. The ability of the vesicles to promote the accumulation of the phenols (especially gallic acid) in the skin was demonstrated, as well as their low toxicity and great ability to protect keratinocytes and fibroblasts from oxidative damage. Additionally, an improvement of the antimicrobial activity of the phenols was shown against different skin pathogens. The co-loading of resveratrol and gallic acid in modified phospholipid vesicles represents an innovative, bifunctional tool for preventing and treating skin affections. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Mineralization of hetero bi-functional reactive dye in aqueous solution by Fenton and photo-Fenton reactions.

    Science.gov (United States)

    Torrades, Francesc; García-Hortal, José Antonio; García-Montaño, Julia

    2015-01-01

    This study focused on the advanced oxidation of the hetero bi-functional reactive dye Sumifix Supra Yellow 3RF (CI Reactive Yellow 145) using dark Fenton and photo-Fenton conditions in a lab-scale experiment. A 2(3) factorial design was used to evaluate the effects of the three key factors: temperature, Fe(II) and H2O2 concentrations, for a dye concentration of 250 mg L(-1) with chemical oxygen demand (COD) of 172 mg L(-1) O2 at pH=3. The response function was the COD reduction. This methodology lets us find the effects and interactions of the studied variables and their roles in the efficiency of the treatment process. In the optimization, the correlation coefficients for the model (R2) were 0.948 and 0.965 for Fenton and photo-Fenton treatments, respectively. Under optimized reaction conditions: pH=3, temperature=298 K, [H2O2]=11.765 mM and [Fe(II)]=1.075 mM; 60 min of treatment resulted in a 79% and 92.2% decrease in COD, for the dye taken as the model organic compound, after Fenton and photo-Fenton treatments, respectively.

  9. Comparison of the octadentate bifunctional chelator DFO*-pPhe-NCS and the clinically used hexadentate bifunctional chelator DFO-pPhe-NCS for {sup 89}Zr-immuno-PET

    Energy Technology Data Exchange (ETDEWEB)

    Vugts, Danielle J.; Klaver, Chris; Sewing, Claudia; Poot, Alex J.; Adamzek, Kevin; Visser, Gerard W.M.; Dongen, Guus A.M.S. van [VU University Medical Center, Department of Radiology and Nuclear Medicine, Amsterdam (Netherlands); Huegli, Seraina; Mari, Cristina; Gasser, Gilles [University of Zurich, Department of Chemistry, Zurich (Switzerland); Valverde, Ibai E. [University of Basel Hospital, Division of Radiopharmaceutical Chemistry, Basel (Switzerland); Mindt, Thomas L. [Institute of Pharmaceutical Sciences, ETH Zurich, Zurich (Switzerland); General Hospital of Vienna, Ludwig Boltzmann Institute for Applied Diagnostics, Vienna (Austria)

    2017-02-15

    All clinical {sup 89}Zr-immuno-PET studies are currently performed with the chelator desferrioxamine (DFO). This chelator provides hexadentate coordination to zirconium, leaving two coordination sites available for coordination with, e.g., water molecules, which are relatively labile ligands. The unsaturated coordination of DFO to zirconium has been suggested to result in impaired stability of the complex in vivo and consequently in unwanted bone uptake of {sup 89}Zr. Aiming at clinical improvements, we report here on a bifunctional isothiocyanate variant of the octadentate chelator DFO* and the in vitro and in vivo comparison of its {sup 89}Zr-DFO*-mAb complex with {sup 89}Zr-DFO-mAb. The bifunctional chelator DFO*-pPhe-NCS was prepared from previously reported DFO* and p-phenylenediisothiocyanate. Subsequently, trastuzumab was conjugated with either DFO*-pPhe-NCS or commercial DFO-pPhe-NCS and radiolabeled with Zr-89 according to published procedures. In vitro stability experiments were carried out in saline, a histidine/sucrose buffer, and blood serum. The in vivo performance of the chelators was compared in N87 tumor-bearing mice by biodistribution studies and PET imaging. In 0.9 % NaCl {sup 89}Zr-DFO*-trastuzumab was more stable than {sup 89}Zr-DFO-trastuzumab; after 72 h incubation at 2-8 C 95 % and 58 % intact tracer were left, respectively, while in a histidine-sucrose buffer no difference was observed, both products were ≥ 92 % intact. In vivo uptake at 144 h post injection (p.i.) in tumors, blood, and most normal organs was similar for both conjugates, except for skin, liver, spleen, ileum, and bone. Tumor uptake was 32.59 ± 11.95 and 29.06 ± 8.66 % ID/g for {sup 89}Zr-DFO*-trastuzumab and {sup 89}Zr-DFO-trastuzumab, respectively. The bone uptake was significantly lower for {sup 89}Zr-DFO*-trastuzumab compared to {sup 89}Zr-DFO-trastuzumab. At 144 h p.i. for {sup 89}Zr-DFO*-trastuzumab and {sup 89}Zr-DFO-trastuzumab, the uptake in sternum was 0.92

  10. Hierarchically scaffolded CoP/CoP2 nanoparticles: controllable synthesis and their application as a well-matched bifunctional electrocatalyst for overall water splitting.

    Science.gov (United States)

    Li, Wan; Zhang, Shilin; Fan, Qining; Zhang, Fazhi; Xu, Sailong

    2017-05-04

    Transition metal phosphide (TMP) nanostructures have stimulated increasing interest for use in water splitting owing to their abundant natural sources and high activity for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Typically, the preparation of hierarchical TMPs involves the utilization of expensive or dangerous phosphorus sources, and, in particular, the understanding of topotactic transformations of the precursors to crystalline phases-which could be utilized to enhance electrocatalytic performance-remains very limited. We, herein, report a controllable preparation of CoP/CoP 2 nanoparticles well dispersed in flower-like Al 2 O 3 scaffolds (f-CoP/CoP 2 /Al 2 O 3 ) as a bifunctional electrocatalyst for the HER and OER via the phosphorization of a flower-like CoAl layered double hydroxide precursor. Characterization by in situ X-ray diffraction (XRD) monitored the topotactic transformation underlying the controllable formation of CoP/CoP 2 via tuning the phosphorization time. Electrocatalytic tests showed that an f-CoP/CoP 2 /Al 2 O 3 electrode exhibited a lower onset potential and higher electrocatalytic activity for the HER and OER in the same alkaline electrolyte than electrodes of flower-like and powdered CoP/Al 2 O 3 . The enhanced electrochemical performance was experimentally supported by measuring the electrochemically active surface area. The f-CoP/CoP 2 /Al 2 O 3 composite further generated a current density of 10 mA cm -2 at 1.65 V when used as a bifunctional catalyst for overall water splitting. Our results demonstrate that the preparation route based on the LDH precursor may provide an alternative for investigating diverse TMPs as bifunctional electrocatalysts for water splitting.

  11. Evolution of Conifer Diterpene Synthases: Diterpene Resin Acid Biosynthesis in Lodgepole Pine and Jack Pine Involves Monofunctional and Bifunctional Diterpene Synthases1[W][OA

    Science.gov (United States)

    Hall, Dawn E.; Zerbe, Philipp; Jancsik, Sharon; Quesada, Alfonso Lara; Dullat, Harpreet; Madilao, Lina L.; Yuen, Macaire; Bohlmann, Jörg

    2013-01-01

    Diterpene resin acids (DRAs) are major components of pine (Pinus spp.) oleoresin. They play critical roles in conifer defense against insects and pathogens and as a renewable resource for industrial bioproducts. The core structures of DRAs are formed in secondary (i.e. specialized) metabolism via cycloisomerization of geranylgeranyl diphosphate (GGPP) by diterpene synthases (diTPSs). Previously described gymnosperm diTPSs of DRA biosynthesis are bifunctional enzymes that catalyze the initial bicyclization of GGPP followed by rearrangement of a (+)-copalyl diphosphate intermediate at two discrete class II and class I active sites. In contrast, similar diterpenes of gibberellin primary (i.e. general) metabolism are produced by the consecutive activity of two monofunctional class II and class I diTPSs. Using high-throughput transcriptome sequencing, we discovered 11 diTPS from jack pine (Pinus banksiana) and lodgepole pine (Pinus contorta). Three of these were orthologous to known conifer bifunctional levopimaradiene/abietadiene synthases. Surprisingly, two sets of orthologous PbdiTPSs and PcdiTPSs were monofunctional class I enzymes that lacked functional class II active sites and converted (+)-copalyl diphosphate, but not GGPP, into isopimaradiene and pimaradiene as major products. Diterpene profiles and transcriptome sequences of lodgepole pine and jack pine are consistent with roles for these diTPSs in DRA biosynthesis. The monofunctional class I diTPSs of DRA biosynthesis form a new clade within the gymnosperm-specific TPS-d3 subfamily that evolved from bifunctional diTPS rather than monofunctional enzymes (TPS-c and TPS-e) of gibberellin metabolism. Homology modeling suggested alterations in the class I active site that may have contributed to their functional specialization relative to other conifer diTPSs. PMID:23370714

  12. Evolution of conifer diterpene synthases: diterpene resin acid biosynthesis in lodgepole pine and jack pine involves monofunctional and bifunctional diterpene synthases.

    Science.gov (United States)

    Hall, Dawn E; Zerbe, Philipp; Jancsik, Sharon; Quesada, Alfonso Lara; Dullat, Harpreet; Madilao, Lina L; Yuen, Macaire; Bohlmann, Jörg

    2013-02-01

    Diterpene resin acids (DRAs) are major components of pine (Pinus spp.) oleoresin. They play critical roles in conifer defense against insects and pathogens and as a renewable resource for industrial bioproducts. The core structures of DRAs are formed in secondary (i.e. specialized) metabolism via cycloisomerization of geranylgeranyl diphosphate (GGPP) by diterpene synthases (diTPSs). Previously described gymnosperm diTPSs of DRA biosynthesis are bifunctional enzymes that catalyze the initial bicyclization of GGPP followed by rearrangement of a (+)-copalyl diphosphate intermediate at two discrete class II and class I active sites. In contrast, similar diterpenes of gibberellin primary (i.e. general) metabolism are produced by the consecutive activity of two monofunctional class II and class I diTPSs. Using high-throughput transcriptome sequencing, we discovered 11 diTPS from jack pine (Pinus banksiana) and lodgepole pine (Pinus contorta). Three of these were orthologous to known conifer bifunctional levopimaradiene/abietadiene synthases. Surprisingly, two sets of orthologous PbdiTPSs and PcdiTPSs were monofunctional class I enzymes that lacked functional class II active sites and converted (+)-copalyl diphosphate, but not GGPP, into isopimaradiene and pimaradiene as major products. Diterpene profiles and transcriptome sequences of lodgepole pine and jack pine are consistent with roles for these diTPSs in DRA biosynthesis. The monofunctional class I diTPSs of DRA biosynthesis form a new clade within the gymnosperm-specific TPS-d3 subfamily that evolved from bifunctional diTPS rather than monofunctional enzymes (TPS-c and TPS-e) of gibberellin metabolism. Homology modeling suggested alterations in the class I active site that may have contributed to their functional specialization relative to other conifer diTPSs.

  13. Fe2.25W0.75O4/reduced graphene oxide nanocomposites for novel bifunctional photocatalyst: One-pot synthesis, magnetically recyclable and enhanced photocatalytic property

    International Nuclear Information System (INIS)

    Guo, Jinxue; Jiang, Bin; Zhang, Xiao; Zhou, Xiaoyu; Hou, Wanguo

    2013-01-01

    Fe 2.25 W 0.75 O 4 /reduced graphene oxide (RGO) composites were prepared for application of novel bifunctional photocatalyst via simple one-pot hydrothermal method, employing graphene oxide (GO), Na 2 WO 4 , FeSO 4 and sodium dodecyl benzene sulfonate (SDBS) as the precursors. Transmission electron microscope (TEM) results indicate that the well-dispersed Fe 2.25 W 0.75 O 4 nanoparticles were deposited on the surface of RGO sheets homogeneously. Magnetic characterization reveals that Fe 2.25 W 0.75 O 4 and Fe 2.25 W 0.75 O 4 /RGO show ferromagnetic behaviors. So this novel bifunctional photocatalyst could achieve magnetic separation and collection with the aid of external magnet. The composites exhibit enhanced photocatalytic performance on degradation of methyl orange (MO) compared with pure Fe 2.25 W 0.75 O 4 under low-power ultraviolet light irradiation due to the introduction of RGO. Moreover, this hybrid catalyst possesses long-term excellent photocatalytic performance due to its good thermal stability. This bifunctional photocatalyst, which combines magnetic property and excellent photocatalytic activity, would be a perfect candidate in applications of catalytic elimination of environmental pollutants and other areas. - Graphical abstract: Magnetically recyclable Fe 2.25 W 0.75 O 4 /reduced graphene oxide nanocomposites with enhanced photocatalytic property Display Omitted - Highlights: ●Fe 2.25 W 0.75 O 4 growth, deposition and GO reduction occurred simultaneously. ●Composite possessed ferromagnetic and enhanced photocatalytic properties. ●Composite is utilized as a magnetically separable and high-efficient photocatalyst. ●Photocatalyst showed good photocatalytic and thermal stability during cyclic use

  14. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

    DEFF Research Database (Denmark)

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela Costinela

    2012-01-01

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen...... reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn2O3 and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V...

  15. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  16. Single-Site Active Iron-Based Bifunctional Oxygen Catalyst for a Compressible and Rechargeable Zinc-Air Battery.

    Science.gov (United States)

    Ma, Longtao; Chen, Shengmei; Pei, Zengxia; Huang, Yan; Liang, Guojin; Mo, Funian; Yang, Qi; Su, Jun; Gao, Yihua; Zapien, Juan Antonio; Zhi, Chunyi

    2018-02-27

    The exploitation of a high-efficient, low-cost, and stable non-noble-metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for a rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersion of an Fe-N x species on a two-dimensional (2D) highly graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an overpotential of 390 mV at 10 mA·cm -2 for OER) in an alkaline medium. Furthermore, an elastic polyacrylamide hydrogel based electrolyte with the capability to retain great elasticity even under a highly corrosive alkaline environment is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery has a low charge-discharge voltage gap (0.78 V at 5 mA·cm -2 ) and large power density (118 mW·cm -2 ). It could be compressed up to 54% strain and bent up to 90° without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on a porous support for a bifunctional oxygen catalyst as cathode integrating a specially designed elastic electrolyte is a feasible strategy for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

  17. Bifunctional bamboo-like CoSe2 arrays for high-performance asymmetric supercapacitor and electrocatalytic oxygen evolution

    Science.gov (United States)

    Chen, Tian; Li, Songzhan; Gui, Pengbin; Wen, Jian; Fu, Xuemei; Fang, Guojia

    2018-05-01

    Bifunctional bamboo-like CoSe2 arrays are synthesized by thermal annealing of Co(CO3)0.5OH grown on carbon cloth in Se atmosphere. The CoSe2 arrays obtained have excellent electrical conductivity, larger electrochemical active surface areas, and can directly serve as a binder-free electrode for supercapacitors and the oxygen evolution reaction (OER). When tested as a supercapacitor electrode, the CoSe2 delivers a higher specific capacitance (544.6 F g‑1 at current density of 1 mA cm‑2) compared with CoO (308.2 F g‑1) or Co3O4 (201.4 F g‑1). In addition, the CoSe2 electrode possesses excellent cycling stability. An asymmetric supercapacitor (ASC) is also assembled based on bamboo-like CoSe2 as a positive electrode and active carbon as a negative electrode in a 3.0 M KOH aqueous electrolyte. Owing to the unique stucture and good electrochemical performance of bamboo-like CoSe2, the as-assembled ACS can achieve a maximum operating voltage window of 1.7 V, a high energy density of 20.2 Wh kg‑1 at a power density of 144.1 W kg‑1, and an outstanding cyclic stability. As the catalyst for the OER, the CoSe2 exhibits a lower potential of 1.55 V (versus RHE) at current density of 10 mA cm‑2, a smaller Tafel slope of 62.5 mV dec‑1 and an also outstanding stability.

  18. Removing organic contaminants with bifunctional iron modified rectorite as efficient adsorbent and visible light photo-Fenton catalyst

    International Nuclear Information System (INIS)

    Zhao, Xiaorong; Zhu, Lihua; Zhang, Yingying; Yan, Jingchun; Lu, Xiaohua; Huang, Yingping; Tang, Heqing

    2012-01-01

    Highlights: ► Rectorite was modified by ultrasonic-assisted ion-exchange and hydrolysis. ► The pillaring increased the layer-to-layer spacing of rectorite. ► The iron-modified rectorite was found to be an excellent adsorbent. ► The iron-modified rectorite showed good visible light photocatalytic ability. ► FeR was highly chemically stable with a wide operating range of pH. - Abstract: Iron-modified rectorite (FeR) was prepared as both adsorbent and catalyst. The iron modification increased layer-to-layer spacing and surface area of rectorite, leading to much increased adsorption of Rhodamine B (RhB) on rectorite. The maximum adsorption capacity of RhB on FeR reached 101 mg g −1 at pH 4.5, being 11 folds of that on the unmodified one. The iron modification also enabled rectorite to have efficient visible light photocatalytic ability. The apparent rate constant for the degradation of RhB (80 μM) at 298 K and pH 4.5 in the presence of H 2 O 2 (6.0 mM) and FeR (0.4 g L −1 ) was evaluated to be 0.0413 min −1 under visible light and 0.122 min −1 under sunlight, respectively. The analysis with electron spin resonance spin-trapping technique supported that the iron modified rectorite effectively catalyzed the decomposition of H 2 O 2 into hydroxyl radicals. On the basis of the characterization and analysis, the new bifunctional material was well clarified as both adsorbent and photocatalyst in the removing of organic pollutants.

  19. Cell tracking with gadophrin-2: a bifunctional contrast agent for MR imaging, optical imaging, and fluorescence microscopy

    International Nuclear Information System (INIS)

    Daldrup-Link, Heike E.; Rudelius, Martina; Piontek, Guido; Schlegel, Juergen; Metz, Stephan; Settles, Marcus; Rummeny, Ernst J.; Pichler, Bernd; Heinzmann, Ulrich; Oostendorp, Robert A.J.

    2004-01-01

    The purpose of this study was to assess the feasibility of use of gadophrin-2 to trace intravenously injected human hematopoietic cells in athymic mice, employing magnetic resonance (MR) imaging, optical imaging (OI), and fluorescence microscopy. Mononuclear peripheral blood cells from GCSF-primed patients were labeled with gadophrin-2 (Schering AG, Berlin, Germany), a paramagnetic and fluorescent metalloporphyrin, using established transfection techniques with cationic liposomes. The labeled cells were evaluated in vitro with electron microscopy and inductively coupled plasma atomic emission spectrometry. Then, 1 x 10 6 -3 x 10 8 labeled cells were injected into 14 nude Balb/c mice and the in vivo cell distribution was evaluated with MR imaging and OI before and 4, 24, and 48 h after intravenous injection (p.i.). Five additional mice served as controls: three mice were untreated controls and two mice were investigated after injection of unlabeled cells. The contrast agent effect was determined quantitatively for MR imaging by calculating signal-to-noise-ratio (SNR) data. After completion of in vivo imaging studies, fluorescence microscopy of excised organs was performed. Intracellular cytoplasmatic uptake of gadophrin-2 was confirmed by electron microscopy. Spectrometry determined an uptake of 31.56 nmol Gd per 10 6 cells. After intravenous injection, the distribution of gadophrin-2 labeled cells in nude mice could be visualized by MR, OI, and fluorescence microscopy. At 4 h p.i., the transplanted cells mainly distributed to lung, liver, and spleen, and 24 h p.i. they also distributed to the bone marrow. Fluorescence microscopy confirmed the distribution of gadophrin-2 labeled cells to these target organs. Gadophrin-2 is suited as a bifunctional contrast agent for MR imaging, OI, and fluorescence microscopy and may be used to combine the advantages of each individual imaging modality for in vivo tracking of intravenously injected hematopoietic cells. (orig.)

  20. Tri-domain Bifunctional Inhibitor of Metallocarboxypeptidases A and Serine Proteases Isolated from Marine Annelid Sabellastarte magnifica*

    Science.gov (United States)

    Alonso-del-Rivero, Maday; Trejo, Sebastian A.; Reytor, Mey L.; Rodriguez-de-la-Vega, Monica; Delfin, Julieta; Diaz, Joaquin; González-González, Yamile; Canals, Francesc; Chavez, Maria Angeles; Aviles, Francesc X.

    2012-01-01

    This study describes a novel bifunctional metallocarboxypeptidase and serine protease inhibitor (SmCI) isolated from the tentacle crown of the annelid Sabellastarte magnifica. SmCI is a 165-residue glycoprotein with a molecular mass of 19.69 kDa (mass spectrometry) and 18 cysteine residues forming nine disulfide bonds. Its cDNA was cloned and sequenced by RT-PCR and nested PCR using degenerated oligonucleotides. Employing this information along with data derived from automatic Edman degradation of peptide fragments, the SmCI sequence was fully characterized, indicating the presence of three bovine pancreatic trypsin inhibitor/Kunitz domains and its high homology with other Kunitz serine protease inhibitors. Enzyme kinetics and structural analyses revealed SmCI to be an inhibitor of human and bovine pancreatic metallocarboxypeptidases of the A-type (but not B-type), with nanomolar Ki values. SmCI is also capable of inhibiting bovine pancreatic trypsin, chymotrypsin, and porcine pancreatic elastase in varying measures. When the inhibitor and its nonglycosylated form (SmCI N23A mutant) were overproduced recombinantly in a Pichia pastoris system, they displayed the dual inhibitory properties of the natural form. Similarly, two bi-domain forms of the inhibitor (recombinant rSmCI D1-D2 and rSmCI D2-D3) as well as its C-terminal domain (rSmCI-D3) were also overproduced. Of these fragments, only the rSmCI D1-D2 bi-domain retained inhibition of metallocarboxypeptidase A but only partially, indicating that the whole tri-domain structure is required for such capability in full. SmCI is the first proteinaceous inhibitor of metallocarboxypeptidases able to act as well on another mechanistic class of proteases (serine-type) and is the first of this kind identified in nature. PMID:22411994

  1. Cloning, functional expression and characterization of a bifunctional 3-hydroxybutanal dehydrogenase /reductase involved in acetone metabolism by Desulfococcus biacutus.

    Science.gov (United States)

    Frey, Jasmin; Rusche, Hendrik; Schink, Bernhard; Schleheck, David

    2016-11-25

    The strictly anaerobic, sulfate-reducing bacterium Desulfococcus biacutus can utilize acetone as sole carbon and energy source for growth. Whereas in aerobic and nitrate-reducing bacteria acetone is activated by carboxylation with CO 2 to acetoacetate, D. biacutus involves CO as a cosubstrate for acetone activation through a different, so far unknown pathway. Proteomic studies indicated that, among others, a predicted medium-chain dehydrogenase/reductase (MDR) superfamily, zinc-dependent alcohol dehydrogenase (locus tag DebiaDRAFT_04514) is specifically and highly produced during growth with acetone. The MDR gene DebiaDRAFT_04514 was cloned and overexpressed in E. coli. The purified recombinant protein required zinc as cofactor, and accepted NADH/NAD + but not NADPH/NADP + as electron donor/acceptor. The pH optimum was at pH 8, and the temperature optimum at 45 °C. Highest specific activities were observed for reduction of C 3 - C 5 -aldehydes with NADH, such as propanal to propanol (380 ± 15 mU mg -1 protein), butanal to butanol (300 ± 24 mU mg -1 ), and 3-hydroxybutanal to 1,3-butanediol (248 ± 60 mU mg -1 ), however, the enzyme also oxidized 3-hydroxybutanal with NAD + to acetoacetaldehyde (83 ± 18 mU mg -1 ). The enzyme might play a key role in acetone degradation by D. biacutus, for example as a bifunctional 3-hydroxybutanal dehydrogenase/reductase. Its recombinant production may represent an important step in the elucidation of the complete degradation pathway.

  2. Hydro-isomerization of n-hexane on bi-functional catalyst: Effect of total and hydrogen partial pressures

    Science.gov (United States)

    Thoa, Dao Thi Kim; Loc, Luu Cam

    2017-09-01

    The effect of both total pressure and hydrogen partial pressure during n-hexane hydro-isomerization over platinum impregnated on HZSM-5 was studied. n-Hexane hydro-isomerization was conducted at atmospheric pressure and 0.7 MPa to observe the influence of total pressure. In order to see the effect of hydrogen partial pressure, the reaction was taken place at different partial pressure of hydrogen varied from 307 hPa to 718 hPa by dilution with nitrogen to keep the total pressure at 0.1 MPa. Physico-chemical characteristics of catalyst were determined by the methods of nitrogen physi-sorption BET, SEM, XRD, TEM, NH3-TPD, TPR, and Hydrogen Pulse Chemi-sorption. Activity of catalyst in the hydro-isomerization of n-hexane was studied in a micro-flow reactor in the temperature range of 225-325 °C; the molar ratio H2/ hydrocarbon: 5.92, concentration of n-hexane: 9.2 mol.%, GHSV 2698 h-1. The obtained catalyst expressed high acid density, good reducing property, high metal dispersion, and good balance between metallic and acidic sites. It is excellent contact for n-hexane hydro-isomerization. At 250 °C, n-hexane conversion and selectivity were as high as 59-76 % and 85-99 %, respectively. It was found that catalytic activity was promoted either by total pressure or hydrogen partial pressure. At total pressure of 0.7 MPa while hydrogen partial pressure of 718 hPa, catalyst produced 63 RON liquid product containing friendly environmental iso-paraffins which is superior blending stock for green gasoline. Hydrogen did not only preserve catalyst actives by depressing hydrocracking and removing coke precursors but also facilitated hydride transfer step in the bi-functional bi-molecular mechanism.

  3. The bifunctional plant receptor, OsCERK1, regulates both chitin-triggered immunity and arbuscular mycorrhizal symbiosis in rice.

    Science.gov (United States)

    Miyata, Kana; Kozaki, Toshinori; Kouzai, Yusuke; Ozawa, Kenjirou; Ishii, Kazuo; Asamizu, Erika; Okabe, Yoshihiro; Umehara, Yosuke; Miyamoto, Ayano; Kobae, Yoshihiro; Akiyama, Kohki; Kaku, Hanae; Nishizawa, Yoko; Shibuya, Naoto; Nakagawa, Tomomi

    2014-11-01

    Plants are constantly exposed to threats from pathogenic microbes and thus developed an innate immune system to protect themselves. On the other hand, many plants also have the ability to establish endosymbiosis with beneficial microbes such as arbuscular mycorrhizal (AM) fungi or rhizobial bacteria, which improves the growth of host plants. How plants evolved these systems managing such opposite plant-microbe interactions is unclear. We show here that knockout (KO) mutants of OsCERK1, a rice receptor kinase essential for chitin signaling, were impaired not only for chitin-triggered defense responses but also for AM symbiosis, indicating the bifunctionality of OsCERK1 in defense and symbiosis. On the other hand, a KO mutant of OsCEBiP, which forms a receptor complex with OsCERK1 and is essential for chitin-triggered immunity, established mycorrhizal symbiosis normally. Therefore, OsCERK1 but not chitin-triggered immunity is required for AM symbiosis. Furthermore, experiments with chimeric receptors showed that the kinase domains of OsCERK1 and homologs from non-leguminous, mycorrhizal plants could trigger nodulation signaling in legume-rhizobium interactions as the kinase domain of Nod factor receptor1 (NFR1), which is essential for triggering the nodulation program in leguminous plants, did. Because leguminous plants are believed to have developed the rhizobial symbiosis on the basis of AM symbiosis, our results suggest that the symbiotic function of ancestral CERK1 in AM symbiosis enabled the molecular evolution to leguminous NFR1 and resulted in the establishment of legume-rhizobia symbiosis. These results also suggest that OsCERK1 and homologs serve as a molecular switch that activates defense or symbiotic responses depending on the infecting microbes. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  4. A new approach in the preparation of dendrimer-based bifunctional diethylenetriaminepentaacetic acid MR contrast agent derivatives.

    Science.gov (United States)

    Nwe, Kido; Xu, Heng; Regino, Celeste Aida S; Bernardo, Marcelino; Ileva, Lilia; Riffle, Lisa; Wong, Karen J; Brechbiel, Martin W

    2009-07-01

    In this paper, we report a new method to prepare and characterize a contrast agent based on a fourth-generation (G4) polyamidoamine (PAMAM) dendrimer conjugated to the gadolinium complex of the bifunctional diethylenetriamine pentaacetic acid derivative (1B4M-DTPA). The method involves preforming the metal-ligand chelate in alcohol prior to conjugation to the dendrimer. The dendrimer-based agent was purified by a Sephadex G-25 column and characterized by elemental analysis. The analysis and SE-HPLC data gave a chelate to dendrimer ratio of 30:1 suggesting conjugation at approximately every other amine terminal on the dendrimer. Molar relaxivity of the agent measured at pH 7.4 displayed a higher value than that of the analogous G4 dendrimer based agent prepared by the postmetal incorporation method (r(1) = 26.9 vs 13.9 mM(-1) s(-1) at 3 T and 22 degrees C). This is hypothesized to be due to the higher hydrophobicity of this conjugate and the lack of available charged carboxylate groups from noncomplexed free ligands that might coordinate to the metal and thus also reduce water exchange sites. Additionally, the distribution populations of compounds that result from the postmetal incorporation route are eliminated from the current product simplifying characterization as quality control issues pertaining to the production of such agents for clinical use as MR contrast agents. In vivo imaging in mice showed a reasonably fast clearance (t(1/2) = 24 min) suggesting a viable agent for use in clinical application.

  5. Two interpenetrating Cu{sup II}/Ni{sup II}-coordinated polymers based on an unsymmetrical bifunctional N/O-tectonic: Syntheses, structures and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yong-Liang [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Department of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shang Luo University, Shang Luo 726000 (China); Wu, Ya-Pan [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Dong, Wen-Wen [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Zhou, Chun-Sheng [Department of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shang Luo University, Shang Luo 726000 (China)

    2015-03-15

    Two new interpenetrating Cu{sup II}/Ni{sup II} coordination polymers, based on a unsymmetrical bifunctional N/O-tectonic 3-(pyrid-4′-yl)-5-(4″-carbonylphenyl)-1,2,4-triazolyl (H{sub 2}pycz), ([Cu-(Hpycz){sub 2}]·2H{sub 2}O){sub n} (1) and ([Ni(Hpycz){sub 2}]·H{sub 2}O){sub n} (2), have been solvothermally synthesized and structure characterization. Single crystal X-ray analysis indicates that compound 1 shows 2-fold parallel interpenetrated 4{sup 4}-sql layers with the same handedness. The overall structure of 1 is achiral—in each layer of doubly interpenetrating nets, the two individual nets have the opposite handedness to the corresponding nets in the adjoining layers—while 2 features a rare 8-fold interpenetrating 6{sup 6}-dia network that belongs to class IIIa interpenetration. In addition, compounds 1 and 2 both show similar paramagnetic characteristic properties. - Graphical abstract: Two new Cu(II)/Ni(II) coordination polymers present 2D parallel 2-fold interpenetrated 4{sup 4}-sql layers and a rare 3D 8-fold interpenetrating 6{sup 6}-dia network. In addition, magnetic susceptibility measurements show similar paramagnetic characteristic for two complexes. - Highlights: • A new unsymmetrical bifunctional N/O-tectonic as 4-connected spacer. • A 2-fold parallel interpenetrated sql layer with the same handedness. • A rare 8-fold interpenetrating dia network (class IIIa)

  6. Ni/CdS bifunctional Ti@TiO2 core-shell nanowire electrode for high-performance nonenzymatic glucose sensing.

    Science.gov (United States)

    Guo, Chunyan; Huo, Huanhuan; Han, Xu; Xu, Cailing; Li, Hulin

    2014-01-07

    In this work, a Ni/CdS bifunctional Ti@TiO2 core-shell nanowire electrode with excellent electrochemical sensing property was successfully constructed through a hydrothermal and electrodeposition method. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) were employed to confirm the synthesis and characterize the morphology of the as-prepared samples. The results revealed that the CdS layer between Ni and TiO2 plays an important role in the uniform nucleation and the following growth of highly dispersive Ni nanoparticle on the Ti@TiO2 core-shell nanowire surface. The bifunctional nanostructured electrode was applied to construct an electrochemical nonenzymatic sensor for the reliable detection of glucose. Under optimized conditions, this nonenzymatic glucose sensor displayed a high sensitivity up to 1136.67 μA mM(-1) cm(-2), a wider liner range of 0.005-12 mM, and a lower detection limit of 0.35 μM for glucose oxidation. The high dispersity of Ni nanoparticles, combined with the anti-poisoning faculty against the intermediate derived from the self-cleaning ability of CdS under the photoexcitation, was considered to be responsible for these enhanced electrochemical performances. Importantly, favorable reproducibility and long-term performance were also obtained thanks to the robust frameworks. All these results indicate this novel electrode is a promising candidate for nonenzymatic glucose sensing.

  7. Induction of 26S proteasome subunit PSMB5 by the bifunctional inducer 3-methylcholanthrene through the Nrf2-ARE, but not the AhR/Arnt-XRE, pathway

    International Nuclear Information System (INIS)

    Kwak, Mi-Kyoung; Kensler, Thomas W.

    2006-01-01

    The 26S proteasome is responsible for degradation of abnormal intracellular proteins, including oxidatively damaged proteins and may play a role as a component of a cellular antioxidative system. However, little is known about regulation of proteasome expression. In the present study, regulation of proteasome expression by the bifunctional enzyme inducer and a specific signaling pathway for this regulation were investigated in murine neuroblastoma cells. Expression of catalytic core subunits including PSMB5 and peptidase activities of the proteasome were elevated following incubation with 3-methylcholanthrene (3-MC). Studies using reporter genes containing the murine Psmb5 promoter showed that transcriptional activity of this gene was enhanced by 3-MC. Overexpression of AhR/Arnt did not affect activation of the Pmsb5 promoter by 3-MC and deletion of the xenobiotic response elements (XREs) from this promoter exerted modest effects on inducibility in response to 3-MC. However, mutation of the proximal AREs of the Psmb5 promoter largely abrogated its inducibility by 3-MC. In addition, this promoter showed a blunted response toward 3-MC in the absence of nrf2; 3-MC incubation increased nuclear levels of Nrf2 only in wild-type cells. Collectively, these results indicate that expression of proteasome subunit PSMB5 is modulated by bifunctional enzyme inducers in a manner independent of the AhR/Arnt-XRE pathway but dependent upon the Nrf2-ARE pathway

  8. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

    Science.gov (United States)

    Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

    2017-04-22

    The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2 O 3 and HY zeolite. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Homogeneous and label-free detection of microRNAs using bifunctional strand displacement amplification-mediated hyperbranched rolling circle amplification.

    Science.gov (United States)

    Zhang, Li-rong; Zhu, Guichi; Zhang, Chun-yang

    2014-07-01

    MicroRNAs (miRNAs) are an emerging class of biomarkers and therapeutic targets for various diseases including cancers. Here, we develop a homogeneous and label-free method for sensitive detection of let-7a miRNA based on bifunctional strand displacement amplification (SDA)-mediated hyperbranched rolling circle amplification (HRCA). The binding of target miRNA with the linear template initiates the bifunctional SDA reaction, generating two different kinds of triggers which can hybridize with the linear template to initiate new rounds of SDA reaction for the production of more and more triggers. In the meantime, the released two different kinds of triggers can function as the first and the second primers, respectively, to initiate the HRCA reaction whose products can be simply monitored by a standard fluorometer with SYBR Green I as the fluorescent indicator. The proposed method exhibits high sensitivity with a detection limit of as low as 1.8 × 10(-13) M and a large dynamic range of 5 orders of magnitude from 0.1 pM to 10 nM, and it can even discriminate the single-base difference among the miRNA family members. Moreover, this method can be used to analyze the total RNA samples from the human lung tissues and might be further applied for sensitive detection of various proteins, small molecules, and metal ions in combination with specific aptamers.

  10. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Ruan, Hao [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Feng, Maoqi [Chemistry & Chemical Engineering Division, Southwest Research Institute, San Antonio TX 78238 USA; Qin, Yuling [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Job, Heather [Pacific Northwest National Laboratory, 902 Battelle Blvd Richland WA 99354 USA; Luo, Langli [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Wang, Chongmin [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Kuhn, Erik [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Chen, Xiaowen [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-03-16

    The synthesis of high-efficiency and low-cost multifunctional catalysts for hydrodeoxygenation (HDO) of waste lignin into advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low molecular weight gaseous side-products. Among all the prepared catalysts, Ru-Cu/HY showed the best HDO performance, giving the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably due to the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all the bifunctional catalysts were proven to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite, and this could be attributed to the “intimacy criterion”. The practical use of the designed catalysts would be promising in lignin valorization.

  11. Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?

    International Nuclear Information System (INIS)

    Dub, Pavel; Gordon, John Cameron; Scott, Brian Lindley

    2017-01-01

    Molecular metal/NH bifunctional Noyori-type catalysts are remarkable in that they are among the most efficient artificial catalysts developed to date for the hydrogenation of carbonyl functionalities (loadings up to ~10 –5 mol %). In addition, these catalysts typically exhibit high C=O/C=C chemo- and enantioselectivities. This unique set of properties is traditionally associated with the operation of an unconventional mechanism for homogeneous catalysts in which the chelating ligand plays a key role in facilitating the catalytic reaction and enabling the aforementioned selectivities by delivering/accepting a proton (H + ) via its N–H bond cleavage/formation. A recently revised mechanism of the Noyori hydrogenation reaction (Dub, P. A. et al. J. Am. Chem. Soc. 2014, 136, 3505) suggests that the N–H bond is not cleaved but serves to stabilize the turnover-determining transition states (TDTSs) via strong N–H···O hydrogen-bonding interactions (HBIs). Here, the present paper shows that this is consistent with the largely ignored experimental fact that alkylation of the N–H functionality within M/NH bifunctional Noyori-type catalysts leads to detrimental catalytic activity. Finally, the purpose of this work is to demonstrate that decreasing the strength of this HBI, ultimately to the limit of its complete absence, are conditions under which the same alkylation may lead to beneficial catalytic activity.

  12. Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography

    DEFF Research Database (Denmark)

    Baier, Sina; Damsgaard, Christian Danvad; Klumpp, Michael

    2017-01-01

    When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesi...

  13. Characterization of Bifunctional Spin Labels for Investigating the Structural and Dynamic Properties of Membrane Proteins Using EPR Spectroscopy.

    Science.gov (United States)

    Sahu, Indra D; Craig, Andrew F; Dunagum, Megan M; McCarrick, Robert M; Lorigan, Gary A

    2017-10-05

    Site-directed spin labeling (SDSL) coupled with electron paramagnetic resonance (EPR) spectroscopy is a very powerful technique to study structural and dynamic properties of membrane proteins. The most widely used spin label is methanthiosulfonate (MTSL). However, the flexibility of this spin label introduces greater uncertainties in EPR measurements obtained for determining structures, side-chain dynamics, and backbone motion of membrane protein systems. Recently, a newer bifunctional spin label (BSL), 3,4-bis(methanethiosulfonylmethyl)-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrol-1-yloxy, has been introduced to overcome the dynamic limitations associated with the MTSL spin label and has been invaluable in determining protein backbone dynamics and inter-residue distances due to its restricted internal motion and fewer size restrictions. While BSL has been successful in providing more accurate information about the structure and dynamics of several proteins, a detailed characterization of the spin label is still lacking. In this study, we characterized BSLs by performing CW-EPR spectral line shape analysis as a function of temperature on spin-labeled sites inside and outside of the membrane for the integral membrane protein KCNE1 in POPC/POPG lipid bilayers and POPC/POPG lipodisq nanoparticles. The experimental data revealed a powder pattern spectral line shape for all of the KCNE1-BSL samples at 296 K, suggesting the motion of BSLs approaches the rigid limit regime for these series of samples. BSLs were further utilized to report for the first time the distance measurement between two BSLs attached on an integral membrane protein KCNE1 in POPC/POPG lipid bilayers at room temperature using dipolar line broadening CW-EPR spectroscopy. The CW dipolar line broadening EPR data revealed a 15 ± 2 Å distance between doubly attached BSLs on KCNE1 (53/57-63/67) which is consistent with molecular dynamics modeling and the solution NMR structure of KCNE1 which yielded a

  14. TCNQ-induced in-situ electrochemical deposition for the synthesis of silver nanodendrites as efficient bifunctional electrocatalysts

    International Nuclear Information System (INIS)

    Chen, Zhengyan; Li, Congling; Ni, Yangyang; Kong, Fantao; Zhang, Yongbo; Kong, Aiguo; Shan, Yongkui

    2017-01-01

    Graphical abstract: Silver nanodendrites with superior electrocatalytic activity for oxygen reduction reaction (ORR) and hydrogen peroxide detection were synthesized by electrodeposition method using organic semiconductor 7,7,8,8-tetracyanoquinodimethane (TCNQ) as the inducer. - Highlights: • AgNDs were obtained by electrodepositing route under the induction of TCNQ. • The AgNDs-TCNQ/GCE showed superior activity comparable to Pt/C for ORR. • The AgNDs-TCNQ/GCE exhibited highly catalytic activity toward H_2O_2 detection. • A novel pathway for synthesizing bifunctional Ag-based electrocatalyst. - Abstract: Sliver (Ag) nanodendrites (AgNDs) directly growing on the glassy carbon electrode (GCE) were obtained by an in-situ electrodepositing route under the induction of organic semiconductor 7,7,8,8-tetracyanoquinodimethane (TCNQ). The morphology of the Ag nanostructures can be controlled by the electrodepositing time, applied potentials, and the concentrations of Ag ions. The AgNDs/TCNQ/GCE obtained at the optimized conditions displays the oxygen reduction reaction (ORR) onset potential of 0.98 V, which is the same as that over Pt/C-JM catalyst (0.98 V). It demonstrated that AgNDs possessed the highest electrocatalytic activity for ORR among the various Ag-based electrocatalysts reported in literature in alkaline electrolyte. At the same time, the performance of AgNDs/TCNQ/GCE toward hydrogen peroxide detection was investigated in a range of the concentration from 10 μM to 17 mM. It also showed the higher catalytic activity for hydrogen peroxide reduction reaction with the hydrogen peroxide detection limit reaching 0.47 μM level. The Tafel polarization curve, electrochemically active surface area, and the electrochemical impedance were measured to understand and explore the catalytic behavior of the prepared AgNDs/TCNQ/GCE. The enhanced performance of AgNDs for ORR and hydrogen peroxide detection can be ascribed to the special tree-like morphology with highly

  15. Bifunctional alkylating agent-mediated MGMT-DNA cross-linking and its proteolytic cleavage in 16HBE cells

    International Nuclear Information System (INIS)

    Cheng, Jin; Ye, Feng; Dan, Guorong; Zhao, Yuanpeng; Wang, Bin; Zhao, Jiqing; Sai, Yan; Zou, Zhongmin

    2016-01-01

    Nitrogen mustard (NM), a bifunctional alkylating agent (BAA), contains two alkyl arms and can act as a cross-linking bridge between DNA and protein to form a DNA-protein cross-link (DPC). O 6 -methylguanine–DNA methyltransferase (MGMT), a DNA repair enzyme for alkyl adducts removal, is found to enhance cell sensitivity to BAAs and to promote damage, possibly due to its stable covalent cross-linking with DNA mediated by BAAs. To investigate MGMT-DNA cross-link (mDPC) formation and its possible dual roles in NM exposure, human bronchial epithelial cell line 16HBE was subjected to different concentrations of HN2, a kind of NM, and we found mDPC was induced by HN2 in a concentration-dependent manner, but the mRNA and total protein of MGMT were suppressed. As early as 1 h after HN2 treatment, high mDPC was achieved and the level maintained for up to 24 h. Quick total DPC (tDPC) and γ-H2AX accumulation were observed. To evaluate the effect of newly predicted protease DVC1 on DPC cleavage, we applied siRNA of MGMT and DVC1, MG132 (proteasome inhibitor), and NMS-873 (p97 inhibitor) and found that proteolysis plays a role. DVC1 was proven to be more important in the cleavage of mDPC than tDPC in a p97-dependent manner. HN2 exposure induced DVC1 upregulation, which was at least partially contributed to MGMT cleavage by proteolysis because HN2-induced mDPC level and DNA damage was closely related with DVC1 expression. Homologous recombination (HR) was also activated. Our findings demonstrated that MGMT might turn into a DNA damage promoter by forming DPC when exposed to HN2. Proteolysis, especially DVC1, plays a crucial role in mDPC repair. - Highlights: • Nitrogen mustard-induced MGMT-DNA cross-linking was detected in a living cell. • Concentration- and time-dependent manners of MGMT-DNA cross-linking were revealed. • Proteolysis played an important role in protein (MGMT)-DNA cross-linking repair. • DVC1 acts as a proteolytic enzyme in cross-linking repair in a p

  16. Ethanol synthesis and water gas shift over bifunctional sulfide catalysts. Final technical progress report, September 12, 1991--December 11, 1994

    Energy Technology Data Exchange (ETDEWEB)

    Klier, K.; Herman, R.G.; Deemer, M.; Richards-Babb, M.; Carr, T.

    1995-07-01

    The objective of this research was to investigate sulfur-resistant catalysts for the conversion of synthesis gas having H{sub 2}/CO {le} 1 into C{sub 1}--C{sub 4} alcohols, especially ethanol, by a highly selective and efficient pathway, while also promoting the water gas shift reaction (WGSR). The catalysts chosen are bifunctional, base-hydrogenation, sulfur-tolerant transition metal sulfides with heavy alkali, e.g. Cs{sup +}, promoter dispersed on their surfaces. The modes of activation of H{sub 2} and CO on MoS{sub 2} and alkali-doped MoS{sub 2} were considered, and computational analyses of the thermodynamic stability of transition metal sulfides and of the electronic structure of these sulfide catalysts were carried out. In the preparation of the cesium-promoted MoS{sub 2} catalysts, a variety of preparation methods using CsOOCH were examined. In all cases, doping with CsOOCH led to a lost of surface area. The undoped molybdenum disulfide catalyst only produced hydrocarbons. Cs-doped MoS{sub 2} catalysts all produced linear alcohols, along with smaller amounts of hydrocarbons. With a 20 wt% CsOOCH/MoS{sub 2} catalyst, temperature, pressure, and flow rate dependences of the synthesis reactions were investigated in the presence and absence of H{sub 2}S in the H{sub 2}/CO = 1/1 synthesis gas during short term testing experiments. It was shown that with a carefully prepared 10 wt% CsOOCH/MoS{sub 2} catalyst, reproducible and high alcohol synthesis activity could be obtained. For example, at 295 C with H{sub 2}/CO = 1 synthesis gas at 8.3 MPa and with GHSV = 7,760 l/kg cat/hr, the total alcohol space time yield was ca 300 g/kg cat/hr (accompanied with a hydrocarbon space time yield of ca 60 g/kg cat/hr). Over a testing period of ca 130 hr, no net deactivation of the catalyst was observed. 90 refs., 82 figs., 14 tabs.

  17. Upgrading pyrolysis bio-oil to biofuel over bifunctional Co-Zn/HZSM-5 catalyst in supercritical methanol

    International Nuclear Information System (INIS)

    Cheng, Shouyun; Wei, Lin; Julson, James; Muthukumarappan, Kasiviswanathan; Kharel, Parashu Ram

    2017-01-01

    Highlights: • Integration of Co-Zn/HZSM-5 and supercritical methanol was used for bio-oil hydrodeoxygenation. • Co-Zn/HZSM-5 exhibited higher effectiveness than Co/HZSM-5 or Zn/HZSM-5. • 15%Co5%Zn/HZSM-5 produced biofuel with the highest hydrocarbons content at 35.33%. • Loading of Co and/or Zn did not change crystalline structure of HZSM-5. • Hydrogenation and esterification are main reactions in bio-oil hydrodeoxygenation. - Abstract: The role of catalyst is essential in processes of upgrading biomass pyrolysis bio-oil into hydrocarbon biofuel. While the majority of heterogeneous catalytic processes are conducted in the presence of gas (nearly ideal) or liquid phase, a growing number of processes are utilizing supercritical fluids (SCFs) as reaction media. Although hydrodeoxygenation (HDO) is proven a promising process for pyrolysis bio-oil upgrading to hydrocarbon biofuel, catalyst efficiency remains a challenge. Integrating heterogeneous catalysts with SCFs in a bio-oil HDO process was investigated in this study. Bifunctional Co-Zn/HZSM-5 catalysts were firstly used to upgrade bio-oil to biofuel in supercritical methanol. The loading of Co and Zn did not change HZSM-5 crystalline structure. Physicochemical properties of biofuel produced by Co and/or Zn loaded HZSM-5 catalysts such as water content, total acid number, viscosity and higher heating value improved. Bimetallic Co-Zn/HZSM-5 catalysts showed enhanced reactions of decarboxylation and decarbonylation that resulted in higher yields of CO and CO 2 . Bimetallic Co-Zn/HZSM-5 catalysts were more effective for bio-oil HDO than monometallic Co/HZSM-5 or Zn/HZSM-5 catalyst , which was attributed to the synergistic effect of Co and Zn on HZSM-5 support. Bimetallic Co-Zn/HZSM-5 catalysts increased biofuel yields and hydrocarbons contents in biofuels in comparison with monometallic Co/HZSM-5 and Zn/HZSM-5 catalysts. 5%Co15%Zn/HZSM-5 catalyst generated the highest biofuel yield at 22.13 wt.%, and 15%Co5

  18. Bacterial biofilm formation versus mammalian cell growth on titanium-based mono- and bi-functional coating

    Directory of Open Access Journals (Sweden)

    G Subbiahdoss

    2010-05-01

    Full Text Available Biomaterials-associated-infections (BAI are serious complications in modern medicine. Although non-adhesive coatings, like polymer-brush coatings, have been shown to prevent bacterial adhesion, they do not support cell growth. Bi-functional coatings are supposed to prevent biofilm formation while supporting tissue integration. Here, bacterial and cellular responses to poly(ethylene glycol (PEG brush-coatings on titanium oxide presenting the integrin-active peptide RGD (arginine-glycine-aspartic acid (bioactive “PEG-RGD” were compared to mono-functional PEG brush-coatings (biopassive “PEG” and bare titanium oxide (TiO2 surfaces under flow. Staphylococcus epidermidis ATCC 35983 was deposited on the surfaces under a shear rate of 11 s-1 for 2 h followed by seeding of U2OS osteoblasts. Subsequently, both S. epidermidis and U2OS cells were grown simultaneously on the surfaces for 48 h under low shear (0.14 s-1. After 2 h, staphylococcal adhesion was reduced to 3.6±1.8 × 103 and 6.0±3.9 × 103 cm-2 on PEG and PEG-RGD coatings respectively, compared to 1.3±0.4 × 105 cm-2 for the TiO2 surface. When allowed to grow for 48 h, biofilms formed on all surfaces. However, biofilms detached from the PEG and PEG-RGD coatings when exposed to an elevated shear (5.6 s-1 U2OS cells neither adhered nor spread on PEG brush-coatings, regardless of the presence of biofilm. In contrast, in the presence of biofilm, U2OS cells adhered and spread on PEG-RGD coatings with a significantly higher surface coverage than on bare TiO2. The detachment of biofilm and the high cell surface coverage revealed the potential significance of PEG-RGD coatings in the context of the “race for the surface” between bacteria and mammalian cells.

  19. In vivo evaluation of a radiogallium-labeled bifunctional radiopharmaceutical, Ga-DOTA-MN2, for hypoxic tumor imaging.

    Science.gov (United States)

    Sano, Kohei; Okada, Mayumi; Hisada, Hayato; Shimokawa, Kenta; Saji, Hideo; Maeda, Minoru; Mukai, Takahiro

    2013-01-01

    On the basis of the findings obtained by X-ray crystallography of Ga-DOTA chelates and the drug design concept of bifunctional radiopharmaceuticals, we previously designed and synthesized a radiogallium-labeled DOTA chelate containing two metronidazole moieties, (67)Ga-DOTA-MN2, for hypoxic tumor imaging. As expected, (67)Ga-DOTA-MN2 exhibited high in vivo stability, although two carboxyl groups in the DOTA skeleton were conjugated with metronidazole moieties. In this study, we evaluated (67/68)Ga-DOTA-MN2 as a nuclear imaging agent for hypoxic tumors. (67)Ga-labeling of DOTA-MN2 with (67)GaCl(3) was achieved with high radiochemical yield (>85%) by 1-min of microwave irradiation (50 W). The pharmacokinetics of (67)Ga-DOTA-MN2 were examined in FM3A tumor-bearing mice, and compared with those of (67)Ga-DOTA-MN1 containing one metronidazole unit and (67)Ga-DOTA. Upon administration, (67)Ga-DOTA-MN2 exhibited higher accumulation in the implanted tumors than (67)Ga-DOTA. Tumor-to-blood ratios of (67)Ga-DOTA-MN2 were about two-fold higher than those of (67)Ga-DOTA-MN1. Autoradiographic analysis showed the heterogeneous localization of (67)Ga-DOTA-MN2 in the tumors, which corresponds to hypoxic regions suggested by well-established hypoxia marker drug, pimonidazole. Furthermore, in positron emission tomography (PET) study, the tumors of mice administered (68)Ga-labeled DOTA-MN2 were clearly imaged by small-animal PET at 1 h after administration. This study demonstrates the potential usefulness of (67/68)Ga-DOTA-MN2 as a nuclear imaging agent for hypoxic tumors and suggests that two functional moieties, such as metronidazole, can be conjugated to radiogallium-DOTA chelate without reducing the complex stability. The present findings provide useful information about the chemical design of radiogallium-labeled radiopharmaceuticals for PET and single photon emission computed tomography (SPECT) studies.

  20. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    Science.gov (United States)

    Yik, Edwin Shyn-Lo

    surfaces. Our interpretations place HDS in a specific class of more general C-X hydrogenolysis reactions, including hydrodeoxygenation (HDO) that has gained popular appeal in recent biomass conversion processes. These hydrodearomatization routes, hydrogenolysis and hydrogenation, act as probes for studying hydrogen spillover, a frequently observed phenomenon in bifunctional systems. Indeed, we observe enhancements solely in the rates of thiophene hydrogenation when monofunctional catalysts, which generate equilibrated concentrations of surface H-species, are mixed with materials (e.g. Al 2O3) that cannot dissociate H2. Conventional mechanisms that suggest gas phase or surface diffusion of atomic H-species (or H +-e- pairs) are implausible across distances along insulating surfaces (i.e. SiO2, Al2O3). We propose, with kinetic-transport models that are consistent with all observed behaviors, that mobility of active H-species occurs through gas phase diffusion of thiophene-derived molecular H-carriers, whose formation rate on HDS sites can control maximum spillover enhancements. This synergy is disrupted when the ability of thiophene to form these H-carriers is suppressed, leading to an absence of spillover-mediated rates and further challenging any diffusive roles of atomic H-species. Such implications help guide optimal designs of bifunctional cascades to permit the uninhibited access and egress of larger molecules within both catalytic functions. (Abstract shortened by UMI.).

  1. Bifunctional sensor of pentachlorophenol and copper ions based on nanostructured hybrid films of humic acid and exfoliated layered double hydroxide via a facile layer-by-layer assembly

    International Nuclear Information System (INIS)

    Yuan, Shuang; Peng, Dinghua; Hu, Xianluo; Gong, Jingming

    2013-01-01

    Graphical abstract: -- Highlights: •A new highly sensitive bifunctional electrochemical sensor developed. •As-prepared sensor fabricated by alternate assembly of HA and exfoliated LDH nanosheets. •Such a newly designed sensor combining the individual properties of HA and LDH nanosheets. •Simultaneous determination of pentachlorophenol and copper ions achieved. •Practical applications demonstrated in water samples. -- Abstract: A new, highly sensitive bifunctional electrochemical sensor for the simultaneous determination of pentachlorophenol (PCP) and copper ions (Cu 2+ ) has been developed, where organic–inorganic hybrid ultrathin films were fabricated by alternate assembly of humic acid (HA) and exfoliated Mg–Al-layered double hydroxide (LDH) nanosheets onto ITO substrates via a layer-by-layer (LBL) approach. The multilayer films were then characterized by means of UV–vis spectrometry, scanning electron microscopy (SEM), and atomic force microscope (AFM). These films were found to have a relatively smooth surface with almost equal amounts of HA incorporated in each cycle. Its electrochemical performance was systematically investigated. Our results demonstrate that such a newly designed (LDH/HA) n multilayer films, combining the individual properties of HA (dual recognition ability for organic herbicides and metal ions) together with LDH nanosheets (a rigid inorganic matrix), can be applied to the simultaneous analysis of PCP and Cu(II) without interference from each other. The LBL assembled nanoarchitectures were further investigated by X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR), which provides insight for bifunctional sensing behavior. Under the optimized conditions, the detection limit was found to be as low as 0.4 nM PCP, well below the guideline value of PCP in drinking water (3.7 nM) set by the United States Environmental Protection Agency (U.S. EPA), and 2.0 nM Cu 2+ , much below the guideline value (2.0 mg L −1

  2. Bi-functional modified-phosphate catalyzed the synthesis of α-α′-(EE)-bis(benzylidene)-cycloalkanones: Microwave versus conventional-heating

    KAUST Repository

    Solhy, Abderrahim

    2011-02-01

    The impregnation of hydroxyapatite (HAP) by NaNO3 leads to a modified-hydroxyapatite which has a bi-functional acid-base property. Sodium-modified-hydroxyapatite (Na-HAP) efficiently catalyzed the cross-aldol condensation of arylaldehydes and cycloketones to afford α-α′- (EE)-bis(benzylidene)-cycloalkanones in good yields under microwave irradiation. Moreover, the methodology described in this paper provides a very easy and efficient synthesis carried out in water as the greenest available solvent under conventional heating. A comparison study between these two different modes of heating was investigated. The catalyst was easily recovered and efficiently re-used. © 2010 Elsevier B.V.

  3. Investigation on the influence of metal ion impurities on the complexation behavior of generator produced {sup 90}Y with bifunctional chelators

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Usha; Gamre, Naresh; Dash, Ashutosh [Isotope Applications and Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai (India)

    2014-05-01

    The {sup 90}Sr/ {sup 90}Y generator is the exclusive source of 'no carrier added' {sup 90}Y for targeted therapy. However, the concomitant presence of trace metals diminishes the complexation of {sup 90}Y with bifunctional chelators (BFCs). A systematic investigation was performed to evaluate the influence of trace metals on the complexation of {sup 90}Y (from an electrochemical generator) with BFCs such as p-SCN-Bn-PCTA, p-SCN-Bn-DTPA and p-SCN-Bn-DOTA. Our study indicates that while p-SCN-Bn-DTPA was least affected by most of the trace metals studied, p-SCN-Bn-PCTA was most sensitive to their presence and hence could be the ligand of choice for assessing the chemical purity of generator derived {sup 90}Y. (author)

  4. [Expression and functions of adaptive response genes in Escherichia coli treated with mono- and bifunctional alkylating agents. Interference with SOS response].

    Science.gov (United States)

    Vasil'eva, S V; Makhova, E V; Moshkovskaia, E Iu

    1999-04-01

    The expression of genes belonging to the Ada regulon of Escherichia coli under the action of mono- and bifunctional alkylating agents--high-efficiency antitumor HMM, ACNU, and BCNU preparations--was studied. The functional specificity of the alkA, alkB, and aidB1 genes concerning both the structure and volume of DNA alkylation and the specificity of cell preadaptation was revealed. Additional experimental evidence for the role of the aidB1 gene as a unique "hazard gene", a component of the E. coli ada operon, was obtained. A phenomenon of positive interference between alternative SOS and Ada responses was observed for the first time upon gene expression.

  5. Construction of bifunctional molecules specific to antigen and antibody’s Fc-fragment by fusion of scFv-antibodies with staphylococcal protein A

    Directory of Open Access Journals (Sweden)

    Kolibo D. V.

    2009-06-01

    Full Text Available Aim. To develop approach for detection of scFv and their complexes with antigens. Methods. The fusion proteins, which include sequences of scFv and staphylococcal protein A, were constructed and the obtained bifunctional molecules were immunochemically analysed. Results. It was shown, that scFv fused with protein A and their complexes with antigens are effectively recognized by labelled immunoglobulins with unrestricted antigenic specificity. Conclusions. The fusion of scFv with protein A fragment is a perspective approach to increase the efficiency of application in ELISA. The obtained scFv, fused with protein A, could be used for development of test-systems for the detection of diphtheria toxin.

  6. Induction and removal of DNA interstrand cross-links in V-79 Chinese hamster cells measured by hydroxylapatite chromatography after treatments with bifunctional furocoumarins

    International Nuclear Information System (INIS)

    Dardalhon, M.; Averbeck, D.

    1988-01-01

    DNA interstrand crosslinks (CL) photoinduced by bifunctional furocoumarins in V-79 Chinese hamster cells were measured by alkaline denaturation and hydroxylapatite chromatography. Treatments with 5-methoxypsoralen (5-MOP), 8-methoxypsoralen (8-MOP) and 4,5',8-trimethylpsoralen (4,5',8-TMP) and 365 nm irradiation (UVA) confer a dose-dependent linear increase in the amount of double-stranded DNA indicating the induction of CL. Determination in alkaline sucrose gradients of the molecular weight of the DNA and estimation of drug-induced strand breakage allowed quantification of the CL induced. 5-MOP was found to be slightly more effective than 8-MOP whereas 4,5',8-TMP was 9 times more effective for the induction of CL. The fate of CL during post-treatment incubation was also followed. Cells in exponential growth phase were found to be efficient in the removal of CL. (Author)

  7. Cuboid Ni2 P as a Bifunctional Catalyst for Efficient Hydrogen Generation from Hydrolysis of Ammonia Borane and Electrocatalytic Hydrogen Evolution.

    Science.gov (United States)

    Du, Yeshuang; Liu, Chao; Cheng, Gongzhen; Luo, Wei

    2017-11-16

    The design of high-performance catalysts for hydrogen generation is highly desirable for the upcoming hydrogen economy. Herein, we report the colloidal synthesis of nanocuboid Ni 2 P by the thermal decomposition of nickel chloride hexahydrate (NiCl 2 ⋅6 H 2 O) and trioctylphosphine. The obtained nanocuboid Ni 2 P was characterized by using powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma atomic emission spectroscopy. For the first time, the as-synthesized nanocuboid Ni 2 P is used as a bifunctional catalyst for hydrogen generation from the hydrolysis of ammonia borane and electrocatalytic hydrogen evolution. Owing to the strong synergistic electronic effect between Ni and P, the as-synthesized Ni 2 P exhibits catalytic performance that is superior to its counterpart without P doping. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator.

    Science.gov (United States)

    Zhu, Yun Guang; Du, Yonghua; Jia, Chuankun; Zhou, Mingyue; Fan, Li; Wang, Xingzhu; Wang, Qing

    2017-05-10

    Redox flow batteries, despite great operation flexibility and scalability for large-scale energy storage, suffer from low energy density and relatively high cost as compared to the state-of-the-art Li-ion batteries. Here we report a redox flow lithium battery, which operates via the redox targeting reactions of LiFePO 4 with a bifunctional redox mediator, 2,3,5,6-tetramethyl-p-phenylenediamine, and presents superb energy density as the Li-ion battery and system flexibility as the redox flow battery. The battery has achieved a tank energy density as high as 1023 Wh/L, power density of 61 mW/cm 2 , and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO 4 , which provides insightful information on the redox targeting process, critical to the device operation and optimization.

  9. Hydroconversion of methyl laurate on bifunctional Ni2P/AlMCM-41 catalyst prepared via in situ phosphorization using triphenylphosphine

    Science.gov (United States)

    Zhao, Sha; Zhang, Zhena; Zhu, Kongying; Chen, Jixiang

    2017-05-01

    A series of Ni2P/AlMCM-41-x bifunctional catalysts with different Si/Al ratios (x) were synthesized by in situ phosphorization of Ni/AlMCM-41-x with triphenylphosphine (nominal Ni/P ratio of 0.75) at 300 °C on a fixed-bed reactor. For comparison, NiP/AlMCM-41-5-TPR was also prepared by the TPR method from the supported nickel phosphate with the Ni/P ratio of 1.0, during which metallic Ni rather than Ni2P formed. TEM images show that Ni and Ni2P particles uniformly distributed in Ni2P/AlMCM-41-x and NiP/AlMCM-41-5-TPR. The Ni2P/AlMCM-41-x acidity increased with decreasing the Si/Al ratio. In the hydroconversion of methyl laurate, the conversions were close to 100% on all catalysts at 360 °C, 3.0 MPa, methyl laurate WHSV of 2 h-1 and H2/methyl laurate ratio of 25. As to Ni2P/AlMCM-41-x, with decreasing the Si/Al ratio, the total selectivity to C11 and C12 hydrocarbons decreased, while the total selectivity to isoundecane and isododecane (Si-C11+i-C12) firstly increased and then decreased. Ni2P/AlMCM-41-5 gave the largest Si-C11+i-C12 of 43.2%. While NiP/AlMCM-41-5-TPR gave higher Si-C11+i-C12 than Ni2P/AlMCM-41-5, it was more active for the undesired Csbnd C bond cleavage and methanation. We propose that the in-situ phosphorization adopted here is a promising approach to preparing Ni2P-based bifunctional catalysts.

  10. Bifunctional coating based on carboxymethyl chitosan with stable conjugated alkaline phosphatase for inhibiting bacterial adhesion and promoting osteogenic differentiation on titanium

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Dong; Neoh, Koon Gee, E-mail: chenkg@nus.edu.sg; Kang, En-Tang

    2016-01-01

    Graphical abstract: - Highlights: • Alkaline phosphatase was immobilized on carboxymethyl chitosan coating on Ti. • The coating is bifunctional; resists bacterial adhesion and enhances cell functions. • Osteogenic differentiation of osteoblasts and stem cells is enhanced on the coating. • The coating remains stable and functional after ethanol treatment and autoclaving. - Abstract: In this work, alkaline phosphatase (ALP) was covalently immobilized on carboxymethyl chitosan (CMCS)-coated polydopamine (PDA)-functionalized Ti to achieve a bifunctional surface. Our results showed ∼89% reduction in Staphylococcus epidermidis adhesion on this surface compared to that on pristine Ti. The ALP-modified Ti supported cell proliferation, and significantly enhanced cellular ALP activity and calcium deposition of osteoblasts, human mesenchymal stem cells (hMSCs) and human adipose-derived stem cells (hADSCs). The extent of enhancement in the functions of these cells is dependent on the surface density of immobilized ALP. The substrate prepared using an ALP solution of 50 μg/cm{sup 2} resulted in 44%, 54% and 129% increase in calcium deposited by osteoblasts, hMSCs and hADSCs, respectively, compared to those cultured on pristine Ti. The ALP-modified substrates also promoted the osteogenic differentiation of hMSCs and hADSCs by up-regulating gene expressions of runt-related transcription factor 2 (RUNX2), osterix (OSX), and osteocalcin (OC) in the two types of stem cells. The surface-immobilized ALP was stable after being subjected to 1 h immersion in 70% ethanol and autoclaving at 121 °C for 20 min. However, the enzymatic bioactivity of the surface-immobilized ALP was reduced by about 50% after these substrates were immersed in phosphate buffered saline (PBS) or PBS containing lysozyme for 14 days.

  11. Structure of the phosphotransferase domain of the bifunctional aminoglycoside-resistance enzyme AAC(6′)-Ie-APH(2′′)-Ia

    Science.gov (United States)

    Smith, Clyde A.; Toth, Marta; Bhattacharya, Monolekha; Frase, Hilary; Vakulenko, Sergei B.

    2014-01-01

    The bifunctional acetyltransferase(6′)-Ie-phosphotransfer­ase(2′′)-Ia [AAC(6′)-Ie-APH(2′′)-Ia] is the most important aminoglycoside-resistance enzyme in Gram-positive bacteria, conferring resistance to almost all known aminoglycoside antibiotics in clinical use. Owing to its importance, this enzyme has been the focus of intensive research since its isolation in the mid-1980s but, despite much effort, structural details of AAC(6′)-Ie-APH(2′′)-Ia have remained elusive. The structure of the Mg2GDP complex of the APH(2′′)-Ia domain of the bifunctional enzyme has now been determined at 2.3 Å resolution. The structure of APH(2′′)-Ia is reminiscent of the structures of other aminoglycoside phosphotransferases, having a two-domain architecture with the nucleotide-binding site located at the junction of the two domains. Unlike the previously characterized APH(2′′)-IIa and APH(2′′)-IVa enzymes, which are capable of utilizing both ATP and GTP as the phosphate donors, APH(2′′)-Ia uses GTP exclusively in the phosphorylation of the aminoglycoside antibiotics, and in this regard closely resembles the GTP-dependent APH(2′′)-IIIa enzyme. In APH(2′′)-Ia this GTP selectivity is governed by the presence of a ‘gatekeeper’ residue, Tyr100, the side chain of which projects into the active site and effectively blocks access to the adenine-binding template. Mutation of this tyrosine residue to a less bulky phenylalanine provides better access for ATP to the NTP-binding template and converts APH(2′′)-Ia into a dual-specificity enzyme. PMID:24914967

  12. Synthesis and study of bifunctional core–shell nanostructures based on ZnO@Gd{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Babayevska, Nataliya, E-mail: natbab@amu.edu.pl; Nowaczyk, Grzegorz; Jarek, Marcin; Załęski, Karol; Jurga, Stefan

    2016-07-05

    Bifunctional nanostructures based on ZnO nanoparticles (NPs) with controlled Gd{sub 2}O{sub 3} shell thicknesses were obtained by simple low-temperature methods (sol–gel technique and seed deposition method). The morphology, nanostructure, phase and chemical composition as well as luminescent and magnetic properties of the obtained core–shell nanostructures were investigated by transmission electron microscopy (HRTEM), energy dispersive x-ray spectroscopy (EDS), x-ray diffraction (XRD) techniques, optical spectroscopy, and SQUID magnetometer. As-obtained ZnO NPs are highly monodispersed and crystalline with mean particles size distribution of about 7 nm. Modification of the ZnO NPs surface by Gd{sub 2}O{sub 3} shell leads to an increase of the ZnO particles size up to 80–160 nm and the formation the Gd{sub 2}O{sub 3} shell with size of 2–4 nm. The dependence of the phase composition, luminescent and magnetic properties on Gd{sub 2}O{sub 3} content are also discussed. - Highlights: • The bifunctional ZnO@Gd{sub 2}O{sub 3} nanostructures were obtained by sol–gel technique. • ZnO@Gd{sub 2}O{sub 3} have intensive luminescence in the visible range under 325 nm excitation. • Gd{sup 3+} content allows to control paramagnetic properties of the ZnO@Gd{sub 2}O{sub 3}. • ZnO@Gd{sub 2}O{sub 3} nanostructures are potential objects for application in medicine.

  13. Heterometallic and homometallic complexes containing bifunctional ligands and their application in high-temperature oxide superconductor materials

    Science.gov (United States)

    Breeze, Steven R.

    We have been interested in the development of soluble precursors for the production of YBasb2Cusb3Osb{7-delta} and Bisb2(Ca,Sr)sbn+1CusbnOsb(2n + 4) + delta, superconductor materials. Several heterometallic and homometallic complexes containing the constituent metals of these superconductors and bifunctional ligands such as aminoalcohols, acetates and thioethers have been isolated and structurally characterized. The thermal decomposition properties and magnetic properties of some of these compounds have been investigated. The first ligand system investigated involved 1,3-bis(dimethylamino)-2-propanol (bdmapH). By varying the ratio of bdmapH, Cu(OCHsb3)sb2, and M(Osb2CCFsb3)sb2 (M = Ca, Sr) several heterometallic complexes have been obtained, including Srsb2Cusb2(bdmap)sb4(Osb2CCFsb3)sb4, CaCu(bdmap)sb2(Osb2CCFsb3)sb3(Hsb2O), Srsb2Cusb4(bdmap)sb6-(Osb2CCFsb3)sb4(musb 3-OH)sb2(THF)sb2 and SrCusb2(bdmap)sb3(Osb2CCFsb3)sb3(THF). With the exception of Srsb2Cusb4(bdmap)sb6(Osb2CCFsb3)sb4(musb 3-OH)sb2(THF)sb2, these compounds thermally decompose to form mixtures of fluorides and oxides. An analogous acetate compound SrCusb2(bdmap)sb3(Osb2CCHsb3)sb3(THF) has been produced, which forms the corresponding oxide at high temperature. A bismuth dimer, Bisb2(bdmap)sb2(Osb2CCHsb3)sb4(Hsb2O), has also been obtained. Superconducting powder of the Bisb2Srsb2CaCusb2Osb{8 + delta} and epitaxial superconducting films of the YBasb2Cusb3Osb{7-delta} superconductor have been produced using the bdmap and acetate ligands as cross-linking reagents. The second ligand system investigated involved di-2-pyridylmethanediol. Only homonuclear complexes have been obtained by using this ligand, including the mononuclear compound Cu ((2-py)sb2CO(OH)) sb2(HOsb2CCH sb3)sb2*CHsb2Clsb2, the tetranuclear compound Cusb4 ((2-py)sb2CO(OH)) sb2(Osb2CCHsb 3)sb6(Hsb2O)sb2*CHsb2Clsb2, and the bismuth dimer Bisb2 ((2-py)sb2CO(OH)) sb2(Osb 2CCFsb3)sb4*(THF)sb2. The tetranuclear Cusb4 compound was found to be

  14. A comparative evaluation of synergistic extraction behaviour of hexavalent uranium with thenoyl tri-fluoro-acetone (HTTA) and 1-phenyl, 3-methyl, 4-benzoyl pyrazolone-5 (HPMBP) using mono-functional and bi-functional neutral donors

    International Nuclear Information System (INIS)

    Pai, S.A.; Lohithakshan, K.V.; Mithapara, P.D.; Aggarwal, S.K.

    2002-01-01

    Synergistic extraction of hexavalent uranium was studied using acidic extractants HTTA/HPMBP with two different bifunctional neutral donors, DHDECMP and CMPO, from HNO 3 medium at various fixed temperatures. The equilibrium constants for the organic phase addition reaction (log K s ) were correlated with the basicity (K h ) of the neutral donors. The data reported earlier for monofunctional neutral donors (DPSO, TBP, TOPO) were used for the comparison. A linear correlation between log K s and log K h was observed for U(VI)/HTTA/S (S = neutral donor) system. However, in U(VI)/HPMBP/S system, the observed log K s values for bifunctional neutral donors were much lower than those expected from linear correlation. This was attributed to the different mechanisms operative in the synergistic extraction i.e. substitution in the former vs. addition in the latter. These conclusions are also supported by the thermodynamic data obtained in the present studies. Nevertheless, it is seen that bifunctional neutral donors act only as monofunctional with both HTTA and HPMBP. (orig.)

  15. Structures of a bi-functional Kunitz-type STI family inhibitor of serine and aspartic proteases: Could the aspartic protease inhibition have evolved from a canonical serine protease-binding loop?

    Science.gov (United States)

    Guerra, Yasel; Valiente, Pedro A; Pons, Tirso; Berry, Colin; Rudiño-Piñera, Enrique

    2016-08-01

    Bi-functional inhibitors from the Kunitz-type soybean trypsin inhibitor (STI) family are glycosylated proteins able to inhibit serine and aspartic proteases. Here we report six crystal structures of the wild-type and a non-glycosylated mutant of the bifunctional inhibitor E3Ad obtained at different pH values and space groups. The crystal structures show that E3Ad adopts the typical β-trefoil fold of the STI family exhibiting some conformational changes due to pH variations and crystal packing. Despite the high sequence identity with a recently reported potato cathepsin D inhibitor (PDI), three-dimensional structures obtained in this work show a significant conformational change in the protease-binding loop proposed for aspartic protease inhibition. The E3Ad binding loop for serine protease inhibition is also proposed, based on structural similarity with a novel non-canonical conformation described for the double-headed inhibitor API-A from the Kunitz-type STI family. In addition, structural and sequence analyses suggest that bifunctional inhibitors of serine and aspartic proteases from the Kunitz-type STI family are more similar to double-headed inhibitor API-A than other inhibitors with a canonical protease-binding loop. Copyright © 2016. Published by Elsevier Inc.

  16. Hydroconversion of methyl laurate on bifunctional Ni{sub 2}P/AlMCM-41 catalyst prepared via in situ phosphorization using triphenylphosphine

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Sha; Zhang, Zhena [Tianjin Key Laboratory of Applied Catalysis Science and Technology, Department of Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Zhu, Kongying, E-mail: ausky@tju.edu.cn [Analysis and Measurement Center, Tianjin University, Tianjin 300072 (China); Chen, Jixiang, E-mail: jxchen@tju.edu.cn [Tianjin Key Laboratory of Applied Catalysis Science and Technology, Department of Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2017-05-15

    Highlights: • Bifunctional Ni{sub 2}P/AlMCM-41 was prepared by in situ phosphorization at 300 °C. • There were similar Ni{sub 2}P particle sizes in Ni{sub 2}P/AlMCM-41 with different Si/Al ratios. • The acid amount of Ni{sub 2}P/AlMCM-41 increased with decreasing the Si/Al ratio. • Ni{sub 2}P/AlMCM-41 with the Si/Al ratio of 5 had the highest activity for isomerization. • Ni{sub 2}P/AlMCM-41 had very low activity for methanation and C−C bond hydrogenolysis. - Abstract: A series of Ni{sub 2}P/AlMCM-41-x bifunctional catalysts with different Si/Al ratios (x) were synthesized by in situ phosphorization of Ni/AlMCM-41-x with triphenylphosphine (nominal Ni/P ratio of 0.75) at 300 °C on a fixed-bed reactor. For comparison, NiP/AlMCM-41-5-TPR was also prepared by the TPR method from the supported nickel phosphate with the Ni/P ratio of 1.0, during which metallic Ni rather than Ni{sub 2}P formed. TEM images show that Ni and Ni{sub 2}P particles uniformly distributed in Ni{sub 2}P/AlMCM-41-x and NiP/AlMCM-41-5-TPR. The Ni{sub 2}P/AlMCM-41-x acidity increased with decreasing the Si/Al ratio. In the hydroconversion of methyl laurate, the conversions were close to 100% on all catalysts at 360 °C, 3.0 MPa, methyl laurate WHSV of 2 h{sup −1} and H{sub 2}/methyl laurate ratio of 25. As to Ni{sub 2}P/AlMCM-41-x, with decreasing the Si/Al ratio, the total selectivity to C11 and C12 hydrocarbons decreased, while the total selectivity to isoundecane and isododecane (S{sub i-C11+i-C12}) firstly increased and then decreased. Ni{sub 2}P/AlMCM-41-5 gave the largest S{sub i-C11+i-C12} of 43.2%. While NiP/AlMCM-41-5-TPR gave higher S{sub i-C11+i-C12} than Ni{sub 2}P/AlMCM-41-5, it was more active for the undesired C−C bond cleavage and methanation. We propose that the in-situ phosphorization adopted here is a promising approach to preparing Ni{sub 2}P-based bifunctional catalysts.

  17. Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

    Energy Technology Data Exchange (ETDEWEB)

    Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)

    2016-10-01

    Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desired overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also

  18. Pt Nanostructures/N-Doped Carbon hybrid, an Efficient Catalyst for Hydrogen Evolution/Oxidation Reactions: Enhancing its Base Media Activity through Bifunctionality of the Catalyst.

    Science.gov (United States)

    Barman, Sudip; Kundu, Manas; Bhowmik, Tanmay; Mishra, Ranjit

    2018-06-04

    Design and synthesis of active catalyst for HER/HOR are important for the development of hydrogen based renewable technologies. We report synthesis of Pt nanostructures-N-doped carbon hybrid (Pt-(PtO2)-NSs/C) for HER/HOR applications. The HER activity of this Pt-(PtOx)-NSs/C catalyst is 4 and 6.5 times better than commercial Pt/C in acid and base. The catalyst exhibits a current density of 10 mA/cm2 at overpotentials of 5 and 51 mV with tafel slopes of 29 and 64mV/dec in in 0.5 M H2SO4 and 0.5 M KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt-(PtOx)-NSs/C and PtOx-free Pt-Nanostructures/C (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt-(PtOx)-NSs/C makes this Pt-catalyst more HER/HOR active in base media. The activity of Pt-(PtOx)NSs/C catalyst is 5 fold higher than that of PtNSs/C catalyst in basic medium although their activity is comparable in acid. Hydrogen binding energy and oxophilicity are the two equivalent descriptors for HER/HOR in basic media. We propose a bi-functional mechanism for the enhanced alkaline HER/HOR activity of Pt(PtOx)-NSs/C catalyst. In bi-functional Pt-(PtOx)-NSs/C catalyst, PtOx provide an active site for OH- adsorption to form OHads which reacts with hydrogen intermediate (Hads), present at neighbouring Pt sites to form H2O leading to enhancement of HOR activity in basic medium This work may provide opportunity to develop catalysts for various renewable energy technologies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. RuO 2 nanoparticles supported on MnO 2 nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yue-Feng; Chen, Yuan; Xu, Gui-Liang; Zhang, Xiao-Ru; Chen, Zonghai; Li, Jun-Tao; Huang, Ling; Amine, Khalil; Sun, Shi-Gang

    2016-10-01

    RuO2 nanoparticles supported on MnO2 nanorods (denoted as np-RuO2/nr-MnO2) were synthesized via a two-step hydrothermal reaction. SEM and TEM images both illustrated that RuO2 nanoparticles are well dispersed on the surface of MnO2 nanorods in the as-prepared np-RuO2/nr-MnO2 material. Electrochemical results demonstrated that the np-RuO2/nr-MnO2 as oxygen cathode of Li-O-2 batteries could maintain a reversible capacity of 500 mA h g(-1) within 75 cycles at a rate of 50 mA g(-1), and a higher capacity of 4000 mA h g(-1) within 20 cycles at a rate as high as 200 mA g(-1). Moreover, the cell with the np-RuO2/nr-MnO2 catalyst presented much lower voltage polarization (about 0.58 V at a rate of 50 mA g(-1)) than that measured with only MnO2 nanorods during charge/discharge processes. The catalytic property of the np-RuO2/nr-MnO2 and MnO2 nanorods were further compared by conducting studies of using rotating disk electrode (RDE), chronoamperommetry and linear sweep voltammetry. The results illustrated that the np-RuO2/nr-MnO2 exhibited excellent bifunctional electrocatalytic activities towards both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, in-situ high-energy X-ray diffraction was employed to trace evolution of species on the np-RuO2/nr-MnO2 cathode during the discharge processes. In-situ XRD patterns demonstrated the formation process of the discharge products that consisted of mainly Li2O2. Ex-situ SEM images were recorded to investigate the morphology and decomposition of the sphere-like Li2O2, which could be observed clearly after discharge process, while are decomposed almost after charge process. The excellent electrochemical performances of the np-RuO2/nr-MnO2 as cathode of Li-O-2 battery could be contributed to the excellent bifunctional electrocatalytic activities for both the ORR and OER, and to the one-dimensional structure which would benefit the diffusion of oxygen and the storage of Li2O2 in the discharge process of

  20. Cloning and analysis of a bifunctional methyltransferase/restriction endonuclease TspGWI, the prototype of a Thermus sp. enzyme family

    Directory of Open Access Journals (Sweden)

    Zylicz-Stachula Agnieszka

    2009-05-01

    Full Text Available Abstract Background Restriction-modification systems are a diverse class of enzymes. They are classified into four major types: I, II, III and IV. We have previously proposed the existence of a Thermus sp. enzyme family, which belongs to type II restriction endonucleases (REases, however, it features also some characteristics of types I and III. Members include related thermophilic endonucleases: TspGWI, TaqII, TspDTI, and Tth111II. Results Here we describe cloning, mutagenesis and analysis of the prototype TspGWI enzyme that recognises the 5'-ACGGA-3' site and cleaves 11/9 nt downstream. We cloned, expressed, and mutagenised the tspgwi gene and investigated the properties of its product, the bifunctional TspGWI restriction/modification enzyme. Since TspGWI does not cleave DNA completely, a cloning method was devised, based on amino acid sequencing of internal proteolytic fragments. The deduced amino acid sequence of the enzyme shares significant sequence similarity with another representative of the Thermus sp. family – TaqII. Interestingly, these enzymes recognise similar, yet different sequences in the DNA. Both enzymes cleave DNA at the same distance, but differ in their ability to cleave single sites and in the requirement of S-adenosylmethionine as an allosteric activator for cleavage. Both the restriction endonuclease (REase and methyltransferase (MTase activities of wild type (wt TspGWI (either recombinant or isolated from Thermus sp. are dependent on the presence of divalent cations. Conclusion TspGWI is a bifunctional protein comprising a tandem arrangement of Type I-like domains; particularly noticeable is the central HsdM-like module comprising a helical domain and a highly conserved S-adenosylmethionine-binding/catalytic MTase domain, containing DPAVGTG and NPPY motifs. TspGWI also possesses an N-terminal PD-(D/EXK nuclease domain related to the corresponding domains in HsdR subunits, but lacks the ATP-dependent translocase module

  1. Y{sub 2}O{sub 3}: Eu{sup 3+}, Tb{sup 3+} spherical particles based anti-reflection and wavelength conversion bi-functional films: Synthesis and application to solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Hui [School of Physics, Northwest University, Xi’an 710069 (China); National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Northwest University, Xi’an 710069 (China); Ji, Ruonan [School of Physics, Northwest University, Xi’an 710069 (China); Hu, Xiaoyun, E-mail: hxy3275@nwu.edu.cn [School of Physics, Northwest University, Xi’an 710069 (China); National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Northwest University, Xi’an 710069 (China); Han, Linzi; Hao, Yuanyuan; Sun, Qian [School of Physics, Northwest University, Xi’an 710069 (China); Zhang, Dekai [School of Physics, Northwest University, Xi’an 710069 (China); National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Northwest University, Xi’an 710069 (China); Fan, Jun [School of Chemical Engineering, Northwest University, Xi’an 710069 (China); Bai, Jintao [School of Physics, Northwest University, Xi’an 710069 (China); National Photoelectric Technology and Functional Materials & Application of Science and Technology International Cooperation Base, Northwest University, Xi’an 710069 (China); and others

    2015-04-25

    Highlights: • Eu{sup 3+} and Tb{sup 3+} co-doped Y{sub 2}O{sub 3} particles were successfully prepared. The as prepared particles can convert UV region photos to visible photons between 460 nm and 640 nm, which just matched the spectral response of most solar cells. • Y{sub 2}O{sub 3} is not only a good photoluminescence host material, but also it has high corrosion resistivity, thermal stability, and transparency from violet to infrared light. Cooperated with SiO{sub 2} sols, it could realize a better anti-reflection property. • As a proof-of-concept application, the as prepared bi-functional films could effectively improve the photoelectric conversion efficiency by 0.23% compared to pure SiO{sub 2} AR coating film and 0.55% compared to glass. - Abstract: In this study, Eu{sup 3+} and Tb{sup 3+} co-doped Y{sub 2}O{sub 3} particles were prepared via the simple, cost-effective urea homogeneous precipitation method without additives. The chosen particles were added in the SiO{sub 2} sols to get anti-reflection (AR) and wavelength conversion bi-functional films. Careful investigations were carried out to find the optimum preparation conditions and proper morphology. SEM images showed that the particle sizes reduced as metal ion/urea ratio decreased. Additionally, the extracted particles turned from sphere to lamellar type when the deionized water, which was used as solvent, reduced to a certain extent. The mechanisms of the morphology formation and diversification were proposed as well. The as prepared materials can convert UV region photos to visible photons between 460 nm and 640 nm, which just matched the spectral response of most solar cells. The spherical sample showed better luminescence performance than the one with lamellar morphology. In addition, the optical transmittance spectra indicated that the films adding spherical particles had better anti-reflective performance, and the best adding amount was 0.08 g. Finally, As a proof-of-concept application

  2. Purification and characterization of novel bi-functional GH3 family β-xylosidase/β-glucosidase from Aspergillus niger ADH-11.

    Science.gov (United States)

    Patel, Harshvadan; Kumar, Adepu Kiran; Shah, Amita

    2018-04-01

    β-Xylosidase plays an important role in xylan degradation by relieving the end product inhibition of endo-xylanase caused by xylo-oligosaccharides. β-Xylosidase has a wide range of applications in food, feed, paper and pulp, pharmaceutical industries and in bioconversion of lignocellulosic biomass. Hence, in the present study focused on purification, biochemical characterization and partial sequencing of purified β-xylosidase from xylanolytic strain Aspergillus niger ADH-11. Acetone precipitation followed by GPC using Sephacryl S-200 yielded 20.59-fold purified β-xylosidase with 58.30% recovery. SDS-PAGE analysis of purified β-xylosidase relieved a monomeric subunit with a molecular weight 120.48kDa. Kinetic parameters of purified β-xylosidase viz Km, Vmax, Kcat and catalytic efficiency were assessed. Purified β-xylosidase was additionally active on p-nitrophenyl-β-d-glucopyranoside substrate also. Moreover, peptide mass fingerprinting analysis support our biochemical studies and showed that the purified protein is a novel β-xylosidase with β-glucosidase activity and belongs to the bi-functional GH3 superfamily. Besides, tolerance of purified β-xylosidase towards glucose and xylose was also assessed. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Fe3O4@polyaniline yolk-shell micro/nanospheres as bifunctional materials for lithium storage and electromagnetic wave absorption

    Science.gov (United States)

    Wang, Xiaoliang; Zhang, Minwei; Zhao, Jianming; Huang, Guoyong; Sun, Hongyu

    2018-01-01

    Unique Fe3O4/polyaniline (PANI) composite with yolk-shell micro/nanostructure (FPys) has been successfully synthesized by a facile silica-assisted in-situ polymerization and subsequent etching strategy. The structural and compositional studies of the FPys composites are performed by employing X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The yolk-shell morphology of the products is confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. When evaluated as anode material for lithium-ion batteries, the as-prepared FPys electrodes deliver superior capacity, better cycling stability and rate capability than those of bare Fe3O4 micro/nanospheres and Fe3O4/PANI core-shell (FPcs) electrodes. Moreover, FPys also exhibits excellent electromagnetic wave absorption performance when comparing to the synthesized Fe3O4-based electromagnetic wave absorbers, in which strong reflection loss and extensive response bandwidth can be achieved simultaneously. The excellent bifunctional properties of FPys material are associated with the specially designed hierarchical micro/nanostructures. The current strategy that application directed structural design can be applied to the synthesis of other multifunctional materials.

  4. Survival and bioactivities of selected probiotic lactobacilli in yogurt fermentation and cold storage: New insights for developing a bi-functional dairy food.

    Science.gov (United States)

    Rutella, Giuseppina Sefora; Tagliazucchi, Davide; Solieri, Lisa

    2016-12-01

    In previous work, we demonstrated that two probiotic strains, namely Lactobacillus casei PRA205 and Lactobacillus rhamnosus PRA331, produce fermented milks with potent angiotensin-converting enzyme (ACE)-inhibitory and antioxidant activities. Here, we tested these strains for the survivability and the release of antihypertensive and antioxidant peptides in yogurt fermentation and cold storage. For these purposes three yogurt batches were compared: one prepared using yogurt starters alone (Lactobacillus delbrueckii subspecies bulgaricus 1932 and Streptococcus thermophilus 99), and the remaining two containing either PRA205 or PRA331 in addition to yogurt starters. Despite the lower viable counts at the fermentation end compared to PRA331, PRA205 overcame PRA331 in survivability during refrigerated storage for 28 days, leading to viable counts (>10(8) CFU/g) higher than the minimum therapeutic threshold (10(6) CFU/g). Analyses of in vitro ACE-inhibitory and antioxidant activities of peptide fractions revealed that yogurt supplemented with PRA205 displays higher amounts of antihypertensive and antioxidant peptides than that produced with PRA331 at the end of fermentation and over storage. Two ACE-inhibitory peptides, Valine-Proline-Proline (VPP) and Isoleucine-Proline-Proline (IPP), were identified and quantified. This study demonstrated that L. casei PRA205 could be used as adjunct culture for producing bi-functional yogurt enriched in bioactive peptides and in viable cells, which bring health benefits to the host as probiotics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Synthesis and functionalization of bifunctional chelates for 64Cu complexation for their applications by positron emission tomography (PET) imaging and radiotherapy

    International Nuclear Information System (INIS)

    Roux, Amandine

    2014-01-01

    This work aimed to develop a new family of bis-pidine-type ligands for copper(II) complexation with applications in Positron Emission Tomography (PET). Indeed, copper 64 is a radioelement whose study in PET imaging is booming. Bis-pidines have the benefit of having a rigid and pre-organized structure for complexation of a large number of transition metals. In this work we present the synthesis and optimization of new ligands whose structural and physico-chemical properties have been studied. One ligand showed very good results because it possesses all of kinetic and thermodynamic parameters which are necessary for its application to PET imaging. Different strategies of functionalization have been studied to obtain bifunctional chelates. A lysine derivative has been coupled to a maleimide function (regio-selective of cysteines), to abiotine (which displays a strong affinity for streptavidin) or to a Bodipy pattern for obtaining a bimodal probe (UV-visible and PET). Finally, we present an extension of this bis-pidine family by increasing the number of coordination functions or by synthesizing tricyclic compounds to modulate the selectivity of these molecules. (author)

  6. The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways

    KAUST Repository

    Tang, Xiaoyan

    2016-10-04

    α-Methylene-γ-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C═C bond and a highly stable five-membered γ-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL)VAP. Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester P(MBL)ROP with Mn up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes, thus affording cross-linked polymer P(MBL)CLP. The formation of the three types of polymers, P(MBL)VAP, P(MBL)CLP, and P(MBL)ROP, can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La–X (X = OR, NR2, R) group. The resulting P(MBL)ROP is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.

  7. Surface functionalization of PLGA nanoparticles by non-covalent insertion of a homo-bifunctional spacer for active targeting in cancer therapy

    Science.gov (United States)

    Thamake, S. I.; Raut, S. L.; Ranjan, A. P.; Gryczynski, Z.; Vishwanatha, J. K.

    2011-01-01

    This work reports the surface functionalization of polymeric PLGA nanoparticles by non-covalent insertion of a homo-bifunctional chemical crosslinker, bis(sulfosuccinimidyl) suberate (BS3) for targeted cancer therapy. We dissolved BS3 in aqueous solution of PVA during formulation of nanoparticles by a modified solid/oil/water emulsion solvent evaporation method. The non-covalent insertion of BS3 was confirmed by Fourier transform infrared (FTIR) spectroscopy. Curcumin and annexin A2 were used as a model drug and a cell specific target, respectively. Nanoparticles were characterized for particle size, zeta potential and surface morphology. The qualitative assessment of antibody attachment was performed by transmission electron microscopy (TEM) as well as confocal microscopy. The optimized formulation showed antibody attachment of 86%. However, antibody attachment was abolished upon blocking the functional groups of BS3. The availability of functional antibodies was evaluated by the presence of a light chain fraction after gel electrophoresis. We further evaluated the in vitro release kinetics of curcumin from antibody coated and uncoated nanoparticles. The release of curcumin is enhanced upon antibody attachment and followed an anomalous release pattern. We also observed that the cellular uptake of nanoparticles was significantly higher in annexin A2 positive cells than in negative cells. Therefore, these results demonstrate the potential use of this method for functionalization as well as to deliver chemotherapeutic agents for treating cancer.

  8. Magnetic amine-functionalized graphene oxide as a novel and recyclable bifunctional nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives

    Directory of Open Access Journals (Sweden)

    Shahnaz Rostamizadeh

    2017-01-01

    Full Text Available The new magnetic amine-functionalized graphene oxide (Fe3O4-GO-NH2 nanocatalyst was prepared through the reaction of 3-aminopropyltriethoxysilane (APTES with magnetic graphene oxide (Fe3O4-GO. It was characterized by XRD, TEM, SEM, FT-IR and EDX techniques. The intrinsic carboxylic acids on the edges of Fe3O4-GO along with the amine groups post grafted to the surface of Fe3O4-GO led to preparation of an acid-base bifunctional magnetically recyclable nanocatalyst. It proved to be efficient nanocatalyst for solvent-free synthesis of pyrano[3,2-c]pyridine derivatives under mild reaction conditions with good to excellent yields. This heterogeneous catalyst also exhibited higher activities than acid or base functionalized mesoporous silica, magnetic GO or basic Al2O3 an even higher than some basic homogeneous catalysts such as triethylamine and piperazine. More importantly, due to the loaded iron oxide nanoparticles, this catalyst could be easily recovered from the reaction mixture using an external magnet and reused without significant decrease in activity even after 7 runs.

  9. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    Science.gov (United States)

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  10. Enzymatic Production of Glutathione by Bifunctional γ-Glutamylcysteine Synthetase/Glutathione Synthetase Coupled with In Vitro Acetate Kinase-Based ATP Generation.

    Science.gov (United States)

    Jiang, Yu; Tao, Rongsheng; Shen, Zhengquan; Sun, Liangdong; Zhu, Fuyun; Yang, Sheng

    2016-12-01

    Glutathione (γ-glutamyl-L-cysteinylglycine, GSH) is a pharmaceutical compound often used in food additives and the cosmetics industry. GSH can be produced biologically from L-glutamic acid, L-cysteine, and glycine through an enzymatic process traditionally involving two sequential adenosine triphosphate (ATP)-dependent reactions catalyzed by γ-glutamylcysteine synthetase (γ-GCS or GSHI, EC 6.3.2.2) and GSH synthetase (GS or GSHII, EC 6.3.2.3). Here, we report the enzymatic production of GSH by recombinant cell-free bifunctional γ-glutamylcysteine synthetase/glutathione synthetase (γ-GCS-GS or GshF) coupled with in vitro acetate kinase-based ATP generation. GSH production by an acetate kinase-integrated Escherichia coli Rosetta(DE3) mutant expressing Streptococcus thermophilus GshF reached 18.3 ± 0.1 g l -1 (59.5 ± 0.3 mM) within 3 h, with a molar yield of 0.75 ± 0.00 mol mol -1 added cysteine and a productivity of 6.1 ± 0.0 g l -1  h -1 . This is the highest GSH titer reported to date. This newly developed biocatalytic process offers a promising approach for meeting the industrial requirements for GSH production.

  11. Effect of Ni and noble metals (Ru, Pd and Pt) on performance of bifunctional MoP/SiO2 for hydroconversion of methyl laurate

    Science.gov (United States)

    Nie, Ziyang; Zhang, Zhena; Chen, Jixiang

    2017-10-01

    SiO2 supported bifunctional MoP catalysts modified with different metal promoters (Ni, Ru, Pd, Pt), where Mo/Ni and Mo/M(M = Ru, Pd and Pt) atomic ratios was respectively 10 and 40, were prepared by TPR method from the phosphate precursors. It was found that the introduction of metal promoters facilitated the reduction of phosphate precursor and enhanced the dispersion of MoP. However, the MoP catalyst acidity was scarcely influenced by the small amount of metal promoters. In the hydroconversion of methyl laurate, the promoters enhanced the MoP catalyst activity for conversion of methyl laurate and hydrogenation of alkenes (intermediate), but reduced isomerization ability. Among the promoters, Ru was an optimum to decrease selectivity to alkenes while maintain high selectivity to iso-alkanes, and Mo40RuP showed better stability than MoP. At 380 °C and 3.0 MPa, the conversion of methyl laurate, the total selectivity to C11 and C12 hydrocarbons and the selectivity to iso-alkanes maintained at 100%, ∼94% and ∼30% on Mo40RuP during 102 h, respectively. The good stability of Mo40RuP is ascribed to that the presence of Ru prevented the sintering of MoP particles and suppressed carbon deposition.

  12. Surface functionalization of PLGA nanoparticles by non-covalent insertion of a homo-bifunctional spacer for active targeting in cancer therapy

    Energy Technology Data Exchange (ETDEWEB)

    Thamake, S I; Raut, S L [Department of Biomedical Sciences, University of North Texas Health Science Center at Fort Worth, Fort Worth, TX 76107 (United States); Ranjan, A P; Vishwanatha, J K [Department of Molecular Biology and Immunology, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States); Gryczynski, Z, E-mail: jamboor.vishwanatha@unthsc.edu [Center for Commercialization of Fluorescence Technology, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States)

    2011-01-21

    This work reports the surface functionalization of polymeric PLGA nanoparticles by non-covalent insertion of a homo-bifunctional chemical crosslinker, bis(sulfosuccinimidyl) suberate (BS3) for targeted cancer therapy. We dissolved BS3 in aqueous solution of PVA during formulation of nanoparticles by a modified solid/oil/water emulsion solvent evaporation method. The non-covalent insertion of BS3 was confirmed by Fourier transform infrared (FTIR) spectroscopy. Curcumin and annexin A2 were used as a model drug and a cell specific target, respectively. Nanoparticles were characterized for particle size, zeta potential and surface morphology. The qualitative assessment of antibody attachment was performed by transmission electron microscopy (TEM) as well as confocal microscopy. The optimized formulation showed antibody attachment of 86%. However, antibody attachment was abolished upon blocking the functional groups of BS3. The availability of functional antibodies was evaluated by the presence of a light chain fraction after gel electrophoresis. We further evaluated the in vitro release kinetics of curcumin from antibody coated and uncoated nanoparticles. The release of curcumin is enhanced upon antibody attachment and followed an anomalous release pattern. We also observed that the cellular uptake of nanoparticles was significantly higher in annexin A2 positive cells than in negative cells. Therefore, these results demonstrate the potential use of this method for functionalization as well as to deliver chemotherapeutic agents for treating cancer.

  13. Development of a bifunctional xylanase-cellulase chimera with enhanced activity on rice and barley straws using a modular xylanase and an endoglucanase procured from camel rumen metagenome.

    Science.gov (United States)

    Khalili Ghadikolaei, Kamran; Akbari Noghabi, Kambiz; Shahbani Zahiri, Hossein

    2017-09-01

    The camel rumen metagenome is an untapped source of glycoside hydrolases. In this study, novel genes encoding for a modular xylanase (XylC) and a cellulase (CelC) were isolated from a camel rumen metagenome and expressed in Escherichia coli BL21 (DE3). XylC with xylanase (Xyn), CBM, and carbohydrate esterase (CE) domains was characterized as a β-1,4-endoxylanase with remarkable catalytic activity on oat-spelt xylan (K cat  = 2919 ± 57 s -1 ). The implication of XylC's modular structure in its high catalytic activity was analyzed by truncation and fusion construction with CelC. The resulting fusions including Cel-CBM, Cel-CBM-CE, and Xyn-CBM-Cel showed remarkable enhancement in CMCase activity with K cat values of 742 ± 12, 1289 ± 34.5, and 2799 ± 51 s -1 compared to CelC with a K cat of 422 ± 3.5 s -1 . It was also shown that the bifunctional Xyn-CBM-Cel with synergistic xylanase/cellulase activities was more efficient than XylC and CelC in hydrolysis of rice and barley straws.

  14. Overexpression, purification and crystallization of the two C-terminal domains of the bifunctional cellulase ctCel9D-Cel44A from Clostridium thermocellum

    International Nuclear Information System (INIS)

    Najmudin, Shabir; Guerreiro, Catarina I. P. D.; Ferreira, Luís M. A.; Romão, Maria J. C.; Fontes, Carlos M. G. A.; Prates, José A. M.

    2005-01-01

    The two C-terminal domains of the cellulase ctCel9D-Cel44A from C. thermocellum cellulosome have been crystallized in tetragonal space group P4 3 2 1 2 and X-ray diffraction data have been collected to 2.1 and 2.8 Å from native and seleno-l-methionine-derivative crystals, respectively. Clostridium thermocellum produces a highly organized multi-enzyme complex of cellulases and hemicellulases for the hydrolysis of plant cell-wall polysaccharides, which is termed the cellulosome. The bifunctional multi-modular cellulase ctCel9D-Cel44A is one of the largest components of the C. thermocellum cellulosome. The enzyme contains two internal catalytic domains belonging to glycoside hydrolase families 9 and 44. The C-terminus of this cellulase, comprising a polycystic kidney-disease module (PKD) and a carbohydrate-binding module (CBM44), has been crystallized. The crystals belong to the tetragonal space group P4 3 2 1 2, containing a single molecule in the asymmetric unit. Native and seleno-l-methionine-derivative crystals diffracted to 2.1 and 2.8 Å, respectively

  15. Development of a plasmid-based expression system in Clostridium thermocellum and its use to screen heterologous expression of bifunctional alcohol dehydrogenases (adhEs).

    Science.gov (United States)

    Hon, Shuen; Lanahan, Anthony A; Tian, Liang; Giannone, Richard J; Hettich, Robert L; Olson, Daniel G; Lynd, Lee R

    2016-12-01

    Clostridium thermocellum is a promising candidate for ethanol production from cellulosic biomass, but requires metabolic engineering to improve ethanol yield. A key gene in the ethanol production pathway is the bifunctional aldehyde and alcohol dehydrogenase, adhE . To explore the effects of overexpressing wild-type, mutant, and exogenous adhE s, we developed a new expression plasmid, pDGO144, that exhibited improved transformation efficiency and better gene expression than its predecessor, pDGO-66. This new expression plasmid will allow for many other metabolic engineering and basic research efforts in C. thermocellum . As proof of concept, we used this plasmid to express 12 different adhE genes (both wild type and mutant) from several organisms. Ethanol production varied between clones immediately after transformation, but tended to converge to a single value after several rounds of serial transfer. The previously described mutant C. thermocellum D494G adhE gave the best ethanol production, which is consistent with previously published results.

  16. Development of a plasmid-based expression system in Clostridium thermocellum and its use to screen heterologous expression of bifunctional alcohol dehydrogenases (adhEs

    Directory of Open Access Journals (Sweden)

    Shuen Hon

    2016-12-01

    Full Text Available Clostridium thermocellum is a promising candidate for ethanol production from cellulosic biomass, but requires metabolic engineering to improve ethanol yield. A key gene in the ethanol production pathway is the bifunctional aldehyde and alcohol dehydrogenase, adhE. To explore the effects of overexpressing wild-type, mutant, and exogenous adhEs, we developed a new expression plasmid, pDGO144, that exhibited improved transformation efficiency and better gene expression than its predecessor, pDGO-66. This new expression plasmid will allow for many other metabolic engineering and basic research efforts in C. thermocellum. As proof of concept, we used this plasmid to express 12 different adhE genes (both wild type and mutant from several organisms. Ethanol production varied between clones immediately after transformation, but tended to converge to a single value after several rounds of serial transfer. The previously described mutant C. thermocellum D494G adhE gave the best ethanol production, which is consistent with previously published results. Keywords: Clostridium Thermocellum, Plasmid, adhE, Structural stability, Gene expression

  17. Synthesis of 3D iron and carbon-based composite as a bifunctional sorbent and catalyst for remediation of organic pollutants

    Science.gov (United States)

    Li, Ling; Shen, Yi; Wang, Zhaomei

    2017-07-01

    We prepared a 3D monolith by integrating graphite nanosheet encapsulated iron nanoparticles (Fe@GNS) into graphite felt (GF) supports. The structural properties of the resulting Fe@GNS/GF monolith are characterized by x-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy and N2 adsorption-desorption isotherms. The Fe@GNS/GF monoliths are utilized as a bifunctional sorbent and catalyst for water remediation. Using Congo red and methyl violet 2B as model pollutants, the sorption and catalytic performance of the Fe@GNS/GF composite are examined. The Fe@GNS/GF monolith possesses maximum sorption capacities of 177 and 142 mg g-1 for the sorption of CR and MV-2B, respectively. It also exhibits rate constants of 0.0563 and 0.0464 min-1 for the catalytic degradation of CR and MV-2B, respectively. As a proof of concept, the Fe@GNS/GF is successfully utilized to decontaminate simulated organic waste water via a combination of sorption and catalytic degradation processes.

  18. One-step production of long-chain hydrocarbons from waste-biomass-derived chemicals using bi-functional heterogeneous catalysts.

    Science.gov (United States)

    Wen, Cun; Barrow, Elizabeth; Hattrick-Simpers, Jason; Lauterbach, Jochen

    2014-02-21

    In this study, we demonstrate the production of long-chain hydrocarbons (C8+) from 2-methylfuran (2MF) and butanal in a single step reactive process by utilizing a bi-functional catalyst with both acid and metallic sites. Our approach utilizes a solid acid for the hydroalkylation function and as a support as well as a transition metal as hydrodeoxygenation catalyst. A series of solid acids was screened, among which MCM-41 demonstrated the best combination of activity and stability. Platinum nanoparticles were then incorporated into the MCM-41. The Pt/MCM-41 catalyst showed 96% yield for C8+ hydrocarbons and the catalytic performance was stable over four reaction cycles of 20 hour each. The reaction pathways for the production of long-chain hydrocarbons is probed with a combination of infrared spectroscopy and steady-state reaction experiments. It is proposed that 2MF and butanal go through hydroalkylation first on the acid site followed by hydrodeoxygenation to produce the hydrocarbon fuels.

  19. Design Of A Bi-Functional α-Fe2O3/Zn2SiO4:Mn2+ By Layer-By-Layer Assembly Method

    Directory of Open Access Journals (Sweden)

    Yu Ri

    2015-06-01

    Full Text Available This work describes the design of bi-functional α-Fe2O3/Zn2SiO4:Mn2+ using a two-step coating process. We propose a combination of pigments (α-Fe2O3 and phosphor (Zn2SiO4:Mn2+ glaze which is assembled using a layer-by-layer method. A silica-coated α-Fe2O3 pigment was obtained by a sol-gel method and a Zn2+ precursor was then added to the silica-coated α-Fe2O3 to create a ZnO layer. Finally, the Zn2SiO4:Mn2+ layer was prepared with the addition of Mn2+ ions to serve as a phosphor precursor in the multi-coated α-Fe2O3, followed by annealing at a temperature above 1000°C. Details of the phase structure, color and optical properties of the multi-functional α-Fe2O3/Zn2SiO4:Mn2+ were characterized by transmission electron microscopy and X-ray diffraction analyses.

  20. Ethanolysis conversion of spent frying oils over aluminium, calcium-phosphate based bi-functional formulated catalysts. Catalytic activity assessment study

    Energy Technology Data Exchange (ETDEWEB)

    Al-Zaini, Essam O.; Chesterfield, Dean; Adesina, Adesoji A. [The Univ. of New South Wales, Sydney (Australia). Reactor Engineering and Technology Group; Olsen, John [The Univ. of New South Wales, Sydney (Australia). School of Mechanical and Manufacturing Engineering

    2013-06-01

    The current study compares the catalytic performance of two bi-functional solid catalysts for the transesterification of waste cooking vegetable oil in presence of bio-ethanol acyl-acceptor. The two catalysts were aluminum oxide and seashell-derived calcium oxide supported K{sub 3}PO{sub 4}. The catalytic activity of the produced catalyst samples were assessed and evaluated in terms of their textural and surface chemical properties. Evaluative runs showed that increased amounts of K{sub 3}PO{sub 4} have differently controlled the textural and surface chemical property of the finally synthesised catalyst samples. The behaviour revealed a strong correlation between the percentage yield of ethyl esters EEY% and acid-base site density and strength between the two types of catalysts. Possible leaching test of the catalysts was also used as a measure of performance and as a result, the optimum catalyst, on the basis of both ester yield and resistance to leaching was identified as the sample containing between 10 and 15wt% of K{sub 3}PO{sub 4} on AlO{sub 3} and CaO respectively. (orig.)

  1. Hollow TiO2@Co9S8 Core-Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production.

    Science.gov (United States)

    Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang; Wang, Yadong; Wang, Xiuli; Lu, Xihong; Xia, Xinhui; Tu, Jiangping

    2018-03-01

    Designing ever more efficient and cost-effective bifunctional electrocatalysts for oxygen/hydrogen evolution reactions (OER/HER) is greatly vital and challenging. Here, a new type of binder-free hollow TiO 2 @Co 9 S 8 core-branch arrays is developed as highly active OER and HER electrocatalysts for stable overall water splitting. Hollow core-branch arrays of TiO 2 @Co 9 S 8 are readily realized by the rational combination of crosslinked Co 9 S 8 nanoflakes on TiO 2 core via a facile and powerful sulfurization strategy. Arising from larger active surface area, richer/shorter transfer channels for ions/electrons, and reinforced structural stability, the as-obtained TiO 2 @Co 9 S 8 core-branch arrays show noticeable exceptional electrocatalytic performance, with low overpotentials of 240 and 139 mV at 10 mA cm -2 as well as low Tafel slopes of 55 and 65 mV Dec -1 for OER and HER in alkaline medium, respectively. Impressively, the electrolysis cell based on the TiO 2 @Co 9 S 8 arrays as both cathode and anode exhibits a remarkably low water splitting voltage of 1.56 V at 10 mA cm -2 and long-term durability with no decay after 10 d. The versatile fabrication protocol and smart branch-core design provide a new way to construct other advanced metal sulfides for energy conversion and storage.

  2. Overexpression, purification and crystallization of the two C-terminal domains of the bifunctional cellulase ctCel9D-Cel44A from Clostridium thermocellum

    Energy Technology Data Exchange (ETDEWEB)

    Najmudin, Shabir [REQUIMTE, Departamento de Química, FCT-UNL, 2829-516 Caparica (Portugal); Guerreiro, Catarina I. P. D.; Ferreira, Luís M. A. [CIISA - Faculdade de Medicina Veterinária, Universidade Técnica de Lisboa, Avenida da Universidade Técnica, 1300-477 Lisboa (Portugal); Romão, Maria J. C. [REQUIMTE, Departamento de Química, FCT-UNL, 2829-516 Caparica (Portugal); Fontes, Carlos M. G. A.; Prates, José A. M., E-mail: japrates@fmv.utl.pt [CIISA - Faculdade de Medicina Veterinária, Universidade Técnica de Lisboa, Avenida da Universidade Técnica, 1300-477 Lisboa (Portugal); REQUIMTE, Departamento de Química, FCT-UNL, 2829-516 Caparica (Portugal)

    2005-12-01

    The two C-terminal domains of the cellulase ctCel9D-Cel44A from C. thermocellum cellulosome have been crystallized in tetragonal space group P4{sub 3}2{sub 1}2 and X-ray diffraction data have been collected to 2.1 and 2.8 Å from native and seleno-l-methionine-derivative crystals, respectively. Clostridium thermocellum produces a highly organized multi-enzyme complex of cellulases and hemicellulases for the hydrolysis of plant cell-wall polysaccharides, which is termed the cellulosome. The bifunctional multi-modular cellulase ctCel9D-Cel44A is one of the largest components of the C. thermocellum cellulosome. The enzyme contains two internal catalytic domains belonging to glycoside hydrolase families 9 and 44. The C-terminus of this cellulase, comprising a polycystic kidney-disease module (PKD) and a carbohydrate-binding module (CBM44), has been crystallized. The crystals belong to the tetragonal space group P4{sub 3}2{sub 1}2, containing a single molecule in the asymmetric unit. Native and seleno-l-methionine-derivative crystals diffracted to 2.1 and 2.8 Å, respectively.

  3. Ni3S2 nanowires grown on nickel foam as an efficient bifunctional electrocatalyst for water splitting with greatly practical prospects

    Science.gov (United States)

    Zhang, Dawei; Li, Jingwei; Luo, Jiaxian; Xu, Peiman; Wei, Licheng; Zhou, Dan; Xu, Weiming; Yuan, Dingsheng

    2018-06-01

    It is essential to synthesize low-cost, earth-abundant bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) for water electrolysis. Herein, we present a one-step sulfurization method to fabricate Ni3S2 nanowires directly grown on Ni foam (Ni3S2 NWs/Ni) as such an electrocatalyst. This synthetic strategy has several advantages including facile preparation, low cost and can even be expanded to large-scale preparation for practical applications. The as-synthesized Ni3S2 NWs/Ni exhibits a low overpotential of 81 and 317 mV to render a current density of 10 mA cm‑2 for the HER and OER, respectively, in 1.0 mol l‑1 KOH solution. The Ni3S2 NWs/Ni was integrated to be the cathode and the anode in the alkaline electrolyzer for overall water splitting with a current density of 10 mA cm‑2 afforded at a cell voltage of 1.63 V. More importantly, this electrolyzer maintained its electrocatalytic activity even after continual water splitting for 30 h. Owing to its simple synthesis process, the earth-abundant electrocatalyst and high performance, this versatile Ni3S2 NWs/Ni electrode will become a promising electrocatalyst for water splitting.

  4. Preparation and characterization of bifunctional dendrimer modified Fe{sub 3}O{sub 4}/CdTe nanoparticles with both luminescent and superparamagnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiuling, E-mail: wxling_self@163.com [Department of Chemical and Biological Engineering, Suzhou University of Science and Technology, Suzhou 215009 (China); Gu, Yinjun; Dong, Shuling [Department of Chemical and Biological Engineering, Suzhou University of Science and Technology, Suzhou 215009 (China); Zhao, Qin [School of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019 (China); Liu, Yongjian [Department of Chemical and Biological Engineering, Suzhou University of Science and Technology, Suzhou 215009 (China)

    2015-10-15

    Highlights: • The fluorescent superparamagnetic dendrimeric Fe{sub 3}O{sub 4}/CdTe nanoparticles are synthesized in this paper. • The synthesized nanocomposites maintain excellent magnetic properties. • The synthesized nanocomposites maintain highly luminescent markers with narrow emission bands. - Abstract: Magnetic nanoparticles Fe{sub 3}O{sub 4} were prepared by hydrothermal coprecipitation of ferric and ferrous ions using NaOH. The surface modification of Fe{sub 3}O{sub 4} nanoparticle by dendrimers has rendered the nanoparticle surface with enriched amine groups which facilitated the adsorption and conjugation of thioglycolic acid (TGA) modified CdTe quantum dots to form a stable hybrid nanostructure. Three generations (first generation: G0F, second generation: G1F, third generation: G3F) of bifunctional dendrimeric Fe{sub 3}O{sub 4}/CdTe nanoparticles were successfully prepared using this technique and characterized by microscopy. The optical and magnetic properties of the dendrimeric Fe{sub 3}O{sub 4}/CdTe nanoparticle were also investigated. The microscopic study reveals 3 different sizes for 3 generations, 16 nm (G0F), 31 nm (G1F) and 47 nm (G3F). Among three generations of nanoparticles, the G1F has the best optical property with a luminescent quantum yield of 25.6% and the G0F has the best magnetic property with a saturation magnetization of 19.3 emμ/g.

  5. Bifunctional composite catalysts using Co3O4 nanofibers immobilized on nonoxidized graphene nanoflakes for high-capacity and long-cycle Li-O2 batteries.

    Science.gov (United States)

    Ryu, Won-Hee; Yoon, Taek-Han; Song, Sung Ho; Jeon, Seokwoo; Park, Yong-Joon; Kim, Il-Doo

    2013-09-11

    Designing a highly efficient catalyst is essential to improve the electrochemical performance of Li-O2 batteries for long-term cycling. Furthermore, these batteries often show significant capacity fading due to the irreversible reaction characteristics of the Li2O2 product. To overcome these limitations, we propose a bifunctional composite catalyst composed of electrospun one-dimensional (1D) Co3O4 nanofibers (NFs) immobilized on both sides of the 2D nonoxidized graphene nanoflakes (GNFs) for an oxygen electrode in Li-O2 batteries. Highly conductive GNFs with noncovalent functionalization can facilitate a homogeneous dispersion in solution, thereby enabling simple and uniform attachment of 1D Co3O4 NFs on GNFs without restacking. High first discharge capacity of 10 500 mAh/g and superior cyclability for 80 cycles with a limited capacity of 1000 mAh/g were achieved by (i) improved catalytic activity of 1D Co3O4 NFs with large surface area, (ii) facile electron transport via interconnected GNFs functionalized by Co3O4 NFs, and (iii) fast O2 diffusion through the ultrathin GNF layer and porous Co3O4 NF networks.

  6. Purification and characterization of the bifunctional uridylyltransferase and the signal transducing proteins GlnB and GlnK from Herbaspirillum seropedicae.

    Science.gov (United States)

    Bonatto, Ana C; Couto, Gustavo H; Souza, Emanuel M; Araújo, Luiza M; Pedrosa, Fabio O; Noindorf, Lilian; Benelli, Elaine M

    2007-10-01

    GlnD is a bifunctional uridylyltransferase/uridylyl-removing enzyme that has a central role in the general nitrogen regulatory system NTR. In enterobacteria, GlnD uridylylates the PII proteins GlnB and GlnK under low levels of fixed nitrogen or ammonium. Under high ammonium levels, GlnD removes UMP from these proteins (deuridylylation). The PII proteins are signal transduction elements that integrate the signals of nitrogen, carbon and energy, and transduce this information to proteins involved in nitrogen metabolism. In Herbaspirillum seropedicae, an endophytic diazotroph isolated from grasses, several genes coding for proteins involved in nitrogen metabolism have been identified and cloned, including glnB, glnK and glnD. In this work, the GlnB, GlnK and GlnD proteins of H. seropedicae were overexpressed in their native forms, purified and used to reconstitute the uridylylation system in vitro. The results show that H. seropedicae GlnD uridylylates GlnB and GlnK trimers producing the forms PII (UMP)(1), PII (UMP)(2) and PII (UMP)(3), in a reaction that requires 2-oxoglutarate and ATP, and is inhibited by glutamine. The quantification of these PII forms indicates that GlnB was more efficiently uridylylated than GlnK in the system used.

  7. Phenotypes in siblings with homozygous mutations of TRAPPC9 and/or MCPH1 support a bifunctional model of MCPH1.

    Science.gov (United States)

    Duerinckx, Sarah; Meuwissen, Marije; Perazzolo, Camille; Desmyter, Laurence; Pirson, Isabelle; Abramowicz, Marc

    2018-04-24

    Autosomal recessive intellectual disability (ARID) is vastly heterogeneous. Truncating mutations of TRAPPC9 were reported in 8 ARID families. Autosomal recessive primary microcephaly (MCPH) represents another subgroup of ARID, itself very heterogeneous, where the size of the brain is very small since birth. MCPH1 plays a role at the centrosome via a BRCT1 domain, and in DNA Damage Repair (DDR) via BRCT2 and BRCT3, and it is not clear which of these two mechanisms causes MCPH in man. We studied the phenotype and sequenced the exome in two siblings with MCPH and their unaffected sister. Homozygous mutations of TRAPPC9 (p.Leu178Pro) and of MCPH1 (p.Arg741X) were found in both affected siblings. Brain MRI showed anomalies previously associated with TRAPPC9 defects, supporting the implication of TRAPPC9 in the phenotype. Importantly, the asymptomatic sister with normal head size was homozygous for the MCPH1 truncating mutation and heterozygous for the TRAPPC9 mutation. The affected siblings represent the first ARID cases with a TRAPPC9 missense mutation and with microcephaly of prenatal onset of. Furthermore, their unaffected sister represents strong evidence that the lack of MCPH1 BRCT3 domain does not cause MCPH in man, supporting a bifunctional model of MCPH1 where the centrosomal function is involved in brain volumic development and not the DDR function. © 2018 The Authors. Molecular Genetics & Genomic Medicine published by Wiley Periodicals, Inc.

  8. Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

    Science.gov (United States)

    Amosa, Mutiu K

    2016-08-01

    Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process.

  9. Effects of a new bifunctional psoralen, 4,4',5'-trimethylazapsoralen and ultraviolet-A radiation on murine dendritic epidermal cells.

    Science.gov (United States)

    Aubin, F; Alcalay, J; Dall'Acqua, F; Kripke, M L

    1990-06-01

    Although some psoralens are therapeutically active in the treatment of cutaneous hyperproliferative diseases when combined with UVA (320-400 nm) radiation, the toxic effects of these compounds have led physicians to seek new photochemotherapeutic agents. One such agent is 4,4',5'-trimethylazapsoralen (TMAP), a new bifunctional psoralen compound. We investigated the effects of repetitive treatments with TMAP plus UVA radiation on the number of dendritic immune cells in murine epidermis and on the induction of phototoxicity. Mice treated 3 times per week for 4 weeks with 129 microgram TMAP plus 10 kJ/m2 UVA radiation exhibited no gross or microscopic evidence of phototoxicity. During this treatment, the numbers of ATPase+, Ia+, and Thy-l+ dendritic epidermal cells were greatly reduced, and by the end of the treatment period, few dendritic immune cells could be detected. We conclude that morphological alterations of cutaneous immune cells can occur in the absence of overt phototoxicity, and that TMAP plus low-dose UVA radiation decreases the numbers of detectable Langerhans cells and Thy-1+ cells in murine skin.

  10. Bifunctional NaYF4:Er3+/Yb3+ submicron rods, implemented in quantum dot sensitized solar cell(Conference Presentation)

    Science.gov (United States)

    Guerrero, J. Pablo; Cerdán Pasarán, Andrea; López-Luke, Tzarara; Ramachari, D.; Esparza, Diego; De la Rosa Cruz, Elder; Romero Arellano, Victor Hugo

    2016-09-01

    In this work are presented the results obtained with solar cells sensitized with quantum dots of cadmium sulphide (CdS) incorporating luminescent materials (NaYF4:Yb/Er). The study revealed that through using a bifunctional layer of NaYF4:Yb/Er submicron rods, the infrared radiation is absorbed in 980nm to generate luminescence in the visible region to 530nm, under the UP-conversion process, in the same way simultaneously, NaYF4:Yb/Er layer causes scattering toward the quantum dots, the emission and scattering generated by this material is reabsorbed by the QD-CdS, and these in turn are absorbing in its range of solar radiation absorption, Thus generates an increase in the electron injection into the semiconductor of TiO2. The results of a cell incorporating NaYF4: Yb/Er at 0.07M shown photoconversion efficiencies of 3.39% improving efficiency with respect to the reference solar cell without using NaYF4: Yb/Er of 1.99%. The obtained values of current and voltage showed a strong dependence of the percentage of NaYF4 Yb/Er, and the mechanism of incorporation of this material.

  11. Highly active, bi-functional and metal-free B4C-nanoparticle-modified graphite felt electrodes for vanadium redox flow batteries

    Science.gov (United States)

    Jiang, H. R.; Shyy, W.; Wu, M. C.; Wei, L.; Zhao, T. S.

    2017-10-01

    The potential of B4C as a metal-free catalyst for vanadium redox reactions is investigated by first-principles calculations. Results show that the central carbon atom of B4C can act as a highly active reaction site for redox reactions, due primarily to the abundant unpaired electrons around it. The catalytic effect is then verified experimentally by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests, both of which demonstrate that B4C nanoparticles can enhance the kinetics for both V2+/V3+ and VO2+/VO2+ redox reactions, indicating a bi-functional effect. The B4C-nanoparticle-modified graphite felt electrodes are finally prepared and tested in vanadium redox flow batteries (VRFBs). It is shown that the batteries with the prepared electrodes exhibit energy efficiencies of 88.9% and 80.0% at the current densities of 80 and 160 mA cm-2, which are 16.6% and 18.8% higher than those with the original graphite felt electrodes. With a further increase in current densities to 240 and 320 mA cm-2, the batteries can still maintain energy efficiencies of 72.0% and 63.8%, respectively. All these results show that the B4C-nanoparticle-modified graphite felt electrode outperforms existing metal-free catalyst modified electrodes, and thus can be promising electrodes for VRFBs.

  12. A comparative study of thermodynamics in synergistic extraction of hexavalent plutonium by HTTA and HPMBP using mono- and bi-functional neutral donors

    International Nuclear Information System (INIS)

    Lohithakshan, K.V.; Mithapara, P.D.; Pai, S.A.; Aggarwal, S.K.

    1996-01-01

    Synergistic extraction of hexavalent plutonium was studied from HNO 3 medium (0.05 M) with HTTA and various neutral donors viz. DPSO, TBP, TOPO (monofunctional) and DBDECMP, DHDECMP, CMPO (bifunctional) using benzene as a diluent. Thermodynamic parameters (Δ G, Δ H, Δ S) were evaluated at 298 K from the experiments performed at four fixed temperatures in 288 to 318 K range. These were compared with the corresponding values reported earlier for Pu(VI) + HPMBP + neutral donor system. The net negative enthalpy changes with HTTA were observed to be low as compared to those with HPMBP. The net entropy changes were found to be either negligibly small (in cases of DPSO, TBP, DBDECMP, DHDECMP) or positive (in cases of CMPO, TOPO) with HTTA in comparison to large negative values with HPMBP. These results were interpreted in terms of different organic phase adduct formation reaction mechanisms i.e. substitution in HTTA vs. addition in HPMBP. Further, the lower net enthalpy changes with HTTA were explained due to a part of the energy used in release of water molecules bonded to plutonium in the plutonium chelate. (orig.)

  13. The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways

    KAUST Repository

    Tang, Xiaoyan; Hong, Miao; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y X

    2016-01-01

    α-Methylene-γ-butyrolactone (MBL), a naturally occurring and biomass-sourced bifunctional monomer, contains both a highly reactive exocyclic C═C bond and a highly stable five-membered γ-butyrolactone ring. Thus, all previous work led to exclusive vinyl-addition polymerization (VAP) product P(MBL)VAP. Now, this work reverses this conventional chemoselectivity to enable the first ring-opening polymerization (ROP) of MBL, thereby producing exclusively unsaturated polyester P(MBL)ROP with Mn up to 21.0 kg/mol. This elusive goal was achieved through uncovering the thermodynamic, catalytic, and processing conditions. A third reaction pathway has also been discovered, which is a crossover propagation between VAP and ROP processes, thus affording cross-linked polymer P(MBL)CLP. The formation of the three types of polymers, P(MBL)VAP, P(MBL)CLP, and P(MBL)ROP, can be readily controlled by adjusting the catalyst (La)/initiator (ROH) ratio, which is determined by the unique chemoselectivity of the La–X (X = OR, NR2, R) group. The resulting P(MBL)ROP is degradable and can be readily postfunctionalized into cross-linked or thiolated materials but, more remarkably, can also be fully recycled back to its monomer thermochemically. Computational studies provided the theoretical basis for, and a mechanistic understanding of, the three different polymerization processes and the origin of the chemoselectivity.

  14. Investigation on the influence of metal ion impurities on the complexation behavior of generator produced {sup 90}Y with different bifunctional chelators

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Usha; Gamre, Naresh; Chakravarty, Rubel; Pillai, Maroor Raghavan Ambikalmajan; Dash, Ashutosh [Bhabha Atomic Research Centre, Trombay, Mumbai (India). Radiopharmaceuticals Div.

    2014-07-01

    While the {sup 90}Sr/{sup 90}Y generator is the exclusive source of obtaining 'no carrier added' {sup 90}Y for targeted therapy, the presence of trace metals in the radiolabeling solutions poses a serious challenge owing to their ability to diminish the {sup 90}Y complexation yields with bifunctional chelators (BFCs). p-SCN-Bn-PCTA is a novel ligand having faster complexation kinetics with a number of radiometals. In this work, a systematic investigation was performed to evaluate the chelating ability of p-SCN-Bn-PCTA for {sup 90}Y and the influence of trace metal ions on it's complexation with {sup 90}Y in comparison to p-SCN-Bn-DTPA and p-SCN-Bn-DOTA using {sup 90}YCl{sub 3} obtained from an electrochemical generator. Results from our study indicate that while p-SCN-Bn-PCTA gave very good radiolabeling yields with {sup 90}Y when the reaction was carried out by heating for few minutes, it was most sensitive to the presence of trace metals, especially Fe(III). An independent and useful observation is that p-SCN-Bn-PCTA could be considered as the ligand of choice for assessing the chemical purity of generator derived {sup 90}Y.

  15. Synthesis and evaluation of novel bifunctional chelating agents based on 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetraacetic acid for radiolabeling proteins

    International Nuclear Information System (INIS)

    Chappell, L.L.; Ma, D.; Milenic, D.E.; Garmestani, K.; Venditto, V.; Beitzel, M.P.; Brechbiel, M.W.

    2003-01-01

    Detailed synthesis of the bifunctional chelating agents 2-methyl-6-(p-isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane-1,4,7,10 -tetraacetic acid (1B4M-DOTA) and 2-(p-isothiocyanatobenzyl)-5, 6-cyclohexano-1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetraacetate (CHX-DOTA) are reported. These chelating agents were compared to 2-(p-isothiocyanatobenzyl)-1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetraacetic acid (C-DOTA) and 1, 4, 7, 10-Tetraaza-N-(1-carboxy-3-(4-nitrophenyl)propyl)-N', N'', N'''-tris(acetic acid) cyclododecane (PA-DOTA) as their 177 Lu radiolabeled conjugates with Herceptin TM . In vitro stability of the immunoconjugates radiolabeled with 177 Lu was assessed by serum stability studies. The in vivo stability of the radiolabeled immunoconjugates and their targeting characteristics were determined by biodistribution studies in LS-174T xenograft tumor-bearing mice. Relative radiolabeling rates and efficiencies were determined for all four immunoconjugates. Insertion of the 1B4M moiety into the DOTA backbone increases radiometal chelation rate and provides complex stability comparable to C-DOTA and PA-DOTA while the CHX-DOTA appears to not form as stable a 177 Lu complex while exhibiting a substantial increase in formation rate. The 1B4M-DOTAmay have potential for radioimmunotherapy applications. Published by Elsevier Inc. All rights reserved

  16. Two bifunctional enzymes from the marine protist Thraustochytrium roseum: biochemical characterization of wax ester synthase/acyl-CoA:diacylglycerol acyltransferase activity catalyzing wax ester and triacylglycerol synthesis.

    Science.gov (United States)

    Zhang, Nannan; Mao, Zejing; Luo, Ling; Wan, Xia; Huang, Fenghong; Gong, Yangmin

    2017-01-01

    Triacylglycerols (TAGs) and wax esters (WEs) are important neutral lipids which serve as energy reservoir in some plants and microorganisms. In recent years, these biologically produced neutral lipids have been regarded as potential alternative energy sources for biofuel production because of the increased interest on developing renewable and environmentally benign alternatives for fossil fuels. In bacteria, the final step in TAG and WE biosynthetic pathway is catalyzed by wax ester synthase/acyl coenzyme A (acyl-CoA):diacylglycerol acyltransferase (WS/DGAT). This bifunctional WS/DGAT enzyme is also a key enzyme in biotechnological production of liquid WE via engineering of plants and microorganisms. To date, knowledge about this class of biologically and biotechnologically important enzymes is mainly from biochemical characterization of WS/DGATs from Arabidopsis, jojoba and some bacteria that can synthesize both TAGs and WEs intracellularly, whereas little is known about WS/DGATs from eukaryotic microorganisms. Here, we report the identification and characterization of two bifunctional WS/DGAT enzymes (designated TrWSD4 and TrWSD5) from the marine protist Thraustochytrium roseum . Both TrWSD4 and TrWSD5 comprise a WS-like acyl-CoA acyltransferase domain and the recombinant proteins purified from Escherichia coli Rosetta (DE3) have substantial WS and lower DGAT activity. They exhibit WS activity towards various-chain-length saturated and polyunsaturated acyl-CoAs and fatty alcohols ranging from C 10 to C 18 . TrWSD4 displays WS activity with the lowest K m value of 0.14 μM and the highest k cat / K m value of 1.46 × 10 5  M -1  s -1 for lauroyl-CoA (C 12:0 ) in the presence of 100 μM hexadecanol, while TrWSD5 exhibits WS activity with the lowest K m value of 0.96 μM and the highest k cat / K m value of 9.83 × 10 4  M -1  s -1 for decanoyl-CoA (C 10:0 ) under the same reaction condition. Both WS/DGAT enzymes have the highest WS activity at 37 and 47

  17. Exfoliated Pd/HNb{sub 3}O{sub 8} nanosheet as highly efficient bifunctional catalyst for one-pot cascade reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Nahaeng; Chung, Young-Min, E-mail: ymchung@kunsan.ac.kr

    2016-05-01

    Graphical abstract: - Highlights: • Ultrathin and highly acidic HNb{sub 3}O{sub 8} nanosheet was prepared by exfoliation of layered niobium oxide. • Pd/HNb{sub 3}O{sub 8} nanosheet showed excellent catalytic performance for one-pot cascade reaction. • The reaction performance of Pd/HNb{sub 3}O{sub 8} nanosheet is 7.1 and 1.2 times higher than that of layered Pd/KNb{sub 3}O{sub 8} or Pd/HNb{sub 3}O{sub 8}, respectively. • Significant promoting effect of support acidity on the reaction performance was observed. - Abstract: Ultrathin two-dimensional metal oxide nanosheets have drawn attention as potential solid acid catalysts owing to their strong acidity, attributed to the bridged OH groups formed on the nanosheets. In this study, a new class of bifunctional acid–metal catalyst was realized by the deposition of Pd on layered niobium oxide (KNb{sub 3}O{sub 8} and HNb{sub 3}O{sub 8}) or its exfoliated nanosheet (Pd/HNb{sub 3}O{sub 8}-NS) and applied to one-pot cascade deacetalization and hydrogenation. It was found that the acid strength of the support exerted a large influence not only on the promotion of the first deacetalization step, but also on the acceleration of the subsequent hydrogenation step. Comparative experiments using a series of Pd/HZSM-5 catalysts with different acidities reconfirmed the crucial role of acid strength on hydrogenation. However, the superior catalytic activity of Pd/HNb{sub 3}O{sub 8}-NS for hydrogenation compared to that of Pd/HZSM-5 of similar acidity suggests a more efficient ensemble effect of the strong acid sites with the nearby metal sites on the nanosheet surface. Among the catalysts used, Pd/HNb{sub 3}O{sub 8}-NS showed the best catalytic performance for one-pot cascade reaction affording the desired product (benzyl alcohol) in approximately 92% yield, which was 7.1 and 1.2 times higher than that of layered Pd/KNb{sub 3}O{sub 8} or Pd/HNb{sub 3}O{sub 8}, respectively. The excellent catalytic performance of Pd/HNb{sub 3

  18. Bi-functional Au/FeS (Au/Co{sub 3}O{sub 4}) composite for in situ SERS monitoring and degradation of organic pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Shuzhen; Cai, Qian; Lu, Kailing; Liao, Fan, E-mail: fliao@suda.edu.cn; Shao, Mingwang, E-mail: mwshao@suda.edu.cn [Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University (China)

    2016-01-15

    The bi-functional Au/FeS (Au/Co{sub 3}O{sub 4}) composite was fabricated by in situ reducing Au nanoparticles onto the surface of FeS (Co{sub 3}O{sub 4}). The as-prepared FeS possessed a multi-structure composed of plenty of nanoplates, which were coated by Au nanoparticles with an average size of ∼47.5 nm. While the Co{sub 3}O{sub 4} showed a thin hexagonal sheet containing Au nanoparticles on its surface with an average size of ∼79.0 nm. Both the as-prepared Au/FeS and Au/Co{sub 3}O{sub 4} composites exhibited excellent SERS performance, capable of enhancing the Raman signals of R6G molecules with the enhancement factor up to 1.81 × 10{sup 6} and 7.60 × 10{sup 4}, respectively. Moreover, Au/FeS (Au/Co{sub 3}O{sub 4}) composite also has been verified to have intrinsic peroxidase-like activity, which could decompose H{sub 2}O{sub 2} into hydroxyl radicals and then degrade organic pollutants into small molecules. Therefore, SERS can be used to real-time and in situ monitoring the degradation process of R6G molecules, employing the Au/FeS (Au/Co{sub 3}O{sub 4}) composite both as SERS substrate and catalyst. Graphical abstract: SERS was used to real-time and in situ monitoring the degradation of R6G, employing the Au/FeS and Au/Co{sub 3}O{sub 4} composites both as SERS substrates and catalysts.

  19. Bi-functional TiO2 cemented Ag grid under layer for enhancing the photovoltaic performance of a large-area dye-sensitized solar cell

    International Nuclear Information System (INIS)

    Lan Zhang; Wu Jihuai; Lin Jianming; Huang, Miaoliang

    2012-01-01

    Graphical abstract: Enhanced photovoltaic performance of large-area DSSC with conductive grids in the photo and counter electrodes. Highlights: ► TiO 2 protected Ag grids is made for using as electrode in large-area DSSC. ► The electrode has high conductivity and low internal resistance. ► TiO 2 protected Ag grids electrode avoids iodine corrosion in electrolyte. ► The TiO 2 layer also play a blocking layer role. ► Above factors enhance the photovoltaic performance of large-area DSSC. - Abstract: A bi-functional TiO 2 cemented Ag grid under layer for enhanced the photovoltaic performance of a large-area dye-sensitized solar cell (DSSC) is prepared with a simple way. The conductive printing paste contains micro-sized Ag powders and nano-sized TiO 2 cementing agent. The conductive printing paste can be well cemented on the FTO glass and form high conductive grids with Ag powders sintered together by the nano-sized TiO 2 particles. The formed conductive grid is protected with a TiO 2 thin layer and TiO 2 sol treatment to avoid the iodine corrosion. The addition of the TiO 2 cemented conductive grid can decrease the internal resistance of the large-area dye-sensitized solar cell when it is prepared in the photo and counter electrodes. Furthermore, the protecting TiO 2 thin layer and the TiO 2 sol treatment can be done on the whole area of the large-area photo electrode to both play as the blocking under layer at the same time, which can also enhance the photovoltaic performance of the large-area dye-sensitized solar cell.

  20. Preparation of acid-base bifunctional mesoporous KIT-6 (KIT: Korea Advanced Institute of Science and Technology) and its catalytic performance in Knoevenagel reaction

    International Nuclear Information System (INIS)

    Xu, Ling; Wang, Chunhua; Guan, Jingqi

    2014-01-01

    Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH 2 containing different aluminum content have been synthesized through post synthetic grafting method. The materials were characterized by X-ray diffraction (XRD), scanning electron micrographs (SEM), transmission electron micrographs (TEM), Fourier-transform infrared spectroscopy (FTIR), IR spectra of pyridine adsorption, NH 3 -TPD and TG analysis. The characterization results indicated that the pore structure of KIT-6 was well kept after the addition of aluminum and grafting of aminopropyl groups. The acid amount of Al-KIT-6 increased with enhancing aluminum content. Catalytic results showed that weak acid and weak base favor the Knoevenagel reaction, while catalysts with strong acid and weak base exhibited worse catalytic behavior. - Graphical abstract: The postulated steps of mechanism for the acid-base catalyzed process are as follows: (1) the aldehyde gets activated by the surface acidic sites which allow the amine undergoes nucleophilic to attack the carbonyl carbon of benzaldehyde. (2) Water is released in the formation of imine intermediate. (3) The ethyl cyanoacetate reacts with the intermediate. (4) The benzylidene ethyl cyanoacetate is formed and the amine is regenerated. - Highlights: • KIT-6 and Al-KIT-6-NH 2 with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH 2 within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH 2 shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction

  1. Preparation of acid-base bifunctional mesoporous KIT-6 (KIT: Korea Advanced Institute of Science and Technology) and its catalytic performance in Knoevenagel reaction

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Ling [College of Chemistry and Chemical Engineering, Inner Mongolia University for Nationalities, Tongliao 028000 (China); Wang, Chunhua [Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun 130023 (China); Guan, Jingqi, E-mail: guanjq@jlu.edu.cn [Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun 130023 (China)

    2014-05-01

    Acid-base bifunctional mesoporous catalysts Al-KIT-6-NH{sub 2} containing different aluminum content have been synthesized through post synthetic grafting method. The materials were characterized by X-ray diffraction (XRD), scanning electron micrographs (SEM), transmission electron micrographs (TEM), Fourier-transform infrared spectroscopy (FTIR), IR spectra of pyridine adsorption, NH{sub 3}-TPD and TG analysis. The characterization results indicated that the pore structure of KIT-6 was well kept after the addition of aluminum and grafting of aminopropyl groups. The acid amount of Al-KIT-6 increased with enhancing aluminum content. Catalytic results showed that weak acid and weak base favor the Knoevenagel reaction, while catalysts with strong acid and weak base exhibited worse catalytic behavior. - Graphical abstract: The postulated steps of mechanism for the acid-base catalyzed process are as follows: (1) the aldehyde gets activated by the surface acidic sites which allow the amine undergoes nucleophilic to attack the carbonyl carbon of benzaldehyde. (2) Water is released in the formation of imine intermediate. (3) The ethyl cyanoacetate reacts with the intermediate. (4) The benzylidene ethyl cyanoacetate is formed and the amine is regenerated. - Highlights: • KIT-6 and Al-KIT-6-NH{sub 2} with different Si/Al ratios has been successfully prepared. • 79.4% Yield was obtained over 46-Al-KIT-6-NH{sub 2} within 20 min in Knoevenagel reaction. • Low Al-content Al-KIT-6-NH{sub 2} shows better catalytic stability than high Al-content catalysts. • There is acid-base synergistic effect in Knoevenagel reaction.

  2. The crystal structure of the bifunctional deaminase/reductase RibD of the riboflavin biosynthetic pathway in Escherichia coli: implications for the reductive mechanism.

    Science.gov (United States)

    Stenmark, Pål; Moche, Martin; Gurmu, Daniel; Nordlund, Pär

    2007-10-12

    We have determined the crystal structure of the bi-functional deaminase/reductase enzyme from Escherichia coli (EcRibD) that catalyzes two consecutive reactions during riboflavin biosynthesis. The polypeptide chain of EcRibD is folded into two domains where the 3D structure of the N-terminal domain (1-145) is similar to cytosine deaminase and the C-terminal domain (146-367) is similar to dihydrofolate reductase. We showed that EcRibD is dimeric and compared our structure to tetrameric RibG, an ortholog from Bacillus subtilis (BsRibG). We have also determined the structure of EcRibD in two binary complexes with the oxidized cofactor (NADP(+)) and with the substrate analogue ribose-5-phosphate (RP5) and superposed these two in order to mimic the ternary complex. Based on this superposition we propose that the invariant Asp200 initiates the reductive reaction by abstracting a proton from the bound substrate and that the pro-R proton from C4 of the cofactor is transferred to C1 of the substrate. A highly flexible loop is found in the reductase active site (159-173) that appears to control cofactor and substrate binding to the reductase active site and was therefore compared to the corresponding Met20 loop of E. coli dihydrofolate reductase (EcDHFR). Lys152, identified by comparing substrate analogue (RP5) coordination in the reductase active site of EcRibD with the homologous reductase from Methanocaldococcus jannaschii (MjaRED), is invariant among bacterial RibD enzymes and could contribute to the various pathways taken during riboflavin biosynthesis in bacteria and yeast.

  3. 3D-modelling of bifunctional core-shell catalysts for the production of fuels from biomass-based synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Wenjin; Lee, Seung Cheol; Li, Hui; Pfeifer, Peter; Dittmeyer, Roland [Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen (Germany). Inst. for Micro Process Engineering (IMVT)

    2013-09-01

    Until now, the main route for the production of DME from synthesis gas in industry is methanol synthesis on a metallic catalyst and subsequent dehydration of methanol on an acid catalyst (two-step process). A single-step process using bifunctional catalysts to perform the two steps simultaneously would be preferred e.g. due to thermodynamic considerations; but this is impeded by the higher volumetric heat release which may cause deactivation of the methanol synthesis catalyst function. Thus we propose to conduct the reaction in a microchannel reactor. However, in order to increase the productivity of the microchannel reactor and to lower the investment costs, we aim at a high selectivity and activity of the catalyst. The continuously removal of methanol by dehydration on an acidic ZSM-5 catalyst as shell improves the thermodynamic conditions of methanol synthesis in the CuO/ZnO/Al{sub 2}O{sub 3} core; thus, the synthesis gas conversion can be higher than that determined by the thermodynamics of pure methanol synthesis. The molecular sieving in the zeolite layer can further lead to higher selectivity of DME at milder reaction conditions. However, mass transport limitation of the synthesis gas to the catalyst core should not hinder the reaction, and therefore a more detailed investigation is required. In order to computer-aided optimize the catalyst structure and the operating conditions for core-shell catalysts, a simulation model should be developed to study the coupled reaction and transport processes in core-shell catalysts. In this simulation model the complicated interaction of diffusion and reaction in the zeolite layer (shell) must be detailed by a network model to describe its structure and the mechanisms effectively. In addition, suitable diffusion and kinetic models are required to describe the mass transport and reactions in the layer. Suitable networks, diffusion and kinetic models are discussed for 3D simulations in this contribution. (orig.)

  4. Co3O4/MnO2/Hierarchically Porous Carbon as Superior Bifunctional Electrodes for Liquid and All-Solid-State Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Li, Xuemei; Dong, Fang; Xu, Nengneng; Zhang, Tao; Li, Kaixi; Qiao, Jinli

    2018-05-09

    The design of efficient, durable, and affordable catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is very indispensable in liquid-type and flexible all-solid-state zinc-air batteries. Herein, we present a high-performance bifunctional catalyst with cobalt and manganese oxides supported on porous carbon (Co 3 O 4 /MnO 2 /PQ-7). The optimized Co 3 O 4 /MnO 2 /PQ-7 exhibited a comparable ORR performance with commercial Pt/C and a more superior OER performance than all of the other prepared catalysts, including commercial Pt/C. When applied to practical aqueous (6.0 M KOH) zinc-air batteries, the Co 3 O 4 /MnO 2 /porous carbon hybrid catalysts exhibited exceptional performance, such as a maximum discharge peak power density as high as 257 mW cm -2 and the most stable charge-discharge durability over 50 h with negligible deactivation to date. More importantly, a series of flexible all-solid-state zinc-air batteries can be fabricated by the Co 3 O 4 /MnO 2 /porous carbon with a layer-by-layer method. The optimal catalyst (Co 3 O 4 /MnO 2 /PQ-7) exhibited an excellent peak power density of 45 mW cm -2 . The discharge potentials almost remained unchanged for 6 h at 5 mA cm -2 and possessed a long cycle life (2.5 h@5 mA cm -2 ). These results make the optimized Co 3 O 4 /MnO 2 /PQ-7 a promising cathode candidate for both liquid-type and flexible all-solid-state zinc-air batteries.

  5. Standardization of methodology to derivatization and radiolabeling of the anti-CD20 monoclonal antibody from bifunctional chelator DOTA-NHS-Ester

    International Nuclear Information System (INIS)

    Massicano, Adriana V.F.; Akanji, Akinkunmi G.; Santos, Josefina S.; Pujatti, Priscilla B.; Couto, Renata M.; Massicano, Felipe; Araujo, Elaine Bortoleti de

    2009-01-01

    Lymphomas are cancers of the lymphatic system, being the most common the non-Hodgkin lymphoma (NHL). The Radioimmunotherapy (RIT), that increase the cytotoxic effect of monoclonal antibodies (mAb), therefore labeling these Mab with different radioisotopes. RIT combines the specificity of the antibody and the toxicity of the radionuclides. The mAb anti-CD20 is used for treatment of relapse or refractory NHL. The labeling of anti- CD20 with 177 Lu, requires a bifunctional chelating agent that is designed to make a 'connect bridge' between the mAb and the radionuclide. The incorporation of the chelating group in mAb structure is called derivatization. The aim of this work is to study the derivatization of anti-CD20 antibody with DOTA-NHS-ester chelating group and labeling parameters to produce 177 Lu-DOTA-Anti CD20. Five milligrams of anti-CD20 were purified by dialysis against phosphate buffer pH 8.0 and derivatized with DOTA-NHS-ester in 1:250, 1:500 and 1:1000 molar ratios. The reaction was conducted for 1 hour in gently mixing at room temperature and remained under refrigeration for 48 hours. The reaction mixture was purified in gel column Sephadex G-50 ; the aliquots that presented greater protein concentration, were mixed and concentrated. The purified antibody conjugated was added to 111-185MBq (3-5mCi) of 177 LuCl3 diluted in 0.4 M acetate buffer pH 5.5. Radiochemical purity was less than 95% in all the molar ratios, indicating necessity of the purification after the labeling. The mAb derivatized showed stable when stored for to 1 month to 4 deg C and 4 days at -20 deg C. (author)

  6. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.

    Science.gov (United States)

    Gul, Sheraz; Ng, Jia Wei Desmond; Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis; Anzenberg, Eitan; Lassalle-Kaiser, Benedikt; Gorlin, Yelena; Weng, Tsu-Chien; Zwart, Petrus H; Zhang, Jin Z; Bergmann, Uwe; Yachandra, Vittal K; Jaramillo, Thomas F; Yano, Junko

    2015-04-14

    Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.

  7. Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

    Science.gov (United States)

    Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

    2018-08-15

    The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

  8. Sulfur mustard induced mast cell degranulation in mouse skin is inhibited by a novel anti-inflammatory and anticholinergic bifunctional prodrug.

    Science.gov (United States)

    Joseph, Laurie B; Composto, Gabriella M; Perez, Roberto M; Kim, Hong-Duck; Casillas, Robert P; Heindel, Ned D; Young, Sherri C; Lacey, Carl J; Saxena, Jaya; Guillon, Christophe D; Croutch, Claire R; Laskin, Jeffrey D; Heck, Diane E

    2018-09-01

    Sulfur mustard (SM, bis(2-chloroethyl sulfide) is a potent vesicating agent known to cause skin inflammation, necrosis and blistering. Evidence suggests that inflammatory cells and mediators that they generate are important in the pathogenic responses to SM. In the present studies we investigated the role of mast cells in SM-induced skin injury using a murine vapor cup exposure model. Mast cells, identified by toluidine blue staining, were localized in the dermis, adjacent to dermal appendages and at the dermal/epidermal junction. In control mice, 48-61% of mast cells were degranulated. SM exposure (1.4g/m 3 in air for 6min) resulted in increased numbers of degranulated mast cells 1-14days post-exposure. Treatment of mice topically with an indomethacin choline bioisostere containing prodrug linked by an aromatic ester-carbonate that targets cyclooxygenases (COX) enzymes and acetylcholinesterase (1% in an ointment) 1-14days after SM reduced skin inflammation and injury and enhanced tissue repair. This was associated with a decrease in mast cell degranulation from 90% to 49% 1-3days post SM, and from 84% to 44% 7-14days post SM. These data suggest that reduced inflammation and injury in response to the bifunctional indomethacin prodrug may be due, at least in part, to abrogating mast cell degranulation. The use of inhibitors of mast cell degranulation may be an effective strategy for mitigating skin injury induced by SM. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. A new preparation of a bifunctional crystalline heterogeneous copper electrocatalyst by electrodeposition using a Robson-type macrocyclic dinuclear copper complex for efficient hydrogen and oxygen evolution from water.

    Science.gov (United States)

    Majumder, Samit; Abdel Haleem, Ashraf; Nagaraju, Perumandla; Naruta, Yoshinori

    2017-07-18

    The development of low-cost, stable bifunctional electrocatalysts, which operate in the same electrolyte with a low overpotential for water splitting, including the oxygen evolution reaction and the hydrogen evolution reaction, remains an attractive prospect and a great challenge. In this study, a water soluble Robson-type macrocyclic dicopper(ii) complex has been used for the first time as a catalyst precursor for the generation of a copper-based bifunctional heterogeneous catalyst film, which can be used for both HER and OER at a near neutral pH. In sodium borate buffer at pH 9.20, this complex decomposed to give a Cu(OH) 2 /Cu 2 O-based thin film on FTO that catalyzes both hydrogen production and water oxidation. The morphology, nature and composition of the thin film were fully characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron, and energy dispersive X-ray spectroscopies. The catalyst film showed high stability during the course of electrolysis in either the cathodic or the anodic direction for more than 4 h. Faradaic efficiencies of ∼92% for HER and ∼96% for OER were achieved. The switch between the two half-reactions of catalytic water splitting was fully reversible in nature.

  10. Design of an effective bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate (ATMP-FA) and optimization by Box-Behnken model for biodiesel esterification synthesis of oleic acid over ATMP-FA.

    Science.gov (United States)

    Liu, Wei; Yin, Ping; Liu, Xiguang; Qu, Rongjun

    2014-12-01

    Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0 °C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Chemical structure of carbamoylating groups and their relationship to bone marrow toxicity and antiglioma activity of bifunctionally alkylating and carbamoylating nitrosoureas.

    Science.gov (United States)

    Ali-Osman, F; Giblin, J; Berger, M; Murphy, M J; Rosenblum, M L

    1985-09-01

    Although the antitumor effects of chloroethylnitrosoureas have been shown to be due primarily to DNA-DNA cross-linking by the alkylating moieties of these agents, the basis of the often accompanying bone marrow toxicity has been more controversial. We report on the relative bone marrow toxicity of four model nitrosoureas with different alkylating and carbamoylating activities: 1,3-bis(2-chloroethyl)-1-nitrosourea; 1,3-bis(trans-4-hydroxycyclohexyl)-1-nitrosourea; chlorozotozin, (2-[3-(2-chloroethyl)-3 -nitrosoureido]-2-deoxy-D-glucopyranose); and -3-(beta-D-glucopyranosyl)-1-nitrosourea. Inhibitions of DNA, RNA, and protein synthesis in murine bone marrow cells and of colony growth of myeloid precursor cells (granulocyte-macrophage colony-forming units) were used as in vitro end points of myelotoxicity. Further, we determined the antiglioma activity of the four nitrosoureas on two human gliomas in a clonogenic tumor cell assay and studied the effect of the non-nitrosourea carbamoylators potassium cyanate, chloroethyl isocyanate, cyclohexyl isocyanate, ethyl isocyanate, and ethyl isothiocyanate on granulocyte-macrophage colony-forming units. The results show that, at equivalent drug exposures, clonogenic glioma cell kill was significant and comparative for 1,3-bis(2-chloroethyl)-1-nitrosourea, 1-(2-chloroethyl)-3-(beta-D-glucopyranosyl)-1-nitrosourea, and chlorozotocin; 1,3-bis(trans-4-hydroxycyclohexyl)-1-nitrosourea showed little activity. In contrast, granulocyte-macrophage colony-forming unit toxicity was low with chlorozotocin and 1-(2-chloroethyl)-3-(beta-D-glucopyranosyl)-1-nitrosourea and very high with 1,3-bis(2-chloroethyl)-1-nitrosourea and 1,3-bis(trans-4-hydroxycyclohexyl)-1-nitrosourea. Of the isocyanates, bone marrow toxicity was highest with chloroethyl isocyanate and cyclohexyl isocyanate, intermediate with ethyl isocyanate, and lowest with KOCN and ethyl isothiocyanate. Our results indicate that (a) bifunctional alkylation is essential for

  12. Bifunctional ferromagnetic Eu-Gd-Bi-codoped hybrid organo-silica red emitting phosphors synthesized by a modified Pechini sol-gel method

    Energy Technology Data Exchange (ETDEWEB)

    Abo-Naf, S.M., E-mail: sm.abo-naf@nrc.sci.eg [Glass Research Department, National Research Centre (NRC), El-Buhouth Str., Dokki, 12622 Cairo (Egypt); Abdel-Hameed, S.A.M.; Marzouk, M.A. [Glass Research Department, National Research Centre (NRC), El-Buhouth Str., Dokki, 12622 Cairo (Egypt); Hamdy, Y.M. [Spectroscopy Department, National Research Centre (NRC), El-Buhouth Str., Dokki, 12622 Cairo (Egypt)

    2017-06-15

    Red phosphor, composed of Eu-Gd-Bi-codoped hybrid organo-silica glass, has been synthesized via a modified Pechini sol-gel process. The synthesized hybrid glass was analyzed with powder X-ray diffraction (XRD), differential thermal analysis coupled with thermogravimetry (DTA-TG) and Fourier transform infrared (FTIR) spectroscopy. XRD and DTA-TG confirmed its amorphous structure up to 1000 °C. Magnetic behavior of the produced phosphor was investigated using vibrating specimen magnetometer (VSM) and the obtained results revealed its unsaturated ferromagnetic behavior. Photoluminescence (PL) properties of the obtained phosphor have been investigated under near-UV excitation at 395 nm. The influence of calcination temperature on the PL intensity and its decay behavior as well as on the ferromagnetic characteristics has been studied to determine the optimal reaction temperature of the phosphor. The PL emission spectra show the characteristic emission bands of Eu{sup 3+} ions in the wavelength range from 580 to 700 nm. These emission spectra have been dominated by the electric dipole {sup 5}D{sub 0}→{sup 7}F{sub 2} transition of the Eu{sup 3+} peaked at 610–620 nm producing the red light emission of the phosphors. It was found that the phosphor performance, expressed by its PL intensity and life time, could be significantly improved by increasing of the heat treatment temperature up to 900 °C. Also, calcination at 900 °C for 6 h greatly increased both of the magnetization and retentivity, while decreased the coercivity value. The organic phenomenon of metal citrate-ethylene glycol chelation and its degradation by calcination were well followed by FTIR spectroscopy. The obtained results are promising and could afford a basis for designing of efficient red phosphors for displays, lighting and bifunctional biosensors for biomedical applications. - Highlights: • Eu-Gd-Bi-codoped hybrid organo-silica phosphor was synthesized by sol-gel method. • Inorganic Eu

  13. Imaging of alpha(v)beta(3) expression by a bifunctional chimeric RGD peptide not cross-reacting with alpha(v)beta(5).

    Science.gov (United States)

    Zannetti, Antonella; Del Vecchio, Silvana; Iommelli, Francesca; Del Gatto, Annarita; De Luca, Stefania; Zaccaro, Laura; Papaccioli, Angela; Sommella, Jvana; Panico, Mariarosaria; Speranza, Antonio; Grieco, Paolo; Novellino, Ettore; Saviano, Michele; Pedone, Carlo; Salvatore, Marco

    2009-08-15

    To test whether a novel bifunctional chimeric peptide comprising a cyclic Arg-Gly-Asp pentapeptide covalently bound to an echistatin domain can discriminate alpha(v)beta(3) from alpha(v)beta(5) integrin, thus allowing the in vivo selective visualization of alpha(v)beta(3) expression by single-photon and positron emission tomography (PET) imaging. The chimeric peptide was preliminarily tested for inhibition of alpha(v)beta(3)-dependent cell adhesion and competition of 125I-echistatin binding to membrane of stably transfected K562 cells expressing alpha(v)beta(3) (Kalpha(v)beta(3)) or alpha(v)beta(5) (Kalpha(v)beta(5)) integrin. The chimeric peptide was then conjugated with diethylenetriaminepentaacetic acid and labeled with 111In for single-photon imaging, whereas a one-step procedure was used for labeling the full-length peptide and a truncated derivative, lacking the last five C-terminal amino acids, with 18F for PET imaging. Nude mice bearing tumors from Kalpha(v)beta(3), Kalpha(v)beta(5), U87MG human glioblastoma, and A431 human epidermoid cells were subjected to single-photon and PET imaging. Adhesion and competitive binding assays showed that the novel chimeric peptide selectively binds to alpha(v)beta(3) integrin and does not cross-react with alpha(v)beta(5). In agreement with in vitro findings, single-photon and PET imaging studies showed that the radiolabeled chimeric peptide selectively localizes in tumor xenografts expressing alphavbeta3 and fails to accumulate in those expressing alpha(v)beta(5) integrin. When 18F-labeled truncated derivative was used for PET imaging, alphavbeta3- and alpha(v)beta(5)-expressing tumors were visualized, indicating that the five C-terminal amino acids are required to differentially bind the two integrins. Our findings indicate that the novel chimeric Arg-Gly-Asp peptide, having no cross-reaction with alphavbeta5 integrin, allows highly selective alphavbeta3 expression imaging and monitoring.

  14. A Novel Bifunctional Amino Acid Racemase With Multiple Substrate Specificity, MalY From Lactobacillus sakei LT-13: Genome-Based Identification and Enzymological Characterization

    Directory of Open Access Journals (Sweden)

    Shiro Kato

    2018-03-01

    addition, Tyr123 was a catalytic residue in the amino acid racemase reaction but strongly affected β-lyase activity. These results showed that Ls-MalY is a novel bifunctional amino acid racemase with multiple substrate specificity; both the amino acid racemase and β-lyase reactions of Ls-MalY were catalyzed at the same active site.

  15. Overexpression of artificially fused bifunctional enzyme 4CL1-CCR: a method for production of secreted 4-hydroxycinnamaldehydes in Escherichia coli.

    Science.gov (United States)

    Liu, Shuxin; Qi, Qi; Chao, Nan; Hou, Jiayin; Rao, Guodong; Xie, Jin; Lu, Hai; Jiang, Xiangning; Gai, Ying

    2015-08-12

    4-Hydroxycinnamaldehydes are important intermediates in several secondary metabolism pathways, including those involved in the biosynthesis of phenolic acids, flavonoids, terpenoids and monolignols. They are also involved in the biosynthesis and degradation of lignins, which are important limiting factors during the processes of papermaking and biofuel production. Access to these aromatic polymers is necessary to explore the secondary biometabolic pathways they are involved in. Coniferaldehyde, sinapaldehyde, p-coumaraldehyde and caffealdehyde are members of the 4-hydroxycinnamaldehyde family. Although coniferaldehyde and sinapaldehyde can be purchased from commercial sources, p-coumaraldehyde and caffealdehyde are not commercially available. Therefore, there is increasing interest in producing 4-hydroxycinnamaldehydes. Here, we attempted to produce 4-hydroxycinnamaldehydes using engineered Escherichia coli. 4-Coumaric acid: coenzyme A ligase (4CL1) and cinnamoyl coenzyme A reductase (CCR) were fused by means of genetic engineering to generate an artificial bifunctional enzyme, 4CL1-CCR, which was overexpressed in cultured E. coli supplemented with phenylpropanoic acids. Three 4-hydroxycinnamaldehydes, p-coumaraldehyde, caffealdehyde and coniferaldehyde, were thereby biosynthesized and secreted into the culture medium. The products were extracted and purified from the culture medium, and identically characterized by the HPLC-PDA-ESI-MSn. The productivity of this new metabolic system were 49 mg/L for p-coumaraldehyde, 19 mg/L for caffealdehyde and 35 mg/L for coniferaldehyde. Extracellular hydroxycinnamoyl-coenzyme A thioesters were not detected, indicating that these thioesters could not pass freely through the cellular membrane. The fusion enzyme 4CL1-CCR can catalyze sequential multistep reactions, thereby avoiding the permeability problem of intermediates, which reveals its superiority over a mixture of individual native enzymes. Moreover, we have described a

  16. Mutual synergy between catalase and peroxidase activities of the bifunctional enzyme KatG is facilitated by electron hole-hopping within the enzyme.

    Science.gov (United States)

    Njuma, Olive J; Davis, Ian; Ndontsa, Elizabeth N; Krewall, Jessica R; Liu, Aimin; Goodwin, Douglas C

    2017-11-10

    KatG is a bifunctional, heme-dependent enzyme in the front-line defense of numerous bacterial and fungal pathogens against H 2 O 2 -induced oxidative damage from host immune responses. Contrary to the expectation that catalase and peroxidase activities should be mutually antagonistic, peroxidatic electron donors (PxEDs) enhance KatG catalase activity. Here, we establish the mechanism of synergistic cooperation between these activities. We show that at low pH values KatG can fully convert H 2 O 2 to O 2 and H 2 O only if a PxED is present in the reaction mixture. Stopped-flow spectroscopy results indicated rapid initial rates of H 2 O 2 disproportionation slowing concomitantly with the accumulation of ferryl-like heme states. These states very slowly returned to resting ( i.e. ferric) enzyme, indicating that they represented catalase-inactive intermediates. We also show that an active-site tryptophan, Trp-321, participates in off-pathway electron transfer. A W321F variant in which the proximal tryptophan was replaced with a non-oxidizable phenylalanine exhibited higher catalase activity and less accumulation of off-pathway heme intermediates. Finally, rapid freeze-quench EPR experiments indicated that both WT and W321F KatG produce the same methionine-tyrosine-tryptophan (MYW) cofactor radical intermediate at the earliest reaction time points and that Trp-321 is the preferred site of off-catalase protein oxidation in the native enzyme. Of note, PxEDs did not affect the formation of the MYW cofactor radical but could reduce non-productive protein-based radical species that accumulate during reaction with H 2 O 2 Our results suggest that catalase-inactive intermediates accumulate because of off-mechanism oxidation, primarily of Trp-321, and PxEDs stimulate KatG catalase activity by preventing the accumulation of inactive intermediates. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  17. Specific combination of compound heterozygous mutations in 17β-hydroxysteroid dehydrogenase type 4 (HSD17B4 defines a new subtype of D-bifunctional protein deficiency

    Directory of Open Access Journals (Sweden)

    McMillan Hugh J

    2012-11-01

    Full Text Available Abstract Background D-bifunctional protein (DBP deficiency is typically apparent within the first month of life with most infants demonstrating hypotonia, psychomotor delay and seizures. Few children survive beyond two years of age. Among patients with prolonged survival all demonstrate severe gross motor delay, absent language development, and severe hearing and visual impairment. DBP contains three catalytically active domains; an N-terminal dehydrogenase, a central hydratase and a C-terminal sterol carrier protein-2-like domain. Three subtypes of the disease are identified based upon the domain affected; DBP type I results from a combined deficiency of dehydrogenase and hydratase activity; DBP type II from isolated hydratase deficiency and DBP type III from isolated dehydrogenase deficiency. Here we report two brothers (16½ and 14 years old with DBP deficiency characterized by normal early childhood followed by sensorineural hearing loss, progressive cerebellar and sensory ataxia and subclinical retinitis pigmentosa. Methods and results Biochemical analysis revealed normal levels of plasma VLCFA, phytanic acid and pristanic acid, and normal bile acids in urine; based on these results no diagnosis was made. Exome analysis was performed using the Agilent SureSelect 50Mb All Exon Kit and the Illumina HiSeq 2000 next-generation-sequencing (NGS platform. Compound heterozygous mutations were identified by exome sequencing and confirmed by Sanger sequencing within the dehydrogenase domain (c.101C>T; p.Ala34Val and hydratase domain (c.1547T>C; p.Ile516Thr of the 17β-hydroxysteroid dehydrogenase type 4 gene (HSD17B4. These mutations have been previously reported in patients with severe-forms of DBP deficiency, however each mutation was reported in combination with another mutation affecting the same domain. Subsequent studies in fibroblasts revealed normal VLCFA levels, normal C26:0 but reduced pristanic acid beta-oxidation activity. Both DBP

  18. 3D hollow sphere Co3O4/MnO2-CNTs: Its high-performance bi-functional cathode catalysis and application in rechargeable zinc-air battery

    Directory of Open Access Journals (Sweden)

    Xuemei Li

    2017-07-01

    Full Text Available There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO2 nanotube-supported Co3O4 nanoparticles and its carbon nanotubes hybrid material (Co3O4/MnO2-CNTs have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co3O4/MnO2, bare MnO2 nanotubes and CNTs, the hybrid Co3O4/MnO2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition (0.1 M KOH. Therefore, high cell performances are achieved which result in an appropriate open circuit voltage (∼1.47 V, a high discharge peak power density (340 mW cm−2 and a large specific capacity (775 mAh g−1 at 10 mA cm−2 for the primary Zn-air battery, a small charge–discharge voltage gap and a high cycle-life (504 cycles at 10 mA cm−2 with 10 min per cycle for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process. Keywords: Bi-functional catalyst, Oxygen reduction reaction, Oxygen evolution reaction, Activity and stability, Rechargeable zinc-air battery

  19. Study of the hydro-isomerization of paraffins with 7 and 8 carbon atoms on bifunctional catalysts; Etude de l'hydroisomerisation des paraffines a 7 et 8 atomes de carbone sur catalyseurs bifonctionnels

    Energy Technology Data Exchange (ETDEWEB)

    Patrigeon, A.

    2000-10-11

    Due to the suppression of lead additives and the trend to decrease the aromatic and olefinic content in gasoline, the interest for new octane enhancement processes has increased, particularly for isomerization of C{sub 7} and C{sub 8} linear paraffins into higher octane number multi-branched paraffins. Up to the present day, no industrial bifunctional catalyst exists due to the high tendency of the paraffins to be cracked limiting the amount of multi-branched products. The aim of this work is to study the possibility of isomerizing linear C{sub 7} and C{sub 8} paraffins in two steps in order to increase the amount of formed multi-branched paraffins. The first step converts linear paraffins into mono-branched paraffins (that step is supposed to be the slowest one) carried out using one bifunctional catalyst. The second step converts the formed mono-branched paraffins into multi-branched paraffins using a second bifunctional catalyst. The aim is to determine the characteristics of the two catalysts. To study the first step, Pt/zeolite or Pt/meso-porous solid catalysts, with different acidities and porosities, were tested in n-heptane and n-octane hydro-conversion. The role of solid porosity on selectivities was clearly established. Molecular modelling was utilised to explain the observed selectivities. To study the second step, the 2-methyl-hexane and 2-methyl-heptane hydro-conversion on Pt/H-beta and Pt/H-Y was carried out. This lead to maximum multi-branched yields similar to those obtained with the n-heptane and n-octane hydro-conversion. That result shows that the two steps isomerization process is not necessarily required because no more multi-branched products are formed. A kinetic study on the n-heptane hydro-conversion was performed. The decomposition of isomerization and cracking reactions into elementary steps has shown the major role of the paraffins physio-sorption step in the zeolite pores. (author)

  20. Facile labelling of an anti-epidermal growth factor receptor Nanobody with 68Ga via a novel bifunctional desferal chelate for immuno-PET.

    Science.gov (United States)

    Vosjan, Maria J W D; Perk, Lars R; Roovers, Rob C; Visser, Gerard W M; Stigter-van Walsum, Marijke; van Bergen En Henegouwen, Paul M P; van Dongen, Guus A M S

    2011-04-01

    The ∼15 kDa variable domains of camelid heavy-chain-only antibodies (called Nanobodies®) have the flexibility to be formatted as monovalent, monospecific, multivalent or multispecific single chain proteins with either fast or slow pharmacokinetics. We report the evaluation of the fast kinetic anti-epidermal growth factor receptor (EGFR) Nanobody 7D12, labelled with (68)Ga via the novel bifunctional chelate (BFC) p-isothiocyanatobenzyl-desferrioxamine (Df-Bz-NCS). Df-Bz-NCS has recently been introduced as the chelate of choice for (89)Zr immuno-positron emission tomography (PET). Nanobody 7D12 was premodified with Df-Bz-NCS at pH 9. Radiolabelling with purified (68)Ga was performed at pH 5.0-6.5 for 5 min at room temperature. For in vitro stability measurements in storage buffer (0.25 M NaOAc with 5 mg ml(-1) gentisic acid, pH 5.5) at 4°C or in human serum at 37°C, a mixture of (67)Ga and (68)Ga was used. Biodistribution and immuno-PET studies of (68)Ga-Df-Bz-NCS-7D12 were performed in nude mice bearing A431 xenografts using (89)Zr-Df-Bz-NCS-7D12 as the reference conjugate. The Df-Bz-NCS chelate was conjugated to Nanobody 7D12 with a chelate to Nanobody molar substitution ratio of 0.2:1. The overall (68)Ga radiochemical yield was 55-70% (not corrected for decay); specific activity was 100-500 MBq/mg. Radiochemical purity of the conjugate was >96%, while the integrity and immunoreactivity were preserved. (68/67)Ga-Df-Bz-NCS-7D12 was stable in storage buffer as well as in human serum during a 5-h incubation period (Nanobody 7D12 showed high uptake in A431 tumours (ranging from 6.1 ± 1.3 to 7.2 ± 1.5%ID/g at 1-3 h after injection) and high tumour to blood ratios, which increased from 8.2 to 14.4 and 25.7 at 1, 2 and 3 h after injection, respectively. High uptake was also observed in the kidneys. Biodistribution was similar to that of the reference conjugate (89)Zr-Df-Bz-NCS-7D12. Tumours were clearly visualized in a PET imaging study. Via a rapid

  1. Facile labelling of an anti-epidermal growth factor receptor nanobody with {sup 68}Ga via a novel bifunctional desferal chelate for immuno-PET

    Energy Technology Data Exchange (ETDEWEB)

    Vosjan, Maria J.W.D.; Perk, Lars R.; Stigter van Walsum, Marijke [VU University Medical Center, Department of Otolaryngology/Head and Neck Surgery, De Boelelaan 1117, P.O. Box 7057, Amsterdam (Netherlands); Roovers, Rob C.; Bergen en Henegouwen, Paul M.P. van [Utrecht University, Cellular Dynamics, Science Faculty, Utrecht (Netherlands); Visser, Gerard W.M. [VU University Medical Center, Department of Nuclear Medicine and PET Research, Amsterdam (Netherlands); Dongen, Guus A.M.S. van [VU University Medical Center, Department of Otolaryngology/Head and Neck Surgery, De Boelelaan 1117, P.O. Box 7057, Amsterdam (Netherlands); VU University Medical Center, Department of Nuclear Medicine and PET Research, Amsterdam (Netherlands)

    2011-04-15

    The {proportional_to}15 kDa variable domains of camelid heavy-chain-only antibodies (called Nanobodies {sup registered}) have the flexibility to be formatted as monovalent, monospecific, multivalent or multispecific single chain proteins with either fast or slow pharmacokinetics. We report the evaluation of the fast kinetic anti-epidermal growth factor receptor (EGFR) Nanobody 7D12, labelled with {sup 68}Ga via the novel bifunctional chelate (BFC) p-isothiocyanatobenzyl-desferrioxamine (Df-Bz-NCS). Df-Bz-NCS has recently been introduced as the chelate of choice for {sup 89}Zr immuno-positron emission tomography (PET). Nanobody 7D12 was premodified with Df-Bz-NCS at pH 9. Radiolabelling with purified {sup 68}Ga was performed at pH 5.0-6.5 for 5 min at room temperature. For in vitro stability measurements in storage buffer (0.25 M NaOAc with 5 mg ml{sup -1} gentisic acid, pH 5.5) at 4 C or in human serum at 37 C, a mixture of {sup 67}Ga and {sup 68}Ga was used. Biodistribution and immuno-PET studies of {sup 68}Ga-Df-Bz-NCS-7D12 were performed in nude mice bearing A431 xenografts using {sup 89}Zr-Df-Bz-NCS-7D12 as the reference conjugate. The Df-Bz-NCS chelate was conjugated to Nanobody 7D12 with a chelate to Nanobody molar substitution ratio of 0.2:1. The overall {sup 68}Ga radiochemical yield was 55-70% (not corrected for decay); specific activity was 100-500 MBq/mg. Radiochemical purity of the conjugate was >96%, while the integrity and immunoreactivity were preserved. {sup 68/67}Ga-Df-Bz-NCS-7D12 was stable in storage buffer as well as in human serum during a 5-h incubation period (<2% radioactivity loss). In biodistribution studies the {sup 68}Ga-labelled Nanobody 7D12 showed high uptake in A431 tumours (ranging from 6.1 {+-} 1.3 to 7.2 {+-} 1.5%ID/g at 1-3 h after injection) and high tumour to blood ratios, which increased from 8.2 to 14.4 and 25.7 at 1, 2 and 3 h after injection, respectively. High uptake was also observed in the kidneys. Biodistribution was

  2. Facile labelling of an anti-epidermal growth factor receptor nanobody with 68Ga via a novel bifunctional desferal chelate for immuno-PET

    International Nuclear Information System (INIS)

    Vosjan, Maria J.W.D.; Perk, Lars R.; Stigter van Walsum, Marijke; Roovers, Rob C.; Bergen en Henegouwen, Paul M.P. van; Visser, Gerard W.M.; Dongen, Guus A.M.S. van

    2011-01-01

    The ∝15 kDa variable domains of camelid heavy-chain-only antibodies (called Nanobodies registered ) have the flexibility to be formatted as monovalent, monospecific, multivalent or multispecific single chain proteins with either fast or slow pharmacokinetics. We report the evaluation of the fast kinetic anti-epidermal growth factor receptor (EGFR) Nanobody 7D12, labelled with 68 Ga via the novel bifunctional chelate (BFC) p-isothiocyanatobenzyl-desferrioxamine (Df-Bz-NCS). Df-Bz-NCS has recently been introduced as the chelate of choice for 89 Zr immuno-positron emission tomography (PET). Nanobody 7D12 was premodified with Df-Bz-NCS at pH 9. Radiolabelling with purified 68 Ga was performed at pH 5.0-6.5 for 5 min at room temperature. For in vitro stability measurements in storage buffer (0.25 M NaOAc with 5 mg ml -1 gentisic acid, pH 5.5) at 4 C or in human serum at 37 C, a mixture of 67 Ga and 68 Ga was used. Biodistribution and immuno-PET studies of 68 Ga-Df-Bz-NCS-7D12 were performed in nude mice bearing A431 xenografts using 89 Zr-Df-Bz-NCS-7D12 as the reference conjugate. The Df-Bz-NCS chelate was conjugated to Nanobody 7D12 with a chelate to Nanobody molar substitution ratio of 0.2:1. The overall 68 Ga radiochemical yield was 55-70% (not corrected for decay); specific activity was 100-500 MBq/mg. Radiochemical purity of the conjugate was >96%, while the integrity and immunoreactivity were preserved. 68/67 Ga-Df-Bz-NCS-7D12 was stable in storage buffer as well as in human serum during a 5-h incubation period ( 68 Ga-labelled Nanobody 7D12 showed high uptake in A431 tumours (ranging from 6.1 ± 1.3 to 7.2 ± 1.5%ID/g at 1-3 h after injection) and high tumour to blood ratios, which increased from 8.2 to 14.4 and 25.7 at 1, 2 and 3 h after injection, respectively. High uptake was also observed in the kidneys. Biodistribution was similar to that of the reference conjugate 89 Zr-Df-Bz-NCS-7D12. Tumours were clearly visualized in a PET imaging study. Via a rapid

  3. Evaluation of the different supported bifunctional electrocatalysts for unified regenerative cells; Evaluacion de diferentes soportes de electrocatalizadores bifuncionales para celdas regenerativas unificadas

    Energy Technology Data Exchange (ETDEWEB)

    Gurrola, M. P.; Torres-Amaya, D. S.; Duron-Torres, S. M.; Escalante-Garcia, I. L. [Universidad Autonoma de Zacatecas, Unidad Academica de Ciencias Quimicas, Zacatecas (Mexico)]. E-mail: duronsm@prodigy.net.mx; Arriaga-Hurtado, L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico)

    2009-09-15

    Unified regenerative fuel cells (URFC) represent an alternative to normal regenerative cells, providing decreased costs and space in one single device. The challenges of these systems are even greater than those for conventional fuel cells, with the most pressing technical problem being the optimization of the oxygen electrode. The high operating potentials of these devices in the electrolyzer mode, E >1.6 V vs. ENH, limit the use of supported Pt/Vulcan electrodes. The electroactivity of Pt is not sufficient to catalyze the oxygen evolution reaction (OER) and at these potentials carbon-based supports undergo corrosion. In addition to studies of materials that function as bifunctional catalysts, a significant amount of research is being aimed at the search of new matrixes for use in supporting electrocatalysts for OER and ORR{sup 1,2}. This work presents the preliminary results of the kinetic study of oxygen reactions on different Pt combinations, with IrO{sub 2} and RuO{sub 2} supported by different forms of carbon and substoichiometric titanium oxide. The studies were conducted using cyclical (CV) and linear (LV) voltamperometry for OER and rotary disc electrode (RDE) for the ORR in watery H{sub 2}SO{sub 4} 0.5M solutions. The chronoamperometry (CA) technique provided information about the electrochemical stability of the electrodes. The results indicate that the performance of the electrodes supported by different forms of carbon decreases gradually as a result of corrosion when consecutive cycles of oxygen reduction and formation reactions occur. Titanium oxide provides the greatest stability to electrodes constructed on that material and thus can potentially support oxygen electrodes based on combinations of Pt, IrO{sub 2} and RuO{sub 2} as binfunctional electrocatalysts for the URFC. [Spanish] Las celdas de combustible regenerativas unificadas (URFC) representan una alternativa a las celdas regenerativas normales que implica disminucion de costos y espacio en

  4. Synthesis of extended bifunctional triptycenes

    Czech Academy of Sciences Publication Activity Database

    Rybáček, Jiří; Závada, Jiří; Holý, Petr

    -, č. 22 (2008), s. 3615-3618 ISSN 0039-7881 R&D Projects: GA ČR GA203/03/0087 Institutional research plan: CEZ:AV0Z40550506 Keywords : anthracenes * arynes * Diels - Alder reaction * quinones * triptycenes Subject RIV: CC - Organic Chemistry Impact factor: 2.470, year: 2008

  5. Optimization Of Process Parameters For The Production Of Bio diesel From Waste Cooking Oil In The Presence Of Bifunctional γ-Al2O3-CeO2 Supported Catalysts

    International Nuclear Information System (INIS)

    Anita Ramli; Muhammad Farooq

    2015-01-01

    Huge quantities of waste cooking oils are produced all over the world every day, especially in the developed countries with 0.5 million ton per year waste cooking oil are being generated in Malaysia alone. Such large amount of waste cooking oil production can create disposal problems and contamination to water and land resources if not disposed properly. The use of waste cooking oil as feedstock for bio diesel production will not only avoid the competition of the same oil resources for food and fuel but will also overcome the waste cooking oil disposal problems. However, waste cooking oil has high acid value, thus would require the oil to undergo esterification with an acid catalyst prior to transesterification with a base catalyst. Therefore, in this study, bifunctional catalyst supports were developed for one-step esterification-transesterification of waste cooking oil by varying the CeO 2 loading on γ-Al 2 O 3 . The bifunctional supports were then impregnated with 5 wt % Mo and characterized using N 2 adsorption-desorption isotherm to determine the surface area of the catalysts while temperature programmed desorption with NH 3 and CO 2 as adsorbents were used to determine the acidity and basicity of the catalysts. Results show that the γ-Al 2 O 3 -CeO 2 supported Mo catalysts are active for the one-step esterification-transesterification of waste cooking oil to produce bio diesel with the Mo/ γ-Al 2 O 3 -20 wt% CeO 2 as the most active catalyst. Optimization of process parameters for the production of bio diesel from waste cooking oil in the presence of this catalyst show that 81.1 % bio diesel yield was produced at 110 degree Celsius with catalyst loading of 7 wt %, agitation speed of 600 rpm, methanol to oil ratio of 30:1 and reaction period of 270 minutes. (author)

  6. Bifunctional electrodes with ir and Ru oxide mixtures and pt for unified regenerative cells; Electrodos bifuncionales basados en mezclas de oxidos de Ir y Ru con Pt para celdas regenerativas unificadas

    Energy Technology Data Exchange (ETDEWEB)

    Duron-Torres, S.M.; Escalante-Garcia, I.L. [Universidad Autonoma de Zacatecas, Zacatecas (Mexico); Cruz, J. C.; Arriaga-Hurtado; L.G. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Pedro Escobedo, Queretaro (Mexico)]. E-mail: duronsm@prodigy.net.mx

    2009-09-15

    Unified regenerative fuel cells (URFC) represent an attractive option to obtain hydrogen and generate energy using a compact device. Nevertheless, the fusion of a fuel cell (PEMFC) and a water electrolyzer continue to be a challenge because of the wide range of conditions to which this type of device is subject. Because of its kinetic characteristics, oxygen reduction reaction (ORR) in PEMFC and oxygen evolution reaction (OER) in PEMWE are the limiting stages of the URFC depending on the mode of operation. The primary focus of research related to URFC is the obtainment of bifunctional electrocatalysts that satisfactorily perform in both oxygen reactions and support the different working conditions found in a fuel cell and an electrolyzer. The present work contributes to the research on bifunctional electrocatalysts and shows some preliminary results from the electrochemical study of different Pt gcc, IrO{sub 2} and RuO{sub 2} mixtures supported in Ebonex® as oxygen electrodes. The electrochemical characterization with cyclic voltamperometry (CV), linear voltamperometry (LV) and electrochemical impedance spectroscopy (EIS) in H{sub 2}SO{sub 4} 0.5 M, in the absence and present of oxygen shows that Ebonex®-supported bifunctional electrodes IrO{sub 2}-Pt and RuO{sub 2}-Pt present reasonable electrocatalytic properties for oxygen evolution and reduction reactions and present the possibility of their use in an URFC. The Ir- based oxide electrodes show greater stability than ruthenium-oxide electrodes. [Spanish] Las celdas de combustible regenerativas unificadas (URFC) representan una atractiva opcion para la obtencion de hidrogeno y generacion de energia en un dispositivo compacto. Sin embargo, la fusion de una celda de combustible (PEMFC) y un electrolizador de agua (PEMWE) sigue siendo un reto por la amplia gama de condiciones a que se sujeta un dispositivo de este tipo. Por sus caracteristicas cineticas, la reaccion de reduccion de oxigeno (ORR) en la PEMFC y la

  7. Synergy of adsorption and visible-light photocatalytic degradation of methylene blue by a bifunctional Z-scheme heterojunction of WO{sub 3}/g-C{sub 3}N{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xin; Jin, Ailing; Jia, Yushuai, E-mail: ysjia@jxnu.edu.cn; Xia, Tonglin; Deng, Chenxin; Zhu, Meihua; Chen, Changfeng; Chen, Xiangshu, E-mail: cxs66cn@jxnu.edu.cn

    2017-05-31

    Highlights: • We designed and fabricated a novel WO{sub 3}/g-C{sub 3}N{sub 4} bifunctional Z-scheme photocatalyst. • Synergistic effect between adsorption and photocatalytic elimination for MB. • The integrated removal efficiency is governed by WO{sub 3} content in the composite. • Adsorption kinetics and isotherm for MB over the photocatalyst were investigated. • A novel Z-scheme photocatalytic mechanism is proposed. - Abstract: A novel bifunctional Z-scheme heterojunction possessing high adsorption and photocatalytic activity, WO{sub 3}/g-C{sub 3}N{sub 4} with well-defined morphology has been successfully synthesized by in-situ liquid phase process and characterized by various analytical techniques. The degradation experiments demonstrate that the Z-scheme photocatalyst shows a synergistic effect between adsorption and photocatalysis for the removal of methylene blue (MB) under visible-light irradiation, with the optimum adsorption and photocatalytic activity both found at 30 wt% WO{sub 3}/g-C{sub 3}N{sub 4}. Under illumination, the photodegradation performance of 30 wt% WO{sub 3}/g-C{sub 3}N{sub 4} is improved to 2.5 and 2.7 times that of pure g-C{sub 3}N{sub 4} and pure WO{sub 3}, respectively. The possible mechanism for the photocatalytic activity enhancement could be attributed to the formation of a Z-scheme heterojunction system based on the active species trapping experiments. Furthermore, the investigations of adsorption kinetics and isotherm show that the adsorption process can be well described by pseudo-second-order kinetic model, and the adsorption capacity of 30 wt% WO{sub 3}/g-C{sub 3}N{sub 4} is enhanced to 4 times that of pure WO{sub 3}, with a maximum of 97.00 mg g{sup −1} determined by Langmuir isotherm. As evidenced by N{sub 2} physisorption, zeta potential and time-resolved photoluminescence measurements, the significant enhancement of the integrated adsorption and photocatalytic degradation efficiency is mainly due to the

  8. Identification of the C-Terminal GH5 Domain from CbCel9B/Man5A as the First Glycoside Hydrolase with Thermal Activation Property from a Multimodular Bifunctional Enzyme.

    Directory of Open Access Journals (Sweden)

    Rong Wang

    Full Text Available Caldicellulosiruptor bescii encodes at least six unique multimodular glycoside hydrolases crucial for plant cell wall polysaccharides degradation, with each having two catalytic domains separated by two to three carbohydrate binding modules. Among the six enzymes, three have one N- or C-terminal GH5 domain with identical amino acid sequences. Despite a few reports on some of these multimodular enzymes, little is known about how the conserved GH5 domains behave, which are believed to be important due to the gene duplication. We thus cloned a representative GH5 domain from the C-terminus of a multimodular protein, i.e. the bifunctional cellulase/mannanase CbCel9B/Man5A which has been reported, and expressed it in Escherichia coli. Without any appending CBMs, the recombinant CbMan5A was still able to hydrolyze a variety of mannan substrates with different backbone linkages or side-chain decorations. While CbMan5A displayed the same pH optimum as CbCel9B/Man5A, it had an increased optimal temperature (90°C and moreover, was activated by heating at 70°C and 80°C, a property not ever reported for the full-length protein. The turnover numbers of CbMan5A on mannan substrates were, however, lower than those of CbCel9B/Man5A. These data suggested that evolution of CbMan5A and the other domains into a single polypeptide is not a simple assembly; rather, the behavior of one module may be affected by the other ones in the full-length enzyme. The differential scanning calorimetry analysis further indicated that heating CbMan5A was not a simple transition state process. To the best knowledge of the authors, CbMan5A is the first glycoside hydrolase with thermal activation property identified from a multimodular bifunctional enzyme.

  9. Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

    Science.gov (United States)

    Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

    2018-01-01

    Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

  10. Fabrication of α-Fe{sub 2}O{sub 3}/TiO{sub 2} bi-functional composites with hierarchical and hollow structures and their application in water treatment

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yinhui, E-mail: lillian09281@hotmail.com; Zhang, Na; Chen, Jianxin, E-mail: chjx2000@126.com; Li, Ruijuan; Li, Liang; Li, Kunyu [Hebei University of Technology, School of Marine Science and Engineering, Engineering Research Center of Seawater Utilization Technology, Ministry of Education (China)

    2016-02-15

    The α-Fe{sub 2}O{sub 3}/TiO{sub 2} bi-functional composites with hierarchical and hollow structures are fabricated through a hydrothermal route. The adsorption performance and photocatalytic activity of the composites towards Pb{sup 2+} are investigated in this work. Different adsorption kinetics models and equilibrium models are used to explore the adsorption behavior of hierarchical α-Fe{sub 2}O{sub 3}/TiO{sub 2} hollow spheres. Experimental data show that adsorption kinetics of the hierarchical α-Fe{sub 2}O{sub 3}/TiO{sub 2} hollow spheres can be fitted well by the pseudo-second-order model, while the isothermal data can be perfectly described by the Langmuir adsorption model. The maximum adsorption capacity of the hierarchical α-Fe{sub 2}O{sub 3}/TiO{sub 2} hollow spheres is 32.36 mg g{sup −1}. Moreover, the hierarchical α-Fe{sub 2}O{sub 3}/TiO{sub 2} hollow spheres possess photocatalytic oxidation character under simulated solar light irradiation. The results demonstrate that the hierarchical α-Fe{sub 2}O{sub 3}/TiO{sub 2} hollow spheres, as effective and cheap materials, can be applied to the removal of heavy metal ions from wastewater.

  11. Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery.

    Science.gov (United States)

    Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

    2016-09-20

    α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm(-2). At 1.0 V of cell voltage, a current density of 324 mA cm(-2) is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm(-2), and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte.

  12. Chemistry of bifunctional photoprobes. 3 -- Correlation between the efficiency of CH insertion by photolabile chelating agents and lifetimes of singlet nitrenes by flash photolysis: First example of photochemical attachment of 99mTc-complex with human serum albumin

    International Nuclear Information System (INIS)

    Pandurangi, R.S.; Lusiak, P.; Kuntz, R.R.; Volkert, W.A.; Rogowski, J.; Platz, M.S.

    1998-01-01

    Systematic functionalization of perfluoroaryl azides with chelating agents capable of complexing transition metals produces a new class of bifunctional photolabile chelating agents (BFPCAs). The strategy is shield the azide functionality from the electronic and steric influence of the electron-rich metal Pd through ester and amide bridges raised CH insertion efficiency to unprecedented levels (>92%) in a model solvent (cyclohexane). In contrast, perfluoroaryl azides attached to chelating agents via hydrazones show no significant CH insertion in cyclohexane upon photolysis. Measurements of the lifetimes of the singlet nitrenes derived from these agents by flash photolysis techniques correlate well with the efficiency of CH insertion by demonstrating longer lifetimes (10--50 times) for singlet nitrenes derived from azidotetrafluorinated esters and amides compared with the related hydrazones, which failed to yield significant CH insertion. A representative BFPCA 12 is chelated to diagnostic radionuclide 99m Tc and covalently attached to human serum albumin via photochemical activation extending the favorable bimolecular insertion characteristics of BFPCA to tracer level concentrations in buffer conditions. Flash photolysis experiments correlate singlet nitrene lifetimes with the efficiency of intermolecular insertion reactions. This work provides new photo-cross-linking technology, useful in radiodiagnostics and radiotherapy in nuclear medicine

  13. A Bifunctional Intronic Element Regulates the Expression of the Arginine/Lysine Transporter Cat-1 via Mechanisms Involving the Purine-rich Element Binding Protein A (Purα)*

    Science.gov (United States)

    Huang, Charlie C.; Chiribau, Calin-Bogdan; Majumder, Mithu; Chiang, Cheng-Ming; Wek, Ronald C.; Kelm, Robert J.; Khalili, Kamel; Snider, Martin D.; Hatzoglou, Maria

    2009-01-01

    Expression of the arginine/lysine transporter Cat-1 is highly induced in proliferating and stressed cells via mechanisms that include transcriptional activation. A bifunctional INE (intronic element) within the first intron of the Cat-1 gene was identified and characterized in this study. The INE had high sequence homology to an amino acid response element and was shown to act as a transcriptional enhancer in unstressed cells by binding the transcription factor, purine-rich element binding protein A (Purα). During endoplasmic reticulum stress, binding of Purα to the INE decreased; the element acted as a positive regulator in early stress by binding of the transcription factor ATF4 and as a negative regulator in prolonged stress by binding the stress-induced C/EBP family member, CHOP. We conclude that transcriptional control of the Cat-1 gene is tightly controlled by multiple cis-DNA elements, contributing to regulation of cationic amino acid transport for cell growth and proliferation. In addition, we propose that genes may use stress-response elements such as the INE to support basal expression in the absence of stress. PMID:19720825

  14. Comparative Evaluation of Using NOTA and DOTA Derivatives as Bifunctional Chelating Agents in the Preparation of 68Ga-Labeled Porphyrin: Impact on Pharmacokinetics and Tumor Uptake in a Mouse Model.

    Science.gov (United States)

    Guleria, Mohini; Das, Tapas; Amirdhanayagam, Jeyachitra; Sarma, Haladhar D; Dash, Ashutosh

    2018-02-01

    Both NOTA (1,4,7-triazacyclononane-1,4,7-triacetic acid) and DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) derivatives have been used as bifunctional chelating agents (BFCAs) for the preparation of 68 Ga-labeled target-specific agents having potential for positron emission tomography (PET) imaging of cancerous lesions. In the present work, the authors have attempted a comparative pharmacokinetic evaluation between 68 Ga-labeled porphyrins prepared using NOTA and DOTA derivatives as the BFCAs. A symmetrical porphyrin derivative, 5,10,15,20-tetrakis(p-carboxymethyleneoxyphenyl)porphyrin, was synthesized and coupled with two different BFCAs viz. p-NH 2 -benzyl-NOTA and p-NH 2 -benzyl-DOTA. Both the porphyrin-BFCA conjugates were radiolabeled with 68 Ga. A comparative bioevaluation involving pharmacokinetics and tumor affinity was performed in a tumor-bearing small animal model. Gallium-68-labeled porphyrin-amido-benzyl-NOTA and porphyrin-amido-benzyl-DOTA complexes were prepared with high radiochemical purity. Both radiolabeled complexes exhibited almost similar stability in human serum and near-identical tumor affinity and pharmacokinetic behavior in animal studies. The present study demonstrates that the pharmacokinetic behavior of 68 Ga-labeled porphyrin derivatives, prepared using either NOTA or DOTA derivatives as BFCAs, remains almost identical and hence both NOTA and DOTA derivatives could be considered equivalent for developing 68 Ga-based PET agents for imaging of tumorous lesions.

  15. Synthesis and catalytic activity of ruthenium complexes modified with chiral racemic per- and polyfluorooxaalkanoates

    Czech Academy of Sciences Publication Activity Database

    Lipovská, P.; Rathouská, L.; Šimůnek, O.; Hošek, J.; Kolaříková, V.; Rybáčková, M.; Cvačka, Josef; Svoboda, Martin; Kvíčala, J.

    2016-01-01

    Roč. 191, Nov (2016), s. 14-22 ISSN 0022-1139 Institutional support: RVO:61388963 Keywords : racemic * chiral * ruthenium complex * perfluorooxaalkanoate * polyfluorooxaalkanoate Subject RIV: CC - Organic Chemistry Impact factor: 2.101, year: 2016

  16. Hydrothermal synthesis of superparamagnetic and red luminescent bifunctional Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er core@shell monodisperse nanoparticles and their subsequent ligand exchange in water

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Zhenli; Du, Sinan; Luo, Yang; Liao, Zhijian; Zuo, Fang, E-mail: polymerzf@swun.cn; Luo, Jianbin; Liu, Dong

    2016-08-15

    Graphical abstract: An efficient hydrothermal method was used to fabricate the superparamagnetic and red luminescent bifunctional Fe{sub 3}O{sub 4}@Mn{sup 2(*)+}-doped NaYF{sub 4}:Yb/Er nanoparticles (NPs) with core@shell structures through a seed-growth procedure. Then using PEG phosphate ligand to displace oleate from the as-synthesized NPs, hydrophilic Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er NPs with good water solubility are obtained. - Highlights: • Homogeneous size distribution of magnetic-upconversion core@shell structured nanoparticles (NPs) were synthesized. • The core@shell nanostructures were obtained by seed-growth method. • The oleic acid coated Fe{sub 3}O{sub 4} NPs were used as seeds and cores. • The magnetic-upconversion NPs emitted red luminescence under a 980 nm laser. • Synthesized magnetic-upconversion NPs were phase transferred using ligand exchange process. - Abstract: We report the use of an efficient hydrothermal method to synthesize superparamagnetic and red luminescent bifunctional Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er nanoparticles (NPs) with core@shell structures via a seed-growth procedure. Oleic acid coated Fe{sub 3}O{sub 4} (OA-Fe{sub 3}O{sub 4}) NPs were initially synthesized using a coprecipitation method. The as-synthesized OA-Fe{sub 3}O{sub 4} NPs were then used as seeds, on which the red upconversion luminescent shell (Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er) was formed. Furthermore, hydrophobic to hydrophilic surface modification of the Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er NPs was achieved via a ligand exchange method where oleic acid was displaced by a PEG phosphate ligand [PEG = poly(ethylene glycol)]. These materials were characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, and vibrating sample magnetometry (VSM). The Fe{sub 3}O{sub 4} cores were uniformly coated with a Mn{sup 2+}-doped NaYF{sub 4}:Yb

  17. Biochemical Characterization of Mycobacterium smegmatis RnhC (MSMEG_4305), a Bifunctional Enzyme Composed of Autonomous N-Terminal Type I RNase H and C-Terminal Acid Phosphatase Domains.

    Science.gov (United States)

    Jacewicz, Agata; Shuman, Stewart

    2015-08-01

    Mycobacterium smegmatis encodes several DNA repair polymerases that are adept at incorporating ribonucleotides, which raises questions about how ribonucleotides in DNA are sensed and removed. RNase H enzymes, of which M. smegmatis encodes four, are strong candidates for a surveillance role. Here, we interrogate the biochemical activity and nucleic acid substrate specificity of M. smegmatis RnhC, a bifunctional RNase H and acid phosphatase. We report that (i) the RnhC nuclease is stringently specific for RNA:DNA hybrid duplexes; (ii) RnhC does not selectively recognize and cleave DNA-RNA or RNA-DNA junctions in duplex nucleic acid; (iii) RnhC cannot incise an embedded monoribonucleotide or diribonucleotide in duplex DNA; (iv) RnhC can incise tracts of 4 or more ribonucleotides embedded in duplex DNA, leaving two or more residual ribonucleotides at the cleaved 3'-OH end and at least one or two ribonucleotides on the 5'-PO4 end; (v) the RNase H activity is inherent in an autonomous 140-amino-acid (aa) N-terminal domain of RnhC; and (vi) the C-terminal 211-aa domain of RnhC is an autonomous acid phosphatase. The cleavage specificity of RnhC is clearly distinct from that of Escherichia coli RNase H2, which selectively incises at an RNA-DNA junction. Thus, we classify RnhC as a type I RNase H. The properties of RnhC are consistent with a role in Okazaki fragment RNA primer removal or in surveillance of oligoribonucleotide tracts embedded in DNA but not in excision repair of single misincorporated ribonucleotides. RNase H enzymes help cleanse the genome of ribonucleotides that are present either as ribotracts (e.g., RNA primers) or as single ribonucleotides embedded in duplex DNA. Mycobacterium smegmatis encodes four RNase H proteins, including RnhC, which is characterized in this study. The nucleic acid substrate and cleavage site specificities of RnhC are consistent with a role in initiating the removal of ribotracts but not in single-ribonucleotide surveillance. Rnh

  18. Characterization of Runella slithyformis HD-Pnk, a bifunctional DNA/RNA end-healing enzyme composed of an N-terminal 2',3' -phosphoesterase HD domain and a C-terminal 5' -OH polynucleotide kinase domain.

    Science.gov (United States)

    Munir, Annum; Shuman, Stewart

    2016-11-28

    5' and 3' end healing are key steps in nucleic acid break repair in which 5' -OH ends are phosphorylated by a polynucleotide kinase and 3' -PO 4 or 2',3' -cyclic-PO 4 ends are hydrolyzed by a phosphoesterase to generate the 5' -PO 4 and 3' -OH termini required for sealing by classic polynucleotide ligases. End healing and sealing enzymes are present in diverse bacterial taxa, often organized as modular units within a single multifunctional polypeptide or as subunits of a repair complex. Here we identify and characterize Runella slithyformis HD-Pnk as a novel bifunctional end-healing enzyme composed of an N-terminal 2',3' -phosphoesterase HD domain and a C-terminal 5' -OH polynucleotide kinase P-loop domain. HD-Pnk phosphorylates 5' -OH polynucleotides (9-mers or longer) in the presence of magnesium and any NTP donor. HD-Pnk dephosphorylates RNA 2',3' -cyclic phosphate, RNA 3' -phosphate, RNA 2' -phosphate, and DNA 3' -phosphate ends in the presence of a transition metal cofactor, which can be nickel, copper or cobalt. HD-Pnkp homologs are present in genera from eleven bacterial phyla and are often encoded in an operon with a putative ATP-dependent polynucleotide ligase. The present study provides insights to the diversity of nucleic acid repair strategies via the characterization of Runella slithyformis HD-Pnkp as the exemplar of a novel clade of dual 5' and 3' end-healing enzymes that phosphorylate 5' -OH termini and dephosphorylate 2',3' -cyclic-PO 4 , 3' -PO 4 , and 2' -PO 4 ends. The distinctive feature of HD-Pnk is its domain composition: a fusion of an N-terminal HD phosphohydrolase module to a C-terminal P-loop polynucleotide kinase module. Homologs of Runella HD-Pnk with the same domain composition, domain order, and similar polypeptide size are distributed widely among genera from eleven bacterial phyla. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  19. Synthesis of a novel 'smart' bifunctional chelating agent 1-(2-[beta,D-galactopyranosyloxy]ethyl)-7-(1-carboxy-3-[4-aminophenyl]propyl)-4,10-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (Gal-PA-DO3A-NH2) and its Gd(III) complex.

    Science.gov (United States)

    Wardle, Nick J; Herlihy, Amy H; So, Po-Wah; Bell, Jimmy D; Bligh, S W Annie

    2007-07-15

    A new synthetic pathway to 1-(2-[beta,D-galactopyranosyloxy]ethyl)-7-(1-carboxy-3-[4-aminophenyl]propyl)-4,10-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (Gal-PA-DO3A-NH2) and 1-(2-[beta,D-galactopyranosyloxy]ethyl)-4,7,10-tris(carboxymethyl)-1, 4,7,10-tetraazacyclododecane (Gal-DO3A) chelating agents was developed involving full hydroxyl- and carboxyl-group protection in precursors to product. Two sequences of cyclen-N-functionalisation were subsequently investigated, one successfully, towards synthesis of the novel 'smart' bifunctional Gal-PA-DO3A-NH2 chelate. The longitudinal proton relaxivities of the neutral [Gd-(Gal-PA-DO3A-NH2)] and [Gd-(Gal-DO3A)] complexes were increased by 28% and 37% in the presence of beta-galactosidase, respectively.

  20. Paclitaxel conjugated Fe{sub 3}O{sub 4}@LaF{sub 3}:Ce{sup 3+},Tb{sup 3+} nanoparticles as bifunctional targeting carriers for Cancer theranostics application

    Energy Technology Data Exchange (ETDEWEB)

    Mangaiyarkarasi, Rajendiran; Chinnathambi, Shanmugavel; Karthikeyan, Subramani; Aruna, Prakasarao; Ganesan, Singaravelu, E-mail: sganesan@annauniv.edu

    2016-02-01

    The bi-functional Chitosan functionalized magnetite doped luminescent rare earth nanoparticles (Fe{sub 3}O{sub 4}@LaF{sub 3}: Ce{sup 3+},Tb{sup 3+}/chi NPs) as a carrier of paclitaxel (PTX) drug was designed using a co-precipitation and facile direct precipitation method. The synthesized nanoparticles are spherical in shape with a typical diameter of 19–37 nm respectively. They are water soluble, super paramagnetic and biocompatible, in which the amino groups on the nanoparticles surface are used for the conjugation with an anticancer drug, paclitaxel. The nature of PTX binding with Fe{sub 3}O{sub 4}@LaF{sub 3}: Ce{sup 3+},Tb{sup 3+}/chi nanoparticles were studied using X-ray diffraction, vibrating sample magnetometer and scanning electron micrograph. The nature of interactions between PTX and Fe{sub 3}O{sub 4}@LaF{sub 3}: Ce{sup 3+},Tb{sup 3+}/chi NPs due to complex formation were conceded out by various spectroscopic methods viz., UV–visible, steady state and excited state fluorescence spectroscopy. The photo-physical characterization reveals that the adsorption and release of PTX from Fe{sub 3}O{sub 4}@LaF{sub 3}:Tb{sup 3+}/chi nanoparticles is quicker when compared with other nanoparticles and also confirms that this may be due to the hydrogen bond formation between the hydroxyl group of drug and amino group of nanoparticles respectively. The maximum loading capacity and entrapment efficiency of 83.69% and 80.51% were attained at a ratio of 5:8 of PTX and Fe{sub 3}O{sub 4}@LaF{sub 3}: Ce{sup 3+},Tb{sup 3+}/chi NPs respectively. In addition with that, antitumoral activity study of PTX conjugated Fe{sub 3}O{sub 4}@LaF{sub 3}:Tb{sup 3+}/chi nanoparticles exhibits increased cytotoxic effects on A549 lung cancer cell lines than that of unconjugated PTX. - Highlights: • Fe{sub 3}O{sub 4}@LaF{sub 3}: Ce{sup 3+},Tb{sup 3+}/chi nanoparticles as a carrier of paclitaxel. • These particles are water soluble, super paramagnetic and biocompatible. • The maximum

  1. A multi-cloak bifunctional device

    Science.gov (United States)

    Raza, Muhammad; Liu, Yichao; Ma, Yungui

    2015-01-01

    Invisibility cloak has attracted the attention of electromagnetic researchers due to its magical properties and marvelous potential applications in the field of applied physics and engineering. Recently, a multiphysics cloaking has put the new spirit into this field. In this paper, we introduce a device, composed of three shells and each shell works as an invisibility cloak for a specific physical phenomenon. Following this technique, a number of cloaks with different implementation approaches can be proposed for distinct physical phenomena in a single structure. Here, we restrict ourselves for the case of two physical behaviors: thermal and electrical conductivities. This type of multi-cloaking structure can be best used in mechanically designed structures to better control heating and electrical effects.

  2. Bifunctional cobalt F-T catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.G.; Coughlin, P.K.; Yang, C.L.; Rabo, J.A.

    1986-03-01

    Results on the catalytic screening of Fischer-Tropsch catalysts containing shape selective components are reported. Catalysts consist of promoted cobalt intimately contacted with Union Carbide molecular sieves and were tested using a Berty type internally recycled reactor. Methods of preparation, promoters and shape selective components were varied and aimed at improving catalyst performance. Catalysts were developed demonstrating high C/sub 5/ + yields with high olefin content and low methane production while maintaining stability under both low and high H/sub 2/:CO ratio conditions.

  3. Bifunctional Bisphosphonates for Delivering Biomolecules to Bone

    Science.gov (United States)

    2012-01-13

    formation could be analyzed after a few weeks. Scanning electron microscopy (SEM), FT-IR, X- ray Diffraction (XRD), and high-resolution X- ray computed...Bisphosphonates: Mode of action and pharmacology, Pediatrics 119 Suppl 2, S150-162. 36. Roelofs, A. J., Thompson, K., Gordon, S., and Rogers, M. J...E., Mahmood, A., Jones, A. G., Cantley, L. C., and Frangioni, J. V. (2001) In vivo near- infrared fluorescence imaging of osteoblastic activity

  4. New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

    OpenAIRE

    Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

    2015-01-01

    Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet meta...

  5. Influence of temperature and light intensity on Ru(II) complex based organic-inorganic device

    International Nuclear Information System (INIS)

    Asubay, Sezai; Durap, Feyyaz; Aydemir, Murat; Baysal, Akin; Ocak, Yusuf Selim; Tombak, Ahmet

    2016-01-01

    An organic-inorganic junction was fabricated by forming [Ru(Cy_2PNHCH_2-C_4H_3O)(η"6-p-cymene)Cl_2] complex thin film using spin coating technique on n-Si and evaporating Au metal on the film. It was seen that the structure had perfect rectification property. Current-voltage (I-V) measurements were carried out in dark and under various illumination conditions (between 50-100 mW/cm"2) and with the temperature range from 303 to 380 K. The structure showed unusually forward and reverse bias temperature and light sensing behaviors. It was seen that the current both in forward and reverse bias increased with the increase in light intensity and temperature.

  6. Facile synthesis of RuII Schiff base complexes: spectral characterization and antimicrobial applications

    International Nuclear Information System (INIS)

    Arunachalam, S.; Padma Priya, N.; Shahul Meeran, H.

    2014-01-01

    Diamagnetic ruthenium (II) complexes of the type (RuCl (CO) (pyridine) (L)) (where L = monobasic tridentate Schiff base ligands) were synthesized by the reactions of Schiff bases derived from the reactions of o-aminobenzoic acid and Knovenegal condensate of β - ketoesters and appropriate ruthenium metal precursor (RuHCl (CO) (PPh 3 ) 2 (py)). Elemental analyses and spectral (FT-IR, UV-Vi s and 1 H, 31 P NMR) studies of all the new synthesized complexes suggest the presence of an octahedral environment around the Ru II ion. Cyclic voltammograms of all the complexes display oxidation and reduction potentials. Superoxide dismutase activity (SOD) of these complexes has also been examined. These complexes were also subjected to study their biocidal activity against Staphylococcus epidermidis, Escherichia coli, Botrytis cinerea and Aspergillus niger. (author)

  7. Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex

    Energy Technology Data Exchange (ETDEWEB)

    Song, Na [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States); Concepcion, Javier J. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Binstead, Robert A. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Rudd, Jennifer A. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Vannucci, Aaron K. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry; Dares, Christopher J. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Coggins, Michael K. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Meyer, Thomas J. [Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry

    2015-04-06

    In aqueous solution above pH 2.4 with 4% (vol/vol) CH3CN, the complex [RuII(bda)(isoq)2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [RuII(CO2-bpy-CO2$-$)(isoq)2(NCCH3)], as shown by 1H and 13C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO43–, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.

  8. The Spectroscopic and Conductive Properties of Ru(II Complexes with Potential Anticancer Properties

    Directory of Open Access Journals (Sweden)

    Adebayo A. Adeniyi

    2014-01-01

    Full Text Available Different density functional methods (DFT have been used to optimize and study the chemistry of five potential anticancer complexes in terms of their electronic, conductive, and spectroscopic properties. Many of the computed properties in addition to the IR and QTAIM analysis of the NMR are dipole moment vector (μi, linear polarizability tensor (αij, first hyperpolarizability tensors (βijk, polarizability exaltation index (Γ, and chemical hardness (η of the complexes. Stable low energy geometries are obtained using basis set with effective core potential (ECP approximation but, in the computation of atomic or molecular properties, the metal Ru atom is better treated with higher all electron basis set like DGDZVP. The spectroscopic features like the IR of the metal-ligand bonds and the isotropic NMR shielding tensor of the coordinated atoms are significantly influenced by the chemical environment of the participating atoms. The carboxylic and pyrazole units are found to significantly enhance the polarizabilities and hyperpolarizabilities of the complexes while the chloride only improves the polarity of the complexes. Fermi contacts (FC have the highest effect followed by the PSO among all the four Ramsey terms which defined the total spin-spin coupling constant J (HZ of these complexes.

  9. Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom

    Science.gov (United States)

    Ding, Xin; Tuikka, Matti; Hirva, Pipsa; Haukka, Matti

    2017-09-01

    Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2'-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]ṡI2 with only one NCSṡṡṡI2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCSṡṡṡI2 and SCNṡṡṡI2 bonding modes. The reason for the observed NCSṡṡṡI2 mode lies most probably in the more favourable packing effects rather than energetic preferences between NCSṡṡṡI2 and SCNṡṡṡI2 contacts.

  10. DNA interactions of dinuclear RuII arene antitumor complexes in cell-free media

    Czech Academy of Sciences Publication Activity Database

    Nováková, Olga; Nazarov, A.A.; Hartinger, Ch.G.; Keppler, B.K.; Brabec, Viktor

    2009-01-01

    Roč. 77, č. 3 (2009), s. 364-374 ISSN 0006-2952 R&D Projects: GA MŠk(CZ) LC06030; GA MŠk(CZ) ME08017; GA MŠk(CZ) OC08003; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN200200651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : dinuclear ruthenium complex * DNA * cross-links Subject RIV: BO - Biophysics Impact factor: 4.254, year: 2009

  11. Thermochemical behaviour of Ru(II) complex–SiO2 microcomposites

    Indian Academy of Sciences (India)

    WINTEC

    both the gel spectra are to be expected accounting for the complex molar mass of ..... (ii) TEOS + OtEOS-produced gel: No principle diffe- rences in the DTG, DTA ... Acknowledgements. The study was carried out with the financial support from.

  12. Synthesis, DNA-binding and photocleavage studies of Ru(II ...

    Indian Academy of Sciences (India)

    Administrator

    (Finngan MAT, USA) using CH3CN as the mobile phase. ..... cence can be quenched, at least partially, by the ad- dition of a ... in good agreement with the linear Stern–Volmer ... helix, resulting in the decrease of its effective length and its ...

  13. A sensor for acetaminophen in a blood medium using a Cu(II)-conducting polymer complex modified electrode

    International Nuclear Information System (INIS)

    Boopathi, Mannan; Won, Mi-Sook; Shim, Yoon-Bo

    2004-01-01

    Complexation of Cu ions in a terthiophene carboxylic acid (TTCA) polymer film resulted an enhanced anodic current for acetaminophen oxidation when compared to polymer coated and bare glassy carbon electrodes in human blood and buffer media. Scanning electron microscopy (SEM) and ESCA experiments indicate the involvement of copper in the electrocatalytic oxidation of acetaminophen. No interference was observed from other biologically important and phenolic compounds used with this modified electrode. Especially, the non-interference from N-acetylcysteine, an antidote for the treatment of acetaminophen poisoning, reveals the proposed method's superiority in medicinal applications. In addition, the present modified electrode avoids surface fouling at higher concentrations of acetaminophen. The calibration range obtained with CV was based between 2.0x10 -5 and 5.0x10 -3 M [r 2 =0.997 (n=5, R.S.D.=2.5%); DL=5.0x10 -6 M (S/N=3)]. The analytical utility of the modified electrode was achieved by analyzing the content of acetaminophen in different drugs without pretreatment using CV and amperometric techniques

  14. Complex Modified Hybrid Projective Synchronization of Different Dimensional Fractional-Order Complex Chaos and Real Hyper-Chaos

    Directory of Open Access Journals (Sweden)

    Jian Liu

    2014-11-01

    Full Text Available This paper introduces a type of modified hybrid projective synchronization with complex transformationmatrix (CMHPS for different dimensional fractional-order complex chaos and fractional-order real hyper-chaos. The transformationmatrix in this type of chaotic synchronization is a non-square matrix, and its elements are complex numbers. Based on the stability theory of fractional-order systems, by employing the feedback control technique, necessary and sufficient criteria on CMHPS are derived. Furthermore, CMHPS between fractional-order real hyper-chaotic Rössler system and other two different dimensional fractional-order complex Lorenz-like chaotic systems is provided as two examples to discuss reduced order and increased order synchronization, respectively.

  15. Chloroplatinum(II) complex-modified MWCNTs paste electrode for electrochemical determination of mercury in skin lightening cosmetics

    International Nuclear Information System (INIS)

    Isa, Illyas Md; Saidin, Mohamad Idris; Ahmad, Mustaffa; Hashim, Norhayati; Bakar, Suriani Abu; Ali, Noorshida Mohd; Si, Suyanta M.

    2017-01-01

    The chemically modified multiwalled carbon nanotubes (MWCNTs) paste electrode with chloroplatinum(II) complex for the determination of mercury is presented. The chloroplatinum(II) complex was characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transforms infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM). The capability of the electron transfer rate on the surface of modified electrode evaluated is by electrochemical impedance spectroscopy (EIS). The square wave stripping voltammetry (SWSV) technique was employed to investigate the performance of chloroplatinum(II) complex-MWCNTs paste electrode for determination of mercury. Several operational parameters such as the composition ratios of the electrode, type of supporting electrolyte, pH of the solution, and the SWSV parameters were thoroughly investigated. Under optimal conditions, the linear range obtained was from 5.0 μM to 0.1 mM with limit detection of 3.7 μM. The interference from other heavy metals such as Ca 2+ , Mg 2+ , Ni 2+ , Zn 2+ , Cd 2+ , Co 2+ , Ba 2+ , Mn 2+ , and Ce 3+ did not influence the electrochemical response. The chloroplatinum(II) complex-MWCNTs paste electrode was successfully applied to determine mercury in skin lightening cosmetics with a good recovery (98.9%–101.1%).

  16. Luminescence and magnetic properties of novel nanoparticle-sheathed 3D Micro-Architectures of Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) for bifunctional application

    Science.gov (United States)

    Krishnan, Rajagopalan; Thirumalai, Jagannathan; Kathiravan, Arunkumar

    2015-01-01

    For the first time, we report the successful synthesis of novel nanoparticle-sheathed bipyramid-like and almond-like Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) 3D hierarchical microstructures through a simple disodium ethylenediaminetetraacetic acid (Na2EDTA) facilitated hydrothermal method. Interestingly, time-dependent experiments confirm that the assembly-disassembly process is responsible for the formation of self-aggregated 3D architectures via Ostwald ripening phenomena. The resultant products are characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and magnetic measurements. The growth and formation mechanisms of the self-assembled 3D micro structures are discussed in detail. To confirm the presence of all the elements in the microstructure, the energy loss induced by the K, L shell electron ionization is observed in order to map the Fe, Gd, Mo, O, and Eu components. The photo luminescence properties of Fe0.5R0.5(MoO4)1.5 doped with Eu3+, Tb3+, Dy3+ are investigated. The room temperature and low temperature magnetic properties suggest that the interaction between the local-fields introduced by the magnetic Fe3+ ions and the R3+ (La, Gd) ions in the dodecahedral sites determine the magnetism in Fe0.5R0.5(MoO4)1.5:Eu3+. This work provides a new approach to synthesizing the novel Fe0.5R0.5(MoO4)1.5:Ln3+ for bi-functional magnetic and luminescence applications.

  17. Characterization of Runella slithyformis HD-Pnk, a Bifunctional DNA/RNA End-Healing Enzyme Composed of an N-Terminal 2′,3′-Phosphoesterase HD Domain and a C-Terminal 5′-OH Polynucleotide Kinase Domain

    Science.gov (United States)

    Munir, Annum

    2016-01-01

    ABSTRACT 5′- and 3′-end-healing reactions are key steps in nucleic acid break repair in which 5′-OH ends are phosphorylated by a polynucleotide kinase (Pnk) and 3′-PO4 or 2′,3′-cyclic-PO4 ends are hydrolyzed by a phosphoesterase to generate the 5′-PO4 and 3′-OH termini required for sealing by classic polynucleotide ligases. End-healing and sealing enzymes are present in diverse bacterial taxa, often organized as modular units within a single multifunctional polypeptide or as subunits of a repair complex. Here we identify and characterize Runella slithyformis HD-Pnk as a novel bifunctional end-healing enzyme composed of an N-terminal 2′,3′-phosphoesterase HD domain and a C-terminal 5′-OH polynucleotide kinase P-loop domain. HD-Pnk phosphorylates 5′-OH polynucleotides (9-mers or longer) in the presence of magnesium and any nucleoside triphosphate donor. HD-Pnk dephosphorylates RNA 2′,3′-cyclic phosphate, RNA 3′-phosphate, RNA 2′-phosphate, and DNA 3′-phosphate ends in the presence of a transition metal cofactor, which can be nickel, copper, or cobalt. HD-Pnk homologs are present in genera from 11 bacterial phyla and are often encoded in an operon with a putative ATP-dependent polynucleotide ligase. IMPORTANCE The present study provides insights regarding the diversity of nucleic acid repair strategies via the characterization of Runella slithyformis HD-Pnk as the exemplar of a novel clade of dual 5′- and 3′-end-healing enzymes that phosphorylate 5′-OH termini and dephosphorylate 2′,3′-cyclic-PO4, 3′-PO4, and 2′-PO4 ends. The distinctive feature of HD-Pnk is its domain composition, i.e., a fusion of an N-terminal HD phosphohydrolase module and a C-terminal P-loop polynucleotide kinase module. Homologs of Runella HD-Pnk with the same domain composition, same domain order, and similar polypeptide sizes are distributed widely among genera from 11 bacterial phyla. PMID:27895092

  18. Pt{sub X}Ru{sub Y}Ir{sub Z} as a bifunctional electrocatalyst for oxygen reduction reaction in a PEM fuel cell; Pt{sub X}Ru{sub Y}Ir{sub Z} como electrocatalizador bifuncional para la reaccion redox del oxigeno en una celda tipo PEM

    Energy Technology Data Exchange (ETDEWEB)

    Morales, L.; Fernandez, A.M. [Centro de Investigacion en Energia, Universidad Nacional Autonoma de Mexico, Temixco, Morelos (Mexico)]. E-mail: limos@cie.unam.mx; Cano, U. [Instituto de Investigaciones Electricas, Cuernavaca, Morelos (Mexico)

    2009-09-15

    This work presents the synthesis and characterization of the ternary material Pt{sub X}Ru{sub Y}Ir{sub Z}, obtained by chemical reduction with NaBH{sub 4}. Two different atomic compositions were developed (sample A and B) in order to observe the kinetic effect, as suggested by the combinatorial libraries. The main objective of this synthesis is to study the oxygen reduction reaction (ORR and OER) and its potential use in the construction of a bifunctional catalyst. In addition, each of the metals are synthesized separately using the same technique in order to make the corresponding comparison. The compounds obtained were characterized by sweep electron microscopy, x-ray diffraction and composition using fluorescence and energy-dispersive x-ray spectroscopy. The results showed a displacement of the x-ray diffraction peaks for Ir and Pt in sample A, and displacement in sample B for Ru and Ir peaks. These changes suggest the possible formation of a solid solution substitution. Separate cyclic and linear voltamperometry studies were performed for the oxygen reduction and release reactions. The electrochemical analysis showed improved kinetic behavior when combining the three metals according to the composition of sample B. [Spanish] En este trabajo se presenta la sintesis y caracterizacion del material ternario Pt{sub X}Ru{sub Y}Ir{sub Z}, elaborado por la tecnica de Reduccion Quimica utilizando al NaBH{sub 4}. Se elaboraron dos composiciones atomicas diferentes (Muestra A y B) con el fin de observar el efecto cinetico, como lo sugieren las librerias combinatorias. El objetivo principal de esta sintesis es para el estudio de la Reaccion Redox del Oxigeno (RRO y REO) y su potencial uso para la construccion de un catalizador bifuncional. Asi mismo, se realiza la sintesis de cada uno de los metales por separado empleando la misma tecnica, con el proposito de realizar la comparacion correspondiente. Los compuestos obtenidos se caracterizaron por Microscopia Electronica de

  19. Surface Grafting of Ru(II) Diazonium-Based Sensitizers on Metal Oxides Enhances Alkaline Stability for Solar Energy Conversion.

    Science.gov (United States)

    Bangle, Rachel; Sampaio, Renato N; Troian-Gautier, Ludovic; Meyer, Gerald J

    2018-01-24

    The electrografting of [Ru(ttt)(tpy-C 6 H 4 -N 2 + )] 3+ , where "ttt" is 4,4',4″-tri-tert-butyl-2,2':6',2″-terpyridine, was investigated on several wide band gap metal oxide surfaces (TiO 2 , SnO 2 , ZrO 2 , ZnO, In 2 O 3 :Sn) and compared to structurally analogous sensitizers that differed only by the anchoring group, i.e., -PO 3 H 2 and -COOH. An optimized procedure for diazonium electrografting to semiconductor metal oxides is presented that allowed surface coverages that ranged between 4.7 × 10 -8 and 10.6 × 10 -8 mol cm -2 depending on the nature of the metal oxide. FTIR analysis showed the disappearance of the diazonium stretch at 2266 cm -1 after electrografting. XPS analysis revealed a characteristic peak of Ru 3d at 285 eV as well as a peak at 531.6 eV that was attributed to O 1s in Ti-O-C bonds. Photocurrents were measured to assess electron injection efficiency of these modified surfaces. The electrografted sensitizers exhibited excellent stability across a range of pHs spanning from 1 to 14, where classical binding groups such as carboxylic and phosphonic derivatives were hydrolyzed.

  20. A Readily Accessible Class of Chiral Cp Ligands and their Application in RuII -Catalyzed Enantioselective Syntheses of Dihydrobenzoindoles.

    Science.gov (United States)

    Wang, Shou-Guo; Park, Sung Hwan; Cramer, Nicolai

    2018-05-04

    Chiral cyclopentadienyl (Cp x ) ligands have a large application potential in enantioselective transition-metal catalysis. However, the development of concise and practical routes to such ligands remains in its infancy. We present a convenient and efficient two-step synthesis of a novel class of chiral Cp x ligands with tunable steric properties that can be readily used for complexation, giving Cp x Rh I , Cp x Ir I , and Cp x Ru II complexes. The potential of this ligand class is demonstrated with the latter in the enantioselective cyclization of azabenzonorbornadienes with alkynes, affording dihydrobenzoindoles in up to 98:2 e.r., significantly outperforming existing binaphthyl-derived Cp x ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Synthesis and Characterization of a Heteroleptic Ru(II Complex of Phenanthroline Containing Oligo-Anthracenyl Carboxylic Acid Moieties

    Directory of Open Access Journals (Sweden)

    Peter A. Ajibade

    2010-09-01

    Full Text Available In an effort to develop new ruthenium(II complexes, this work describes the design, synthesis and characterization of a ruthenium(II functionalized phenanthroline complex with extended π-conjugation. The ligand were L1 (4,7-bis(2,3-dimethylacrylic acid-1,10-phenanthroline, synthesized by a direct aromatic substitution reaction, and L2 (4,7-bis(trianthracenyl-2,3-dimethylacrylic acid-1,10-phenanthroline, which was synthesized by the dehalogenation of halogenated aromatic compounds using a zero-valent palladium cross-catalyzed reaction in the absence of magnesium-diene complexes and/or cyclooctadienyl nickel (0 catalysts to generate a new carbon-carbon bond (C-C bond polymerized hydrocarbon units. The ruthenium complex [RuL1L2(NCS2] showed improved photophysical properties (red-shifted metal-to-ligand charge-transfer transition absorptions and enhanced molar extinction coefficients, luminescence and interesting electrochemical properties. Cyclic and square wave voltammetry revealed five major redox processes. The number of electron(s transferred by the ruthenium complex was determined by chronocoulometry in each case. The results show that processes I, II and III are multi-electron transfer reactions while processes IV and V involved one-electron transfer reaction. The photophysical property of the complex makes it a promising candidate in the design of chemosensors and photosensitizers, while its redox-active nature makes the complex a potential mediator of electron transfer in photochemical processes.

  2. Theoretical study on the antitumor properties of Ru(II) complexes containing 2-pyridyl, 2-pyridine-4-carboxylic acid ligands

    Science.gov (United States)

    Erkan kariper, Sultan; Sayin, Koray; Karakaş, Duran

    2017-12-01

    [Ru(bipy)2(CppH)]2+(1), [Ru(bipy)2(Cpp-NH-Hex-COOH)]2+(2), [Ru(dppz)2(CppH)]2+(3) and [Ru(dppz)2(Cpp-NH-Hex-COOH)]2+(4) were calculated by Hartree-Fock (HF), Density Functional Theory (DFT) hybrid B3LYP and Moller-Plesset Perturbation (MPn n = 2,3) theory method and CEP-4G, CEP-31G, CEP-121G, LANL2DZ, LANL2MB, SDD basic sets and a mixed basic set with the keyword GEN in gas phase and water. Structure parameters obtained from optimized structures were compared with experimental parameters. M062X/(6-31G(d))(CEP-4G) level was taken into account for the most appropriate calculation level. IR, UV-VIS and NMR spectrums were examined for structural characterization. The optimal structure was identified via structure parameters, IR, UV-VIS and NMR spectrums. For the most compatible structure, the highest molecular orbital energy (EHOMO) which one of the most effective chemical determiners on the antitumor activity of the complexes, the lowest molecular orbital energy (ELUMO), LUMO-HOMO energy gap, hardness (η), softness (σ), electronegativity (χ), chemical potential (μ), electrophilicity index (ω), molar volume (V), dipole moment (DM), total negative charge (TNC), enthalpy (H), entropy (S) and total energy (E) were calculated. The causes of anticancer activity of the complexes have been studied.

  3. Synthesis and DNA-interactions of new Co(III), Fe(II), Ni(II), Ru(II ...

    Indian Academy of Sciences (India)

    Administrator

    phen) or a modified phen, are particularly attractive species for developing new diagnostic and therapeutic agents that can recognise and cleave DNA. The ligands or the metal in these complexes can be varied in an easily controlled manner ...

  4. Investigation of bifunctional ester additives for methanol-gasoline system

    International Nuclear Information System (INIS)

    Zhang, J.; Yang, C.; Tang, Y.; Du, Q.; Song, N.; Zhang, Z.

    2014-01-01

    To explore new and multifunctional additives for methanol-gasoline, tartaric ester were synthesized and screened as phase stabilizer and saturation vapor pressure depressor for methanol-gasoline. The effect of the esters structure on the efficiency was discussed. The results show that the stabilities of the blends depend on the length of the glycolic esters alkoxy group. In addition, the tartaric esters also can depress the saturation vapor pressure of methanol-gasoline effectively in M15. Effect of the structure on the efficiency was also discussed. (author)

  5. Targeting Prostate Cancer with Bifunctional Modulators of the Androgen Receptor

    Science.gov (United States)

    2015-06-01

    Wittmann, B.; Dwyer, M.; Cui, H.; Dye, D.; McDonnell, D.; Norris , J. Inhibition of prostate cancer cell growth by second-site androgen receptor antagonists...Wittmann, B.; Dwyer, M.; Cui, H.; Dye, D.; McDonnell, D.; Norris , J. Inhibition of prostate cancer cell growth by second-site androgen receptor...important clin- ical problem in diseases such as asthma (51, 52), ne- phrotic syndrome (53), and malignancies such as acute lymphoblastic leukemia (54

  6. Synthesis of a novel bicyclic bifunctional chelating agent

    International Nuclear Information System (INIS)

    Sweet, M.P.; Mease, R.C.; Joshi, V.; Srivastava, S.C.

    1994-01-01

    Semi-rigid ligands such as cyclohexyl EDTA (CDTA) and 4-isothiocyanato-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (4-ICE) form chelates that are more stable in vivo compared to those of EDTA or DTPA. The authors have synthesized a new class of ligands in which the metal-binding polyaminocarboxylate groups are incorporated onto the rigid bicyclo[2.2.2]octane ring system. These ligands are expected to contribute to even higher in vivo stability of radiometal complexes. The synthesis of the first in this series of ligands (2.3-diaminobicyclo[2.2.2]octane-N,N,N',N'-tetraacetic acid, BODTA) began with a Diels-Alder reaction of 1,3-diacetylimidazolin-2-one and 1,3-cyclohexadiene. Base hydrolysis afforded the diamine. Following alkylation of the diamine with ethyl iodoacetate and hydrogenation of the double bond, hydrolysis of the esters gave BODTA. For initial conjugation with proteins, an average of one carboxylic acid of BODTA was converted into an NHS ester. In vivo testing of radioimmunoconjugates, prepared using this method, is in progress

  7. Catalytic characterization of bi-functional catalysts derived from Pd ...

    Indian Academy of Sciences (India)

    Unknown

    1995; Lyubovsky and Pfefferle 1999; Sales et al 1999;. Hill et al 2000). ... For a catalytic system, whose activity ... catalytic systems containing Pd, supported on various acid- ..... Further studies are needed to optimize a balance between.

  8. Designing bifunctional alkene isomerization catalysts using predictive modelling

    NARCIS (Netherlands)

    Landman, I.R.; Paulson, E.R.; Rheingold, A.L.; Grotjahn, D.B.; Rothenberg, G.

    2017-01-01

    Controlling the isomerization of alkenes is important for the manufacturing of fuel additives, fine-chemicals and pharmaceuticals. But even if isomerization seems to be a simple unimolecular process, the factors that govern catalyst performance are far from clear. Here we present a set of models

  9. A yeast mutant specifically sensitive to bifunctional alkylation

    International Nuclear Information System (INIS)

    Ruhland, A.; Kircher, M.; Wilborn, F.; Brendel, M.

    1981-01-01

    A mutation that specifically confers sensitivity to bi- and tri-functional alkylating agents is presented. No or little cross-sensitivity to radiation or monofunctional agents could be detected. Sensitivity does not seem to be due to preferential alkylation of mutant DNA as parent and mutant strain exhibit the same amount of DNA alkylation and the same pattern of DNA lesions including interstrand crosslinks. The mutation is due to a defect in a nuclear gene which has been designated SNM1 (sensitive to nitrogen mustard); it may control an important step in the repair of DNA interstrand crosslinks (orig.(AJ)

  10. Bifunctional dendrons for multiple carbohydrate presentation via carbonyl chemistry

    Directory of Open Access Journals (Sweden)

    Davide Bini

    2014-07-01

    Full Text Available The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

  11. Use of Bifunctional Immunotherapeutic Agents to Target Breast Cancer

    Science.gov (United States)

    2007-07-01

    Science 270, 1500–1502. 32. Pasqualini , R., Koivunen, E., and Ruoslahti, E. (1997) v integrins as receptors for tumor targeting by circulating ligands...Nat. Biotech- nol. 15, 542–546. 33. Arap, W., Pasqualini , R., and Ruoslahti, E. (1998) Cancer treatment by targeted drug delivery to tumor...Cancer Res. 2, 663–673. 47. Arap, W., Pasqualini , R., and Ruoslahti, E. (1998) Cancer treatment by targeted drug delivery to tumor vasculature in a

  12. Novel phosphonium salts and bifunctional organocatalysts in asymmetric synthesis

    OpenAIRE

    Moore, Graham

    2013-01-01

    This thesis details the syntheses of catalysts and their applications in asymmetric reactions. Initially, the project focused on phase transfer catalysts; quaternary phosphonium salts derived from diethyl tartrate or from commercially available phosphorus compounds and their use primarily in the alkylation of N,N-diphenyl methylene glycine tert-butyl ester. Although some of the salts showed the ability to catalyse the alkylation reaction, all products obtained were racemic. The project then f...

  13. Bifunctional activity of deoxyhypusine synthase/hydroxylase from Trichomonas vaginalis.

    Science.gov (United States)

    Quintas-Granados, Laura Itzel; Carvajal Gamez, Bertha Isabel; Villalpando, Jose Luis; Ortega-Lopez, Jaime; Arroyo, Rossana; Azuara-Liceaga, Elisa; Álvarez-Sánchez, María Elizbeth

    2016-04-01

    The Trichomonas vaginalis genome analysis suggested the presence of a putative deoxyhypusine synthase (TvDHS) that catalyzes the posttranslational modification of eIF-5A. Herein, we expressed and purified the recombinant TvDHS (rTvDHS) protein (43 kDa) and the recombinant TveIF-5A (rTveIF-5A) precursor protein (46 kDa). A 41 kDa band of the native TvDHS was recognized by western blot analysis in T. vaginalis total protein extract by a mouse polyclonal anti-rTvDHS antibody. The enzymatic activity of rTvDHS was determined by in vitro rTveIF-5A precursor modification. The modification reaction was performed by using ((3)H)-spermidine, and the biochemical analysis showed that rTvDHS exhibited Km value of 0.6 μM. The rTvDHS activity was inhibited by the spermidine analog, N″-guanyl-1,7-diamino-heptane (GC7). Native gel electrophoresis analysis showed two bands corresponding to an rTvDHS-rTveIF-5A complex and an intermediate form of rTveIF-5A. The two forms were subsequently separated by ion exchange chromatography to identify the hypusine residue by MS/MS analysis. Moreover, mutations in TvDHS showed that the putative HE motif present in this enzyme is involved in the hydroxylation of TveIF-5A. We observed that only hypusine-containing TveIF-5A was bound to an RNA hairpin ERE structure from the cox-2 gene, which contains the AAAUGUCACAC consensus sequence. Interestingly, 2DE-WB assays, using parasites that were grown in DAB-culture conditions and transferred to exogenous putrescine, showed the new isoform of TveIF-5A. In summary, our results indicate that T. vaginalis contains an active TvDHS capable of modifying the precursor TveIF-5A protein, which subsequently exhibits RNA binding activity. Copyright © 2015. Published by Elsevier B.V.

  14. Bifunctional anode catalysts for direct methanol fuel cells

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios

    2012-01-01

    Using the binding energy of OH* and CO* on close-packed surfaces as reactivity descriptors, we screen bulk and surface alloy catalysts for methanol electro-oxidation activity. Using these two descriptors, we illustrate that a good methanol electro-oxidation catalyst must have three key properties......: (1) the ability to activate methanol, (2) the ability to activate water, and (3) the ability to react off surface intermediates (such as CO* and OH*). Based on this analysis, an alloy catalyst made up of Cu and Pt should have a synergistic effect facilitating the activity towards methanol electro-oxidation....... Adding Cu to a Pt(111) surface increases the methanol oxidation current by more than a factor of three, supporting our theoretical predictions for improved electrocatalysts....

  15. A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes-manganese complex modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Salimi, Abdollah, E-mail: absalimi@uok.ac.i [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Mahdioun, Monierosadat; Noorbakhsh, Abdollah [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Abdolmaleki, Amir [Department of Chemistry, Isfahan University of Technology, Isfahan, 84156/83111 (Iran, Islamic Republic of); Ghavami, Raoof [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2011-03-30

    A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20-100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1-12). The surface coverages and heterogeneous electron transfer rate constants (k{sub s}) of immobilized Mn-complex were approximately 1.58 x 10{sup -10} mole cm{sup -2} and 48.84 s{sup -1}. The modified electrode showed excellent electrocatalytic activity toward H{sub 2}O{sub 2} reduction. Detection limit, sensitivity, linear concentration range and k{sub cat} for H{sub 2}O{sub 2} were, 0.2 {mu}M and 692 nA {mu}M{sup -1} cm{sup -2}, 1 {mu}M to 1.5 mM and 7.96({+-}0.2) x 10{sup 3} M{sup -1} s{sup -1}, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.

  16. A novel non-enzymatic hydrogen peroxide sensor based on single walled carbon nanotubes-manganese complex modified glassy carbon electrode

    International Nuclear Information System (INIS)

    Salimi, Abdollah; Mahdioun, Monierosadat; Noorbakhsh, Abdollah; Abdolmaleki, Amir; Ghavami, Raoof

    2011-01-01

    A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20-100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1-12). The surface coverages and heterogeneous electron transfer rate constants (k s ) of immobilized Mn-complex were approximately 1.58 x 10 -10 mole cm -2 and 48.84 s -1 . The modified electrode showed excellent electrocatalytic activity toward H 2 O 2 reduction. Detection limit, sensitivity, linear concentration range and k cat for H 2 O 2 were, 0.2 μM and 692 nA μM -1 cm -2 , 1 μM to 1.5 mM and 7.96(±0.2) x 10 3 M -1 s -1 , respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.

  17. Photoelectrocatalytic oxidation of glucose at a ruthenium complex modified titanium dioxide electrode promoted by uric acid and ascorbic acid for photoelectrochemical fuel cells

    Science.gov (United States)

    Lu, Shuo-Jian; Ji, Shi-Bo; Liu, Jun-Chen; Li, Hong; Li, Wei-Shan

    2015-01-01

    The simultaneous presence of uric acid (UA) and ascorbic acid (AA) is first found to largely promote the photoelectrocatalytic oxidation of glucose (GLU) at an indium-tin oxide (ITO) or TiO2 nanoparticles/ITO electrode modified with [Ru(tatp)3]2+ (tatp = 1,4,8,9-tetra-aza-triphenylene) possessing good redox activity and nanoparticle size distribution. A well-defined electrocatalytic peak for GLU oxidation is shown at 0.265 V (vs. SCE) under approximate physiological conditions upon incorporation of UA and AA. The [Ru(tatp)3]2+/ITO electrode exhibits attractive amperometric oxidation responses towards GLU, UA and AA, while controlled potentiostatically at 0.3 V, 0.7 V and 1.0 V, respectively, indicating high sensitivity and excellent reproducibility. On basis of the photoelectrocatalysis of [Ru(tatp)3]2+/TiO2/ITO anode, a GLU concentration-dependent photoelectrochemical fuel cell vs. SCE is elaborately assembled. The proposed free-enzyme photoelectrochemical fuel cell employing 0.1 M GLU associated with 0.01 M UA and 0.01 M AA as fuel shows open-circuit photovoltage of 0.608 V, short-circuit photocurrent density of 124.5 μA cm-2 and maximum power density of 21.75 μW cm-2 at 0.455 V, fill factor of 0.32 and photoenergy conversion efficiency of 36.65%, respectively.

  18. Synthesis, photophysical and preliminary investigation of the dye-sensitized solar cells properties of functionalized anthracenyl-based bipyridyl and phenanthrolyl Ru(II) complexes

    CSIR Research Space (South Africa)

    Adeloye, AO

    2013-01-01

    Full Text Available .Ali S, Arta S, Sina H, Siguang C, Pierre G P and Sylvie M 2008 J. New Mat. Electrochem. Systems 11 281 39.Ruhle S, Greenshtein M, Chen S G, Merson A, Pizen H, Sukenik S, Cahen D and Zaban A 2005 J. Phys. Chem. B 109 18907 40.Hoshikawa T, Kikuchi R...

  19. Synthesis and characterization of poly(phenylacetylene)s with Ru(II) bis-terpyridine complexes in the side-chain.

    Science.gov (United States)

    Breul, Alexander M; Kübel, Joachim; Häupler, Bernhard; Friebe, Christian; Hager, Martin D; Winter, Andreas; Dietzek, Benjamin; Schubert, Ulrich S

    2014-04-01

    An alkyne-functionalized ruthenium(II) bis-terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size-exclusion chromatography (SEC), (1) H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV-vis absorption spectroscopy. In addition, spectro-electrochemical measurements are carried out. Time-resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)2 (2+) model complex. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Electronic optimization of heteroleptic Ru(II) bipyridine complexes by remote substituents: synthesis, characterization, and application to dye-sensitized solar cells.

    Science.gov (United States)

    Han, Won-Sik; Han, Jung-Kyu; Kim, Hyun-Young; Choi, Mi Jin; Kang, Yong-Soo; Pac, Chyongjin; Kang, Sang Ook

    2011-04-18

    We prepared a series of new heteroleptic ruthenium(II) complexes, Ru(NCS)(2)LL' (3a-3e), where L is 4,4'-di(hydroxycarbonyl)-2,2'-bipyridine and L' is 4,4'-di(p-X-phenyl)-2,2'-pyridine (X = CN (a), F (b), H (c), OMe (d), and NMe(2) (e)), in an attempt to explore the structure-activity relationships in their photophysical and electrochemical behavior and in their performance in dye-sensitized solar cells (DSSCs). When substituent X is changed from electron-donating NMe(2) to electron-withdrawing CN, the absorption and emission maxima reveal systematic bathochromic shifts. The redox potentials of these dyes are also significantly influenced by X. The electronic properties of the dyes were theoretically analyzed using density functional theory calculations; the results show good correlations with the experimental results. The solar-cell performance of DSSCs based on dye-grafted nanocrystalline TiO(2) using 3a-3e and standard N3 (bis[(4,4'-carboxy-2,2'-bipyridine)(thiocyanato)]ruthenium(II)) were compared, revealing substantial dependences on the dye structures, particularly on the remote substituent X. The 3d-based device showed the best performance: η = 8.30%, J(SC) = 16.0 mA·cm(-2), V(OC) = 717 mV, and ff = 0.72. These values are better than N3-based device.

  1. Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts

    KAUST Repository

    Poater, Albert

    2013-07-01

    The reactivity of a new family of complexes with general formula [Ru IV(T)(R-D)(O)]2+ (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has been analyzed. There is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; 1 leads to the regioselective oxidation at the ring alkene position, whereas 2 leads to the oxidation at the terminal position. Although computational calculations indicate small energy differences, both the geometry through steric maps and the electronic parameters of the reactants via conceptual DFT, or charges via NPA, explain the reactivity differences found for the catalysts depending on the substituents of the oxazoline ligands. © 2013 Elsevier B.V. All rights reserved.

  2. Ligand-based photooxidations of dithiomaltolato complexes of Ru(II) and Zn(II): photolytic CH activation and evidence of singlet oxygen generation and quenching.

    Science.gov (United States)

    Bruner, Britain; Walker, Malin Backlund; Ghimire, Mukunda M; Zhang, Dong; Selke, Matthias; Klausmeyer, Kevin K; Omary, Mohammad A; Farmer, Patrick J

    2014-08-14

    The complex [Ru(bpy)2(ttma)](+) (bpy = 2,2'-bipyridine; ttma = 3-hydroxy-2-methyl-thiopyran-4-thionate, 1, has previously been shown to undergo an unusual C-H activation of the dithiomaltolato ligand upon outer-sphere oxidation. The reaction generated alcohol and aldehyde products 2 and 3 from C-H oxidation of the pendant methyl group. In this report, we demonstrate that the same products are formed upon photolysis of 1 in presence of mild oxidants such as methyl viologen, [Ru(NH3)6](3+) and [Co(NH3)5Cl](2+), which do not oxidize 1 in the dark. This reactivity is engendered only upon excitation into an absorption band attributed to the ttma ligand. Analogous experiments with the homoleptic Zn(ttma)2, 4, also result in reduction of electron acceptors upon excitation of the ttma absorption band. Complexes 1 and 4 exhibit short-lived visible fluorescence and long-lived near-infrared phosphorescence bands. Singlet oxygen is both generated and quenched during aerobic excitation of 1 or 4, but is not involved in the C-H activation process.

  3. Simple and cheap steric and electronic characterization of the reactivity of Ru(II) complexes containing oxazoline ligands as epoxidation catalysts

    KAUST Repository

    Poater, Albert; Falivene, Laura; Cavallo, Luigi; Llobet, Antoni A.; Rodrí guez, Montserrat Carmen Rí os; Romero, Isabel; Solà , Miquel

    2013-01-01

    The reactivity of a new family of complexes with general formula [Ru IV(T)(R-D)(O)]2+ (T = trispyrazolylmethane (tpm); D = N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4, 5-dihydrooxazole-2-carbimidate, R = Bz (1); iPr (2)) has

  4. Role of the sulfonamide moiety of Ru(II) half-sandwich complexes in the asymmetric transfer hydrogenation of 3,4-dihydroisoquinolines

    Czech Academy of Sciences Publication Activity Database

    Matuška, O.; Zápal, J.; Hrdličková, R.; Mikoška, M.; Pecháček, J.; Vilhanová, B.; Václavík, Jiří; Kuzma, M.; Kačer, P.

    2016-01-01

    Roč. 118, č. 1 (2016), s. 215-222 ISSN 1878-5190 Institutional support: RVO:61388963 Keywords : ruthenium * asymmetric transfer hydrogenation * dihydroisoquinolines * sulfonamide Subject RIV: CC - Organic Chemistry Impact factor: 1.264, year: 2016

  5. Role of the sulfonamide moiety of Ru(II) half-sandwich complexes in the asymmetric transfer hydrogenation of 3,4-dihydroisoquinolines

    Czech Academy of Sciences Publication Activity Database

    Matuška, O.; Zápal, Jakub; Hrdličková, R.; Mikoška, M.; Pecháček, J.; Vilhanová, B.; Václavík, Jiří; Kuzma, Marek; Kačer, P.

    2016-01-01

    Roč. 118, č. 1 (2016), s. 215-222 ISSN 1878-5190 R&D Projects: GA ČR GAP106/12/1276; GA ČR(CZ) GA15-08992S; GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : Ruthenium * Asymmetric transfer hydrogenation * Dihydroisoquinolines Subject RIV: EE - Microbiology, Virology Impact factor: 1.264, year: 2016

  6. Molecular Engineering, Photophysical and Electrochemical Characterizations of Novel Ru(II) and BODIPY Sensitizers for Mesoporous TiO2 Solar Cells

    Science.gov (United States)

    Cheema, Hammad Arshad

    To realize the dream of a low carbon society and ensure the wide spread application of renewable energy sources such as solar energy, photovoltaic devices should be highly efficient, cost-effective and stable for at least 20 years. Dye sensitized solar cells (DSCs) are photovoltaic cells that mimic the natural photosynthesis. In a DSC, the dye absorbs photons from incident light and converts those photons to electric charges, which are then extracted to the outer circuit through semiconductor TiO2, whereas the mediator regenerates the oxidized dye. A sensitizer is the pivotal component in the device in terms of determining the spectral response, color, photocurrent density, long term stability, and thickness of a DSC. The breakthrough report by O'Regan and Gratzel in 1991 has garnered more than 18,673 citations (as of October 9, 2014), which indicates the immense scientific interest to better understand and improve the fundamental science of this technology. With the aforementioned in mind, this study has focused on the molecular engineering of novel sensitizers to provide a better understanding of structure-property relationships of novel sensitizers for DSCs. The characterization of sensitizers (HD-1-mono, HD-2-mono and HD-2) for photovoltaic applications showed that the photocurrent response of DSCs can be increased by using mono-ancillary ligand instead of bis-ancillary ligands, which is of great commercial value considering the difference in the molecular weights of both dyes. The results of this work were published in Journal of Materials Chemistry A (doi:10.1039/c4ta01942c) and ACS Applied Materials and Interfaces (doi: 10.1021/am502400b). Furthermore, structure-property relationships were investigated in Ru (II) sensitizers HL-41 and HL-42 in order to elucidate the steric effects of electron donating ancillary ligands on photocurrent and photovoltage, as discussed in Chapter 4. It was found that the electron donating group (ethoxy) ortho to the CH=CH spacer precludes coplanarity of the naphthalene moiety, thus decreasing the extracted photocurrent response from solar device. The findings were published in Dyes and Pigments (doi:10.1016/j.dyepig.2014.08.005). For HD-7 and HD-8, intriguing difference caused by structural isomerization based on anthracene and phenanthrene stilbazole type ancillary ligands, respectively in Ru (II) sensitizers was investigated using femtosecond transient absorption spectroscopy. It was found that the excited electrons in HD-7 are prone to ISC (intersystem crossing) much more than that in HD-8 and those triplet electrons are not being injected in TiO2 efficiently as discussed in Chapter 5. To achieve long term stability, we combined the strong electron donor characteristics of carbazole and the hydrophobic nature of long alkyl chains, C7 (HD-14 ), C18 (HD-15) and C2 (NCSU-10), tethered to N-carbazole. HD-15 showed strikingly good long term light soaking stability and maintained up to 98% of initial efficiency value compared to 92% for HD-14 and 78% for NCSU-10, as discussed in Chapter 6. Boron dipyromethene (BODIPY) dyes HB-1, HB-2 and HB-3 were synthesized and fully characterized for dye solar cells. It was found that having long alkyl chains tethered to the donor groups alone are not sufficient for achieving highly efficient photovoltaic response from BODIPY dyes (Chapter 7). Thus, replacement of fluorines from BODIPY core with long alkoxy chains has been suggested for future work.

  7. Development of a Bifunctional Andrographolide-Based Chemical Probe for Pharmacological Study.

    Science.gov (United States)

    Hsu, Ya-Hsin; Hsu, Yu-Ling; Liu, Sheng-Hung; Liao, Hsin-Chia; Lee, Po-Xuan; Lin, Chao-Hsiung; Lo, Lee-Chiang; Fu, Shu-Ling

    2016-01-01

    Andrographolide (ANDRO) is a lactone diterpenoid compound present in the medicinal plant Andrographis paniculata which is clinically applied for multiple human diseases in Asia and Europe. The pharmacological activities of andrographolide have been widely demonstrated, including anti-inflammation, anti-cancer and hepatoprotection. However, the pharmacological mechanism of andrographolide remains unclear. Therefore, further characterization on the kinetics and molecular targets of andrographolide is essential. In this study, we described the synthesis and characterization of a novel fluorescent andrographolide derivative (ANDRO-NBD). ANDRO-NBD exhibited a comparable anti-cancer spectrum to andrographolide: ANDRO-NBD was cytotoxic to various types of cancer cells and suppressed the migration activity of melanoma cells; ANDRO-NBD treatment induced the cleavage of heat shock protein 90 (Hsp90) and the downregulation of its client oncoproteins, v-Src and Bcr-abl. Notably, ANDRO-NBD showed superior inhibitory effects to andrographolide in all anticancer assays we have performed. In addition, ANDRO-NBD was further used as a fluorescent probe to investigate the uptake kinetics, cellular distribution and molecular targets of andrographolide. Our data revealed that ANDRO-NBD entered cells rapidly and its fluorescent signal could be detected in nucleus, cytoplasm, mitochondria, and lysosome. Moreover, we demonstrated that ANDRO-NBD was covalently bound to several putative target proteins of andrographolide, including NF-κB and hnRNPK. In summary, we developed a fluorescent andrographolide probe with comparable bioactivity to andrographolide, which serves as a powerful tool to explore the pharmacological mechanism of andrographolide.

  8. Development of a Bifunctional Andrographolide-Based Chemical Probe for Pharmacological Study.

    Directory of Open Access Journals (Sweden)

    Ya-Hsin Hsu

    Full Text Available Andrographolide (ANDRO is a lactone diterpenoid compound present in the medicinal plant Andrographis paniculata which is clinically applied for multiple human diseases in Asia and Europe. The pharmacological activities of andrographolide have been widely demonstrated, including anti-inflammation, anti-cancer and hepatoprotection. However, the pharmacological mechanism of andrographolide remains unclear. Therefore, further characterization on the kinetics and molecular targets of andrographolide is essential. In this study, we described the synthesis and characterization of a novel fluorescent andrographolide derivative (ANDRO-NBD. ANDRO-NBD exhibited a comparable anti-cancer spectrum to andrographolide: ANDRO-NBD was cytotoxic to various types of cancer cells and suppressed the migration activity of melanoma cells; ANDRO-NBD treatment induced the cleavage of heat shock protein 90 (Hsp90 and the downregulation of its client oncoproteins, v-Src and Bcr-abl. Notably, ANDRO-NBD showed superior inhibitory effects to andrographolide in all anticancer assays we have performed. In addition, ANDRO-NBD was further used as a fluorescent probe to investigate the uptake kinetics, cellular distribution and molecular targets of andrographolide. Our data revealed that ANDRO-NBD entered cells rapidly and its fluorescent signal could be detected in nucleus, cytoplasm, mitochondria, and lysosome. Moreover, we demonstrated that ANDRO-NBD was covalently bound to several putative target proteins of andrographolide, including NF-κB and hnRNPK. In summary, we developed a fluorescent andrographolide probe with comparable bioactivity to andrographolide, which serves as a powerful tool to explore the pharmacological mechanism of andrographolide.

  9. In-111 BLEDTA: a conjugate of bleomycin with a bifunctional chelating agent for tumor localization

    International Nuclear Information System (INIS)

    Goodwin, D.A.; Meares, C.F.; DeRiemer, L.H.; Diamanti, C.I.; Goode, R.L.

    1979-01-01

    BLEDTA, a bleomycin A 2 analog containing an EDTA group was labeled in the EDTA group to a specific activity of 70 mCi/mg and used for animal and human studies. KHJJ mouse tumor uptake was higher than the orange Co-57 bleomycin isomer and the tumor/organ ratios were >1 for all organs except the kidney. In 29 biopsy proven cancer patients the scan done 24 hours post I.V. with 1-2 mCi of In-111 BLEDTA was positive in all clinically known sites in 18, and in some clinically known sites in 11. The In-111 BLEDTA clinical results are similar to reported Co-57 bleomycin clinical studies, and the method is proposed as an alternate way to produce a stable biologically active bleomycin labeled with In-111

  10. Combining the Physical Adsorption Approach and the Covalent Attachment Method to Prepare a Bifunctional Bioreactor

    Directory of Open Access Journals (Sweden)

    Zhi Wang

    2012-09-01

    Full Text Available Aminopropyl-functionalized SBA-15 mesoporous silica was used as a support to adsorb myoglobin. Then, in order to avoid the leakage of adsorbed myoglobin, lysozyme was covalently tethered to the internal and external surface of the mesoporous silica with glutaraldehyde as the coupling agent. The property of amino-functionalized mesoporous silica was characterized by N2 adsorption-desorption and thermogravimetric (TG analysis. The feature of the silica-based matrix before and after myoglobin adsorption was identified by fourier transform infrared (FTIR and UV/VIS measurement. With o-dianisidine and H2O2 as the substrate, the peroxidase activity of adsorbed myoglobin was determined. With Micrococus lysodeilicus as the substrate, the antibacterial activity of covalently tethered lysozyme was measured. Results demonstrated that the final product not only presented peroxidase activity of the myoglobin but yielded antibacterial activity of the lysozyme.

  11. Microwave assisted bi-functional activation of β-bromo-tert-alcohols

    Indian Academy of Sciences (India)

    Spice and Flavour Science Department, CSIR-Central Food Technological Research Institute, .... ethanol at 2 atm pressure to afford (-)-p-menthane. α-. Terpineol was ..... time (min) Temp (◦C). 1. 52. 75 ... and 1c is the choice of the metal salt.

  12. Effect of Platinum in Bifunctional Isomerization of n-Butane over Acid Zeolites

    Czech Academy of Sciences Publication Activity Database

    Babůrek, Evžen; Nováková, Jana

    2000-01-01

    Roč. 190, č. 1 (2000), s. 241-251 ISSN 0926-860X R&D Projects: GA AV ČR IAA4040710 Institutional research plan: CEZ:AV0Z4040901; CEZ:A54/98:Z4-040-9-ii Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.576, year: 2000

  13. Bifunctional lanthanum phosphate substrates as novel adsorbents and biocatalyst supports for perchlorate removal

    Energy Technology Data Exchange (ETDEWEB)

    Sankar, Sasidharan [Materials Science and Technology Division (India); Prajeesh, Gangadharan Puthiya Veetil; Anupama, Vijaya Nadaraja [Process Engineering and Environmental Technology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Industrial Estate P.O., Thiruvananthapuram 695019 (India); Krishnakumar, Bhaskaran [Process Engineering and Environmental Technology Division, CSIR – National Institute for Interdisciplinary Science and Technology, Industrial Estate P.O., Thiruvananthapuram 695019 (India); Academy of Scientific and Industrial Research (AcSIR) (India); Hareesh, Padinhattayil [Materials Science and Technology Division (India); Nair, Balagopal N. [R and D Centre, Noritake Co. Ltd., Aichi (Japan); Warrier, Krishna Gopakumar [Materials Science and Technology Division (India); Academy of Scientific and Industrial Research (AcSIR) (India); Hareesh, Unnikrishnan Nair Saraswathy, E-mail: hareesh@niist.res.in [Materials Science and Technology Division (India); Academy of Scientific and Industrial Research (AcSIR) (India)

    2014-06-30

    Graphical abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign thermal gelation process, performed the role of dual functional sorbent facilitating perchlorate adsorption and bioremediation through the growth of perchlorate reducing microbial colonies. - Highlights: • Lanthanum phosphate monoliths as efficient perchlorate adsorbents. • And also as substrates for biofilm (perchlorate reducing bacteria) growth. • Environmentally benign thermal gelation process for substrate fabrication. • 98% adsorption efficiency for perchlorate concentrations up to 100 μg/L. • The regenerated monoliths show nearly 100% reusability. - Abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign colloidal forming process employing methyl cellulose, are reported here as excellent adsorbents of perchlorate with >98% efficiency and with 100% reusability. Additionally, the effectiveness of such substrates as biocatalyst supports that facilitate biofilm formation of perchlorate reducing microbes (Serratia marcescens NIIST 5) is also demonstrated for the first time. The adsorption of perchlorate ions is attributed to the pore structure of lanthanum phosphate substrate and the microbial attachment is primarily ascribed to its intrinsic hydrophobic property. Lanthanum phosphate thus emerges as a dual functional material that possesses an integrated adsorption/bioremediation property for the effective removal of ClO{sub 4}{sup −} which is an increasingly important environmental contaminant.

  14. A bi-functional xyloglucan galactosyltransferase is an indispensable salt stress tolerance determinant in arabidop

    KAUST Repository

    Li, Wenbo; Guan, Qingmei; Wang, Zhenyu; Wang, Yingdian; Zhu, Jianhua

    2013-01-01

    Salinity is an abiotic stress that substantially limits crop production worldwide. To identify salt stress tolerance determinants, we screened for Arabidopsis mutants that are hypersensitive to salt stress and designated these mutants as short root

  15. Bifunctional, Chemically Patterned Flat Stamps for Microcontact Printing of Polar Inks

    NARCIS (Netherlands)

    Duan, X.; Sadhu, V.B.; Perl, A.; Péter, M.; Reinhoudt, David; Huskens, Jurriaan

    2008-01-01

    Different methods to create chemically patterned, flat PDMS stamps with two different chemical functionalities were compared. The best method for making such stamps, functionalized with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFDTS) and 3-(aminopropyl)triethoxysilane (APTS), appeared to be full

  16. Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination

    KAUST Repository

    Moulin, Solenne; Dentel, Hé lè ne; Pagnoux-Ozherelyeva, Anastassiya; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Lohier, Jean Franç ois; Renaud, Jean Luc

    2013-01-01

    . Festival of amination: Two series of modified Knölker's complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight

  17. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, M.S.

    1976-10-06

    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure.

  18. Bi-functional properties of Fe3O4@YPO4:Eu hybrid nanoparticles: hyperthermia application.

    Science.gov (United States)

    Prasad, A I; Parchur, A K; Juluri, R R; Jadhav, N; Pandey, B N; Ningthoujam, R S; Vatsa, R K

    2013-04-14

    Magnetic nanoparticles based hyperthermia therapy is a possible low cost and effective technique for killing cancer tissues in the human body. Fe3O4 and Fe3O4@YPO4:5Eu hybrid magnetic nanoparticles are prepared by co-precipitation method and their average particle sizes are found to be ∼10 and 25 nm, respectively. The particles are spherical, non-agglomerated and highly dispersible in water. The crystallinity of as-prepared YPO4:5Eu sample is more than Fe3O4@YPO4:5Eu hybrid magnetic nanoparticles. The chemical bonds interaction between Fe3O4 and YPO4:5Eu is confirmed through FeO-P. The magnetization of hybrid nanocomposite shows magnetization Ms = 11.1 emu g(-1) with zero coercivity (measured at 2 × 10(-4) Oe) at room temperature indicating superparamagnetic behaviour. They attain hyperthermia temperature (~42 °C) under AC magnetic field showing characteristic induction heating of the prepared nanohybrid and they will be potential material for biological application. Samples produce the red emission peaks at 618 nm and 695 nm, which are in range of biological window. The quantum yield of YPO4:5Eu sample is found to be 12%. Eu(3+) present on surface and core could be distinguished from luminescence decay study. Very high specific absorption rate up to 100 W g(-1) could be achieved. The intracellular uptake of nanocomposites is found in mouse fibrosarcoma (Wehi 164) tumor cells by Prussian blue staining.

  19. Design and Synthesis of Bifunctional Oxime Reactivators of OP- inhibited Cholinesterase

    Science.gov (United States)

    2013-08-01

    N O O OH N O O O O N OH O O N N O O N N N O N N N N N O N+ N N N OH MeOH/APS THP NaBH4 MsCl HN N p-Toluenesulfonic Acid Swern Oxidation H2N O S O O O...pendant general acid groups. Compound 8 has been delivered to ICD for testing (synthesis and characterization below). This strategy is in place to...as a THP ether and the trifluoromethylketone installed by coupling the organolithium with trifluoroacetylpiperidine. We again used our direct

  20. CONVERSION OF (±-CITRONELLAL AND ITS DERIVATIVES TO (--MENTHOL USING BIFUNCTIONAL NICKEL ZEOLITE CATALYSTS

    Directory of Open Access Journals (Sweden)

    Indri Badria Adilina

    2015-06-01

    Full Text Available (±-Citronellal and its derivatives were converted to (--menthol by a one-pot reaction system using zeolite based nickel catalysts. The catalysts were prepared by immobilization of nickel on natural zeolite (NZ or synthetic zeolite (ZSM-5 by a simple cation exchange method. Calcination and hydrogen treatment procedures were able to significantly increase the surface area and pore volume of NZ based catalysts whereas negligible changes in the properties were observed for that of ZSM-5. Catalytic reactions were carried out at 70ºC by stirring the mixture in the air for cyclization of (±-citronellal to (±-isopulegol followed by hydrogenation towards the desired (--menthol at 2 Mpa of H2 pressure. The Ni/NZ catalyst was able to convert a (±-citronellal derivative yielding 9% (--menthol (36% selectivity with conversion up to 24%, whereas Ni/ZSM5 catalyst directly converted 65% (±-citronellal to give 4% menthol (6% selectivity. These zeolite based catalysts are therefore potential materials for the conversion of biomass feed stock to value-added chemicals.

  1. Radiation-induced crosslinking of polyethylene in the presence of bifunctional vinyl monomers

    International Nuclear Information System (INIS)

    Joshi, M.S.

    1976-01-01

    The apparent crosslinking produced by the radiation grafting of two monomers to polyethylene, acrylic acid and acrylonitrile, was investigated. Evidence is presented to show that covalent crosslinks are not produced during the radiation grafting step; covalent crosslinks are produced by the post-irradiation heat treatment associated with measurements of gel; the enhancement in gel fraction and physical properties arises from true crosslinks rather than chain entanglements; and there may be practical value associated with the sensitization of crosslinking produced by the methods employed in this work. The effect of monomer-solvent composition on the graft and gel yield was studied. Viscoelastic properties of grafted films were determined above the melting point of pure polyethylene. The kinetic data, infrared spectra, and viscoelastic properties are the bases for the following mechanism: (1) Acrylic acid-g-PE: Acrylic acid enters the film in the form of a hydrogen bonded dimer and undergoes a grafting reaction that produces hydrogen-bond crosslinks. The heat treatment during the conventional methods for determining of crosslinks convert them into intermolecular anhydride bonds. (2) Acrylonitrile-g-PE: In this, the post-grafting crosslinking is the result of a thermally induced chain reaction leading to an uninterrupted conjugated sequence. The length of the ring structure increases with time and temperature, and the intensity of color increases with the length of the ring structure

  2. Development of a Tetrathioether (S4) Bifunctional Chelate System for Rh-105

    Science.gov (United States)

    2013-07-01

    olt s...500 0 500 1000 1500 mV olt s -500 0 500 1000 1500 (B) Free Rhodium Chloride Minutes 0 2 4 6 8 10 12 mV olt s 0 2000 4000 mV olt s 0 2000 4000 (C) Rh-S4...Diol prepared in water Minutes 0 2 4 6 8 10 12 mV olts 0 2000 4000 mV olts 0 2000 4000 (D) 105 Rh-S4Diol with cold [Rh-S4(OH)2-Diol] +

  3. Branch-specific plasticity of a bifunctional dopamine circuit encodes protein hunger.

    Science.gov (United States)

    Liu, Qili; Tabuchi, Masashi; Liu, Sha; Kodama, Lay; Horiuchi, Wakako; Daniels, Jay; Chiu, Lucinda; Baldoni, Daniel; Wu, Mark N

    2017-05-05

    Free-living animals must not only regulate the amount of food they consume but also choose which types of food to ingest. The shifting of food preference driven by nutrient-specific hunger can be essential for survival, yet little is known about the underlying mechanisms. We identified a dopamine circuit that encodes protein-specific hunger in Drosophila The activity of these neurons increased after substantial protein deprivation. Activation of this circuit simultaneously promoted protein intake and restricted sugar consumption, via signaling to distinct downstream neurons. Protein starvation triggered branch-specific plastic changes in these dopaminergic neurons, thus enabling sustained protein consumption. These studies reveal a crucial circuit mechanism by which animals adjust their dietary strategy to maintain protein homeostasis. Copyright © 2017, American Association for the Advancement of Science.

  4. Tobacco Nectarin III is a bifunctional enzyme with monodehydroascorbate reductase and carbonic anhydrase activities.

    Science.gov (United States)

    Carter, Clay J; Thornburg, Robert W

    2004-02-01

    Tobacco plants secrete a limited array of proteins (nectarins) into their floral nectar. N-terminal sequencing of the Nectarin II ( NEC2; 35kD) and the Nectarin III ( NEC3; 40kD) proteins revealed that they both share identity with dioscorin, the major soluble protein of yam tubers. These sequences also revealed that NEC2 is a breakdown product of NEC3. Using these N-terminal peptide sequences, degenerate oligonucleotides were designed that permitted the isolation of a partial NEC3 cDNA. This cDNA was then used to probe a nectary specific cDNA library and a full-length NEC3 cDNA clone was isolated. Complete sequence analysis confirmed the identity of NEC3 as a dioscorin-like protein. MALDI-TOF mass spectrometric fingerprinting of tryptic peptides derived from the purified NEC3 confirmed that this protein was encoded by the isolated cDNA. NEC3 was shown to possess both carbonic anhydrase and monodehydroascorbate reductase activities. RT-PCR based expression analyses demonstrated that NEC3 transcript is expressed throughout nectary development as well as in other floral organs. A proposed function in the maintenance of pH and oxidative balance in nectar is discussed.

  5. Dual mechanism bifunctional polymers for the complexation of lanthanides and actinides

    International Nuclear Information System (INIS)

    Alexandratos, S.D.; Quillen, D.R.; McDowell, W.J.

    1985-01-01

    Phosphinic acid ion exchange/redox resins are synthesized by the reaction between polystyrene beads and phosphorus trichloride followed by base hydrolysis. The reaction requires a temperature of 73 0 C for full functionalization to occur. The effect of lower functionalization temperatures on resin acid capacity was determined and the concomitant effect on ion exchange investigated. The acid capacity was found to vary from 1.09 mequiv/g to 4.79 mequiv/g in the functionalization temperature range studied (15 0 C to 73 0 C). The percent resin sites loaded with zinc ions is independent of the actual capacity but the time to attain that percent loading increases from 5 minutes to 60 minutes as the absolute amount of zinc loaded increases. The extracting ability of the phosphinic acid resin for europium, thorium, uranium, americium, and plutonium was examined as a function of acid concentration from acid nitrate solutions both at varying and constant ionic strength. The phosphinic resins show better extraction for these ions than the sulfonic resins, especially from high acid solution (4M HNO 3 ) due to the superior coordination ability of the phosphoryl oxygen. They also show a much higher selectivity for the ions tested over sodium. For example, under conditions where sulfonic resins absorb 53% of the plutonium in solution, the phosphinic acid resins absorb 99%

  6. Bifunctional (cyclopentadienone)iron-tricarbonyl complexes: Synthesis, computational studies and application in reductive amination

    KAUST Repository

    Moulin, Solenne

    2013-11-15

    Reductive amination under hydrogen pressure is a valuable process in organic chemistry to access amine derivatives from aldehydes or ketones. Knölker\\'s complex has been shown to be an efficient iron catalyst in this reaction. To determine the influence of the substituents on the cyclopentadienone ancillary ligand, a series of modified Knölker\\'s complexes was synthesised and fully characterised. These complexes were also transformed into their analogous acetonitrile iron-dicarbonyl complexes. Catalytic activities of these complexes were evaluated and compared in a model reaction. The scope of this reaction is also reported. For mechanistic insights, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Festival of amination: Two series of modified Knölker\\'s complexes were synthesised and applied in the reductive amination of various carbonyl derivatives with primary or secondary amines (see scheme, TIPS = triisopropylsilyl). For a mechanistic insight, deuterium-labelling experiments and DFT calculations were undertaken and are also presented. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Bifunctional properties of hydrothermal synthesized BaMF4 (M = Co, Ni and Zn

    Directory of Open Access Journals (Sweden)

    Farheen N. Sayed

    2013-07-01

    Full Text Available BaMF4 (M = Co, Ni and Zn samples having orthorhombic structure have been synthesized by a mild hydrothermal method and characterized by x-ray diffraction (XRD, magnetic and electrical measurements. Single phase formation of these compounds has been found to be dependent on various factors like reaction time, pH, temperature etc. All the samples showed ferroelectricity, which decreases with increase in temperature. BaMF4 (M = Co, Ni samples show 10-15 times more leakage current compared to that of BaZnF4 at higher applied field. Absence of multivalent ions in BaZnF4 can be the reason for its minimum leakage current. All the samples except, BaZnF4, exhibit weak room temperature ferromagnetism also.

  8. Catalytic Activity of a Bifunctional Catalyst for Hydrotreatment of Jatropha curcas L. Seed Oil

    Directory of Open Access Journals (Sweden)

    J. García-Dávila

    2018-01-01

    Full Text Available The hydrotreating process of vegetable oils (HPVO involves the transformation of vegetable oil triglycerides into straight chain alkanes, which are carried out by deoxygenation reactions, generating multiple hydrocarbon compounds, cuts similar to heavy vacuum oil. The HPVO is applied to Jatropha curcas oil on USY zeolite supported with gamma alumina and platinum deposition on the catalytic as hydrogenation component. The acid of additional activity of the supports allows the development of catalytic routes that the intervention of catalytic centers of different nature reaches the desired product. The products of the hydrotreating reaction with Jatropha curcas seed oil triglycerides were identified by Fourier transform infrared spectroscopy and by mass spectroscopy to identify and analyze the generated intermediate and final hydrocarbon compounds.

  9. Bifunctional Membrane for High Energy, Long Shelf Life Li-S Batteries, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — The adoption of high energy lithium sulfur batteries hinges on significant improvements in charge/recharge cycle life. Cycle life is limited by migration of...

  10. Pluronic-lysozyme conjugates as anti-adhesive and antibacterial bifunctional polymers for surface coating

    NARCIS (Netherlands)

    Muszanska, A.K.; Busscher, H.J.; Herrmann, A.; Mei, van der H.C.; Norde, W.

    2011-01-01

    This paper describes the preparation and characterization of polymer protein conjugates composed of a synthetic triblock copolymer with a central polypropylene oxide (PPO) block and two terminal polyethylene oxide (PEO) segments, Pluronic F-127, and the antibacterial enzyme lysozyme attached to the

  11. Characterisation of two bifunctional cellulase-xylanase enzymes isolated from a bovine rumen metagenome library

    CSIR Research Space (South Africa)

    Rashamuse, KJ

    2013-02-01

    Full Text Available ample raw material for fuel production [21] without causing reduction in food stock. Bio-fuel can be produced by pre-treatment, either physical or chemical, of cellulosic material, followed by fermentation of released sugars to yield fuel ethanol.... Currently cellulytic enzymes are used in the pre-treatment step [21, 19] to assist in degradation of cellulose to yield fermentable sugars. To reduce cost in biofuel production there is a need for enzyme preparations with broader substrate ranges...

  12. Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

    Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

  13. Bifunctional lanthanum phosphate substrates as novel adsorbents and biocatalyst supports for perchlorate removal

    International Nuclear Information System (INIS)

    Sankar, Sasidharan; Prajeesh, Gangadharan Puthiya Veetil; Anupama, Vijaya Nadaraja; Krishnakumar, Bhaskaran; Hareesh, Padinhattayil; Nair, Balagopal N.; Warrier, Krishna Gopakumar; Hareesh, Unnikrishnan Nair Saraswathy

    2014-01-01

    Graphical abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign thermal gelation process, performed the role of dual functional sorbent facilitating perchlorate adsorption and bioremediation through the growth of perchlorate reducing microbial colonies. - Highlights: • Lanthanum phosphate monoliths as efficient perchlorate adsorbents. • And also as substrates for biofilm (perchlorate reducing bacteria) growth. • Environmentally benign thermal gelation process for substrate fabrication. • 98% adsorption efficiency for perchlorate concentrations up to 100 μg/L. • The regenerated monoliths show nearly 100% reusability. - Abstract: Porous lanthanum phosphate substrates, obtained by an environmentally benign colloidal forming process employing methyl cellulose, are reported here as excellent adsorbents of perchlorate with >98% efficiency and with 100% reusability. Additionally, the effectiveness of such substrates as biocatalyst supports that facilitate biofilm formation of perchlorate reducing microbes (Serratia marcescens NIIST 5) is also demonstrated for the first time. The adsorption of perchlorate ions is attributed to the pore structure of lanthanum phosphate substrate and the microbial attachment is primarily ascribed to its intrinsic hydrophobic property. Lanthanum phosphate thus emerges as a dual functional material that possesses an integrated adsorption/bioremediation property for the effective removal of ClO 4 − which is an increasingly important environmental contaminant

  14. Mechanism of bactericidal activity of Silver Nitrate - a concentration dependent bi-functional molecule

    Directory of Open Access Journals (Sweden)

    Sureshbabu Ram Kumar Pandian

    2010-10-01

    Full Text Available Silver nitrate imparts different functions on bacteria depending upon its concentration. At lower concentration it induced synthesis of nanoparticles, whereas at higher concentrations it induced cell death. Bacillus licheniformis was used as model system. The MIC was 5 mM, and it induced catalase production, apoptotic body formation and DNA fragmentation.

  15. Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Gang [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Yang, Ce [Chemical Science and Engineering Division, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Zhao, Wanpeng [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Li, Qianru [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Wang, Ning [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China; Li, Tao [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Zhou, Hua [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 Cass Avenue Lemont IL 60439 USA; Chen, Hangrong [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China; Shi, Jianlin [State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-xi Road Shanghai 200050 P. R. China

    2017-11-06

    The introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble-metal-free electrocatalysts for clean energy conversion applications, however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs is investigated for the first time. It is found that the active cobalt-nitrogen sites tend to be selectively constructed on the surface of N-doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt-sites-dependent activity for ORR and HER in acidic media. And the remarkably enhanced catalytic activities approaching that of benchmark Pt/C in acidic medium has been obtained on the catalyst dominated with cobalt-nitrogen sites, confirmed by the advanced spectroscopic . Our finding demonstrates a general paradigm of anion-regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.

  16. Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces

    DEFF Research Database (Denmark)

    Jovanov, Zarko; Hansen, Heine A.; Varela Gasque, Ana Sofia

    2016-01-01

    Electrolysis could enable the large-scale conversion of CO2 to fuels and small molecules. This perspective discusses the state-of-the-art understanding of CO2 and CO reduction electrocatalysis and provides an overview of the most promising approaches undertaken thus far. We set to explore "bifunc...

  17. Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

    Science.gov (United States)

    Schatzschneider, Ulrich; Barton, Jacqueline K

    2004-07-21

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

  18. Bifunctional Rhodium Intercalator Conjugates as Mismatch-Directing DNA Alkylating Agents

    OpenAIRE

    Schatzschneider, Ulrich; Barton, Jacqueline K.

    2004-01-01

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covale...

  19. Bifunctional electroluminescent and photovoltaic devices using bathocuproine as electron-transporting material and an electron acceptor

    International Nuclear Information System (INIS)

    Chen, L.L.; Li, W.L.; Li, M.T.; Chu, B.

    2007-01-01

    Electroluminescence (EL) devices, using 4, 4',4''-tris (2-methylphenyl- phenylamino) triphenylamine (m-MTDATA) as hole-transporting material and bathocuproine (BCP) as an electron-transporting material, were fabricated, which emitted bright green light peaked at 520 nm instead of the emission of m-MTDATA or BCP. It was attributed to the exciplex formation and emission at the interface of m-MTDATA and BCP. EL performance was significantly enhanced by a thin mixed layer (5 nm) of m-MTDATA and BCP inserted between the two organic layers of the original m-MTDATA/BCP bilayer device. The trilayer device showed maximum luminance of 1,205 cd/m 2 at 8 V. At a luminance of 100 cd/m 2 , the power efficiency is 1.64 cd/A. Commission International De L'Eclairoge (CIE) color coordinates of the output spectrum of the devices at 8 V are x=0.244 and y=0.464. These devices also showed photovoltaic (PV) properties, which were sensitive to UV light. The PV diode exhibits high open-circuit voltage (V oc ) of 2.10 V under illumination of 365 nm UV light with 2 mW/cm 2 . And the short-circuit current (I sc ) of 92.5x10 -6 A/cm 2 , fill factor (FF) of 0.30 and power conversion efficiency (η e ) of 2.91% are respectively achieved. It is considered that strong exciplex emission in an EL device is a good indicator of efficient charge transfer at the organic interface, which is a basic requirement for good PV performance. Both the bilayer and trilayer devices showed EL and PV properties, suggesting their potential use as multifunction devices

  20. The conversion of dimethyl ether over Pt/H-ZSM5. A bifunctional catalyzed reaction

    NARCIS (Netherlands)

    Engelen, C.W.R.; Wolthuizen, J.P.; Hooff, van J.H.C.; Imelik, B.; Naccache, C.; Coudurier, G.

    1985-01-01

    At low temperatures dimethylether mixed with hydrogen reacts over a platinum loaded H-ZSM5 catalyst selectivity to methane. Two successive steps can be distinguished; first the acid-catalyzed formation of a trimethyloxoniumion, followed by a metal-catalyzed hydrogenation to methane. Experiments with

  1. Bifunctional ion exchange resin with thiol and quaternary ammonium groups for the sorption of arsenate

    Czech Academy of Sciences Publication Activity Database

    Hrubý, Martin; Korostyatynets, V.; Beneš, Milan J.; Matějka, Z.

    2003-01-01

    Roč. 68, č. 11 (2003), s. 2159-2170 ISSN 0010-0765 R&D Projects: GA ČR GA203/01/1310 Institutional research plan: CEZ:AV0Z4050913 Keywords : ion exchange rs * functionalized resin s * polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.041, year: 2003

  2. Bifunctional effects of fucoidan on the expression of inducible nitric oxide synthase

    International Nuclear Information System (INIS)

    Yang, Jin Won; Yoon, Se Young; Oh, Soo Jin; Kim, Sang Kyum; Kang, Keon Wook

    2006-01-01

    Algal fucoidan is a marine sulfated polysaccharide with a wide variety of biological activities including anti-thrombotic and anti-inflammatory effects. This study evaluated the effect of fucoidan on the expression of inducible nitric oxide synthase (iNOS) in a macrophage cell line, RAW264.7. Low concentration range of fucoidan (10 μg/ml) increased the basal expression level of iNOS in quiescent macrophages. However, we found for the first time that fucoidan inhibited the release of nitric oxide (NO) in RAW264.7 cells stimulated with lipopolysaccharide (LPS). Western blot analysis revealed that fucoidan suppressed the LPS-induced expression of the inducible nitric oxide synthase (iNOS) gene. Moreover, the activation of both nuclear factor-κB (NF-κB) and activator protein 1 (AP-1) are key steps in the transcriptional activation of the iNOS gene. Here, it was revealed that fucoidan selectively suppressed AP-1 activation, and that the activation of AP-1 appears to be essential for the induction of iNOS in activated macrophages. This inhibitory effect on AP-1 activation by fucoidan might be associated with its NO blocking and anti-inflammatory effects

  3. A bifunctional amorphous polymer exhibiting equal linear and circular photoinduced birefringences.

    Science.gov (United States)

    Royes, Jorge; Provenzano, Clementina; Pagliusi, Pasquale; Tejedor, Rosa M; Piñol, Milagros; Oriol, Luis

    2014-11-01

    The large and reversible photoinduced linear and circular birefringences in azo-compounds are at the basis of the interest in these materials, which are potentially useful for several applications. Since the onset of the linear and circular anisotropies relies on orientational processes, which typically occur on the molecular and supramolecular length scale, respectively, a circular birefringence at least one order of magnitude lower than the linear one is usually observed. Here, the synthesis and characterization of an amorphous polymer with a dimeric repeating unit containing a cyanoazobenzene and a cyanobiphenyl moiety are reported, in which identical optical linear and circular birefringences are induced for proper light dose and ellipticity. A pump-probe technique and an analytical method based on the Stokes-Mueller formalism are used to investigate the photoinduced effects and to evaluate the anisotropies. The peculiar photoresponse of the polymer makes it a good candidate for applications in smart functional devices. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Linkage of α-cyclodextrin-terminated poly(dimethylsiloxanes by inclusion of quasi bifunctional ferrocene

    Directory of Open Access Journals (Sweden)

    Helmut Ritter

    2013-07-01

    Full Text Available We report the noncovalent linkage of terminally substituted oligo(dimethylsiloxanes bearing α-cyclodextrins (α-CD as host end groups for the cyclopentadienyl rings of ferrocene. This double complexation of unsubstituted ferrocene leads to a supramolecuar formation of the siloxane strands. Structural characterization was performed by the use of 1H NMR and IR spectroscopy and by mass spectrometry. Electron microscopy studies and dynamic light scattering measurements show a significant decrease of the derivative size after the complexation with ferrocene. In addition, further evidence for the successful complexation of the end groups was verified by the shifts of the protons in the 1H NMR spectra and in the correlation signals of the 2D ROESY NMR spectra.

  5. Bifunctional phenolic-choline conjugates as anti-oxidants and acetylcholinesterase inhibitors

    Czech Academy of Sciences Publication Activity Database

    Šebestík, Jaroslav; Marques, S. M.; Falé, P. L.; Santos, S.; Arduíno, D. M.; Cardoso, S. M.; Oliveira, S. M.; Serralheiro, M. L. M.; Santos, A. M.

    Roč. 26, č. 4 (485), s. 497 ISSN 1475-6366 Institutional research plan: CEZ:AV0Z40550506 Keywords : acetylcholinesterase inhibitors * antioxidants * hybrid ligands * anti-neurodegeneratives * Alzheimer´s disease Subject RIV: CC - Organic Chemistry

  6. Lactoferrin binding protein B - a bi-functional bacterial receptor protein.

    Directory of Open Access Journals (Sweden)

    Nicholas K H Ostan

    2017-03-01

    Full Text Available Lactoferrin binding protein B (LbpB is a bi-lobed outer membrane-bound lipoprotein that comprises part of the lactoferrin (Lf receptor complex in Neisseria meningitidis and other Gram-negative pathogens. Recent studies have demonstrated that LbpB plays a role in protecting the bacteria from cationic antimicrobial peptides due to large regions rich in anionic residues in the C-terminal lobe. Relative to its homolog, transferrin-binding protein B (TbpB, there currently is little evidence for its role in iron acquisition and relatively little structural and biophysical information on its interaction with Lf. In this study, a combination of crosslinking and deuterium exchange coupled to mass spectrometry, information-driven computational docking, bio-layer interferometry, and site-directed mutagenesis was used to probe LbpB:hLf complexes. The formation of a 1:1 complex of iron-loaded Lf and LbpB involves an interaction between the Lf C-lobe and LbpB N-lobe, comparable to TbpB, consistent with a potential role in iron acquisition. The Lf N-lobe is also capable of binding to negatively charged regions of the LbpB C-lobe and possibly other sites such that a variety of higher order complexes are formed. Our results are consistent with LbpB serving dual roles focused primarily on iron acquisition when exposed to limited levels of iron-loaded Lf on the mucosal surface and effectively binding apo Lf when exposed to high levels at sites of inflammation.

  7. Influence of metal loading on hydrocracking of rapeseed oil using bifunctional micro-/mesoporous composite materials

    Energy Technology Data Exchange (ETDEWEB)

    Gille, T.; Busse, O.; Reschetilowski, W. [Technische Univ. Dresden (Germany). Inst. of Industrial Chemistry

    2013-11-01

    Hydrocracking of rapeseed oil has been investigated in a fixed bed reactor under integral conditions. A synthesized micro-/mesoporous composite material Al-MCM-41/ZSM-5 modified by different metal loadings (NiMo, PtNiMo, Pt) was used as catalyst system. It could be demonstrated that the support material and their metal loading influence the product selectivity as well as the deactivation tendencies of the catalyst sample. (orig.)

  8. Silver-Copper Nanoalloy Catalyst Layer for Bifunctional Air Electrodes in Alkaline Media.

    Science.gov (United States)

    Wu, Xiaoqiang; Chen, Fuyi; Jin, Yachao; Zhang, Nan; Johnston, Roy L

    2015-08-19

    A carbon-free and binder-free catalyst layer composed of a Ag-Cu nanoalloy on Ni foam was used as the air cathode in a zinc-air battery for the first time. The Ag-Cu catalyst was prepared using pulsed laser deposition. The structures of the catalysts were found to consist of crystalline Ag-Cu nanoalloy particles with an average size of 2.58 nm embedded in amorphous Cu films. As observed in the X-ray photoelectron spectra, the Ag 3d core levels shifted to higher binding energies, whereas the Cu 2p core levels shifted to lower binding energies, indicating alloying of the silver and copper. Rotating disk electrode measurements indicated that the oxygen reduction reaction (ORR) proceeded through a four-electron pathway on the Ag50Cu50 and Ag90Cu10 nanoalloy catalysts in alkaline solution. Moreover, the catalytic activity of Ag50Cu50 in the ORR is more efficient than that of Ag90Cu10. By performing charge and discharge cycling measurements, the Ag50Cu50 catalyst layer was confirmed to have a maximum power density of approximately 86.3 mW cm(-2) and an acceptable cell voltage at 0.863 V for current densities up to 100 mA cm(-2) in primary zinc-air batteries. In addition, a round-trip efficiency of approximately 50% at a current density of 20 mA cm(-2) was also obtained in the test.

  9. A bi-functional xyloglucan galactosyltransferase is an indispensable salt stress tolerance determinant in arabidop

    KAUST Repository

    Li, Wenbo

    2013-07-01

    Salinity is an abiotic stress that substantially limits crop production worldwide. To identify salt stress tolerance determinants, we screened for Arabidopsis mutants that are hypersensitive to salt stress and designated these mutants as short root in salt medium (rsa). One of these mutants, rsa3-1, is hypersensitive to NaCl and LiCl but not to CsCl or to general osmotic stress. Reactive oxygen species (ROS) over-accumulate in rsa3-1 plants under salt stress. Gene expression profiling with Affymetrix microarray analysis revealed that RSA3 controls expression of many genes including genes encoding proteins for ROS detoxification under salt stress. Map-based cloning showed that RSA3 encodes a xyloglucan galactosyltransferase, which is allelic to a gene previously named MUR3/KAM1. The RSA3/ MUR3/KAM1-encoded xylogluscan galactosyltransferase regulates actin microfilament organization (and thereby contributes to endomembrane distribution) and is also involved in cell wall biosynthesis. In rsa3-1, actin cannot assemble and form bundles as it does in the wild-type but instead aggregates in the cytoplasm. Furthermore, addition of phalloidin, which prevents actin depolymerization, can rescue salt hypersensitivity of rsa3-1. Together, these results suggest that RSA3/MUR3/KAM1 along with other cell wall-associated proteins plays a critical role in salt stress tolerance by maintaining the proper organization of actin microfilaments in order to minimize damage caused by excessive ROS. © 2013 The Author.

  10. Engineering Pichia pastoris for Efficient Production of a Novel Bifunctional Strongylocentrotus purpuratus Invertebrate-Type Lysozyme.

    Science.gov (United States)

    Huang, Peng; Shi, Jinlei; Sun, Qingwen; Dong, Xianping; Zhang, Ning

    2018-04-13

    Lysozymes are known as ubiquitously distributed immune effectors with hydrolytic activity against peptidoglycan, the major bacterial cell wall polymer, to trigger cell lysis. In the present study, the full-length cDNA sequence of a novel sea urchin Strongylocentrotus purpuratus invertebrate-type lysozyme (sp-iLys) was synthesized according to the codon usage bias of Pichia pastoris and was cloned into a constitutive expression plasmid pPIC9K. The resulting plasmid, pPIC9K-sp-iLys, was integrated into the genome of P. pastoris strain GS115. The bioactive recombinant sp-iLys was successfully secreted into the culture broth by positive transformants. The highest lytic activity of 960 U/mL of culture supernatant was reached in fed-batch fermentation. Using chitin affinity chromatography and gel-filtration chromatography, recombinant sp-iLys was produced with a yield of 94.5 mg/L and purity of > 99%. Recombinant sp-iLys reached its peak lytic activity of 8560 U/mg at pH 6.0 and 30 °C and showed antimicrobial activities against Gram-negative bacteria (Vibrio vulnificus, Vibrio parahemolyticus, and Aeromonas hydrophila) and Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis). In addition, recombinant sp-iLys displayed isopeptidase activity which reached the peak at pH 7.5 and 37 °C with the presence of 0.05 M Na + . In conclusion, this report describes the heterologous expression of recombinant sp-iLys in P. pastoris on a preparative-scale, which possesses lytic activity and isopeptidase activity. This suggests that sp-iLys might play an important role in the innate immunity of S. purpuratus.

  11. The bifunctional autophagic flux by 2-deoxyglucose to control survival or growth of prostate cancer cells

    International Nuclear Information System (INIS)

    Jeon, Jeong Yong; Kim, Seung Won; Park, Ki Cheong; Yun, Mijin

    2015-01-01

    Recent reports using metabolism regulating drugs showed that nutrient deprivation was an efficient tool to suppress cancer progression. In addition, autophagy control is emerging to prevent cancer cell survival. Autophagy breaks down the unnecessary cytoplasmic components into anabolic units and energy sources, which are the most important sources for making the ATP that maintains homeostasis in cancer cell growth and survival. Therefore, the glucose analog 2-deoxyglucose (2DG) has been used as an anticancer reagent due to its inhibition of glycolysis. Prostate cancer cells (PC3) were treated with 2DG for 6 h or 48 h to analyze the changing of cell cycle and autophagic flux. Rapamycin and LC3B overexpressing vectors were administered to PC3 cells for autophagy induction and chloroquine and shBeclin1 plasmid were used to inhibit autophagy in PC3 cells to analyze PC3 cells growth and survival. The samples for western blotting were prepared in each culture condition to confirm the expression level of autophagy related and regulating proteins. We demonstrated that 2DG inhibits PC3 cells growth and had discriminating effects on autophagy regulation based on the different time period of 2DG treatment to control cell survival. Short-term treatment of 2DG induced autophagic flux, which increased microtubule associated protein 1 light chain 3B (LC3B) conversion rates and reduced p62 levels. However, 2DG induced autophagic flux is remarkably reduced over an extended time period of 2DG treatment for 48 h despite autophagy inducing internal signaling being maintained. The relationship between cell growth and autophagy was proved. Increased autophagic flux by rapamycin or LC3B overexpression powerfully reduced cell growth, while autophagy inhibition with shBeclin1 plasmid or chloroquine had no significant effect on regulating cell growth. Given these results, maintaining increased autophagic flux was more effective at inhibiting cancer cell progression than inhibition of autophagic flux, which is necessary for the survival of PC3 cells. Autophagic flux should be tightly regulated to maintain metabolic homeostasis for cancer cell growth and survival in PC3 cells and is a suitable target for cancer therapy. The online version of this article (doi:10.1186/s12885-015-1640-z) contains supplementary material, which is available to authorized users

  12. Hydrocracking of ethyl laurate on bifunctional micro-/mesoporous composite materials

    Energy Technology Data Exchange (ETDEWEB)

    Adam, M.; Busse, O.; Reschetilowski, W. [Technische Univ. Dresden (Germany). Inst. for Industrial Chemistry

    2011-07-01

    Hydrocracking of ethyl laurate (dodecanoic acid ethyl ester) as a representative model compound of vegetable oil has been investigated in a fixed bed reactor under integral conditions. A synthesized micro-/mesoporous composite support material Al-MCM-41/ZSM-5 modified by different metal loadings (NiMo, NiW, PtNiW) was used as catalyst system. It could be demonstrated that the metal loading and reducibility influence product selectivity as well as deactivation behavior of catalyst samples. (orig.)

  13. Bifunctional electroluminescent and photovoltaic devices using bathocuproine as electron-transporting material and an electron acceptor

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L.L. [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun, 130033 (China); Graduate School of the Chinese Academy of Sciences, Beijing, 100039 (China); Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024 (China); Li, W.L. [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun, 130033 (China)]. E-mail: wllioel@yahoo.com.cn; Li, M.T. [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun, 130033 (China); Graduate School of the Chinese Academy of Sciences, Beijing, 100039 (China); Chu, B. [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun, 130033 (China)

    2007-01-15

    Electroluminescence (EL) devices, using 4, 4',4''-tris (2-methylphenyl- phenylamino) triphenylamine (m-MTDATA) as hole-transporting material and bathocuproine (BCP) as an electron-transporting material, were fabricated, which emitted bright green light peaked at 520 nm instead of the emission of m-MTDATA or BCP. It was attributed to the exciplex formation and emission at the interface of m-MTDATA and BCP. EL performance was significantly enhanced by a thin mixed layer (5 nm) of m-MTDATA and BCP inserted between the two organic layers of the original m-MTDATA/BCP bilayer device. The trilayer device showed maximum luminance of 1,205 cd/m{sup 2} at 8 V. At a luminance of 100 cd/m{sup 2}, the power efficiency is 1.64 cd/A. Commission International De L'Eclairoge (CIE) color coordinates of the output spectrum of the devices at 8 V are x=0.244 and y=0.464. These devices also showed photovoltaic (PV) properties, which were sensitive to UV light. The PV diode exhibits high open-circuit voltage (V {sub oc}) of 2.10 V under illumination of 365 nm UV light with 2 mW/cm{sup 2}. And the short-circuit current (I {sub sc}) of 92.5x10{sup -6} A/cm{sup 2}, fill factor (FF) of 0.30 and power conversion efficiency ({eta} {sub e}) of 2.91% are respectively achieved. It is considered that strong exciplex emission in an EL device is a good indicator of efficient charge transfer at the organic interface, which is a basic requirement for good PV performance. Both the bilayer and trilayer devices showed EL and PV properties, suggesting their potential use as multifunction devices.

  14. Activation of trans geometry in bifunctional mononuclear platinum complexes by a non-bulky methylamine ligand

    Czech Academy of Sciences Publication Activity Database

    Frýbortová, M.; Nováková, Olga; Štěpánková, Jana; Novohradský, Vojtěch; Gibson, D.; Kašpárková, Jana; Brabec, Viktor

    2013-01-01

    Roč. 126, SEP2013 (2013), s. 46-54 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GAP301/10/0598; GA ČR(CZ) GA13-08273S Institutional research plan: CEZ:AV0Z50040702 Institutional support: RVO:68081707 Keywords : HETEROCYCLIC AMINE LIGAND * INTERSTRAND CROSS-LINKS * DNA-BINDING MODE Subject RIV: BO - Biophysics Impact factor: 3.274, year: 2013

  15. Aldosterone and cortisol co-secreting bifunctional adrenal cortical carcinoma: A rare event

    Directory of Open Access Journals (Sweden)

    Puskar Shyam Chowdhury

    2014-01-01

    Full Text Available Adrenocortical carcinoma (ACC co-secreting aldosterone and cortisol is extremely rare. We report the case of a 37-yearold female who presented with paresis and facial puffiness. Evaluation revealed hypertension, hyperglycemia, severe hypokalemia and hyperaldosteronemia with elevated plasma aldosterone to renin ratio (ARR. Urinary free cortisol estimation showed elevated levels. Computed tomography scan revealed a right adrenal mass. Radical adrenalectomy specimen revealed ACC (T3N1. Post-operatively, the patient became normotensive and euglycemic with normalization of urinary cortisol and ARR. This case highlights the need for a complete evaluation in patients of hyperaldosteronism if overlapping symptoms of hypercortisolism are encountered, to avoid post-operative adrenal crisis.

  16. The Golgi localized bifunctional UDP-rhamnose/UDP-galactose transporter family of Arabidopsis

    DEFF Research Database (Denmark)

    Rautengarten, Carsten; Ebert, Berit; Moreno, Ignacio

    2014-01-01

    Delivery of nucleotide sugar substrates into the Golgi apparatus and endoplasmic reticulum for processes such as cell wall biosynthesis and protein glycosylation is critical for plant growth and development. Plant genomes encode large families of uncharacterized nucleotide sugar transporters that...

  17. Chrysanthemyl diphosphate synthase operates in planta as a bifunctional enzyme with chrysanthemol synthase activity

    DEFF Research Database (Denmark)

    Yang, Ting; Gao, Liping; Hu, Hao

    2014-01-01

    Chrysanthemyl diphosphate synthase (CDS) is the first path-way-specific enzyme in the biosynthesis of pyrethrins, the most widely used plant-derived pesticide. CDS catalyzes c1′-2-3 cyclopropanation reactions of two molecules of dimethylallyl diphosphate (DMAPP) to yield chrysanthemyl diphosphate...

  18. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-08

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

  19. Superparamagnetic Bifunctional Bisphosphonates Nanoparticles: A Potential MRI Contrast Agent for Osteoporosis Therapy and Diagnostic

    Directory of Open Access Journals (Sweden)

    Y. Lalatonne

    2010-01-01

    Full Text Available A bone targeting nanosystem is reported here which combined magnetic contrast agent for Magnetic Resonance Imaging (MRI and a therapeutic agent (bisphosphonates into one drug delivery system. This new targeting nanoplatform consists of superparamagnetic γFe2O3 nanoparticles conjugated to 1,5-dihydroxy-1,5,5-tris-phosphono-pentyl-phosphonic acid (di-HMBPs molecules with a bisphosphonate function at the outer of the nanoparticle surface for bone targeting. The as-synthesized nanoparticles were evaluated as a specific MRI contrast agent by adsorption study onto hydroxyapatite and MRI measurment. The strong adsorption of the bisphosphonates nanoparticles to hydroxyapatite and their use as MRI T2∗ contrast agent were demonstrated. Cellular tests performed on human osteosarcoma cells (MG63 show that γFe2O3@di-HMBP hybrid nanomaterial has no citoxity effect in cell viability and may act as a diagnostic and therapeutic system.

  20. Pt-Si Bifunctional Surfaces for CO and Methanol Electro-Oxidation

    DEFF Research Database (Denmark)

    Permyakova, Anastasia A.; Han, Binghong; Jensen, Jens Oluf

    2015-01-01

    and storage. Here we report on Pt-Si bulk samples prepared by arc-melting, for the first time, with high activities toward the electro-oxidation of CO and methanol. Increasing the Si concentration on the surface was correlated with the shifts of onset oxidation potentials to lower values and higher activities...... for CO and methanol electro-oxidation. It is proposed that the reaction on the Pt-Si catalyst could follow a Langmuir-Hinshelwood type of mechanism, where substantially enhanced catalytic activity is attributed to the fine-tuning of the surface Pt-Si atomic structure....

  1. Bifunctional amine-tethered ruthenium(II) arene complexes form monofunctional adducts on DNA

    Czech Academy of Sciences Publication Activity Database

    Melchart, M.; Habtemariam, A.; Nováková, Olga; Moggach, S.A.; Fabbiani, F.P.A.; Parsons, S.; Brabec, Viktor; Sadler, P.J.

    2007-01-01

    Roč. 46, č. 21 (2007), s. 8950-8962 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA305/05/2030; GA ČR(CZ) GA203/06/1239; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN200200651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : DNA * ruthenium * cancer Subject RIV: BO - Biophysics Impact factor: 4.123, year: 2007

  2. Photoluminescence study on amino functionalized dysprosium oxide-zinc oxide composite bifunctional nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Joseph, Aswathy; Praveen, G.L; Abha, K.; Lekha, G.M [Department of Chemistry, University of Kerala, Kariavattom, Kerala 695581 (India); George, Sony, E-mail: emailtosony@gmail.com [Department of Chemistry, University of Kerala, Kariavattom, Kerala 695581 (India)

    2012-08-15

    An organic dispersion of 9-15 nm size stable dysprosium oxide incorporated zinc oxide nanocomposites exhibiting luminescence in the visible region has been synthesised by a wet chemical precipitation technique at room temperature. Tetraethoxysilane TEOS [(C{sub 2}H{sub 5}O){sub 4}Si], (3-aminopropyl) trimethoxysilane (APTS) and a 1:1 mixture of TEOS-APTS have been used as capping agents to control the particle size as well as to achieve uniform dispersion of composite nanoparticles in methanol medium. X-ray diffractometer (XRD) analysis reveals the formation phase of amino-functionalised colloidal dysprosium oxide incorporated ZnO composite nanoparticles to be of zincite structure. The Transmission Electron Microscopy (TEM) images show that the particles are spheroids in shape, having average crystalline sizes ranging from 9 to 15 nm. The photoluminescence (PL) observed in these composites has been attributed to the presence of near band edge excitonic emission and existence of defect centres. The time correlated single photon counting studies of the composite nanoparticles exhibited three decay pathways. The enhanced PL emission intensity of solid state fluorescence spectra of samples is attributed to the absence of vibrational relaxation process. - Highlights: Black-Right-Pointing-Pointer Nano-composites are synthesised using a one step wet chemical precipitation method. Black-Right-Pointing-Pointer A significant fluorescence life time of 8.25 ns is obtained for the nano-composite. Black-Right-Pointing-Pointer Nano-composite particles exhibited pale yellow fluorescence rather than blue. Black-Right-Pointing-Pointer Vibrational cascade free enhanced fluorescence is obtained for the dry sample.

  3. Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

    Science.gov (United States)

    Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

    2018-05-01

    The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

  4. Starch as a source, starch as a sink: the bifunctional role of starch in carbon allocation.

    Science.gov (United States)

    MacNeill, Gregory J; Mehrpouyan, Sahar; Minow, Mark A A; Patterson, Jenelle A; Tetlow, Ian J; Emes, Michael J

    2017-07-20

    Starch commands a central role in the carbon budget of the majority of plants on earth, and its biological role changes during development and in response to the environment. Throughout the life of a plant, starch plays a dual role in carbon allocation, acting as both a source, releasing carbon reserves in leaves for growth and development, and as a sink, either as a dedicated starch store in its own right (in seeds and tubers), or as a temporary reserve of carbon contributing to sink strength, in organs such as flowers, fruits, and developing non-starchy seeds. The presence of starch in tissues and organs thus has a profound impact on the physiology of the growing plant as its synthesis and degradation governs the availability of free sugars, which in turn control various growth and developmental processes. This review attempts to summarize the large body of information currently available on starch metabolism and its relationship to wider aspects of carbon metabolism and plant nutrition. It highlights gaps in our knowledge and points to research areas that show promise for bioengineering and manipulation of starch metabolism in order to achieve more desirable phenotypes such as increased yield or plant biomass. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  5. Synthesis and thermal properties of hetero-bifunctional PLA oligomers and their stereocomplexes

    NARCIS (Netherlands)

    ten Breteler, M.R.; Feijen, Jan; Dijkstra, Pieter J.; Signori, F.; Signori, F.

    2013-01-01

    Abstract Hetero-telechelic, low-molecular-weight polylactides (PLAs) were prepared by the zinc-catalyzed ring-opening polymerization of l-lactide or d-lactide using functional initiators and subsequent reaction with termination reagents, yielding –OH, –COOH, –NH2 and –SH as functional chain ends.

  6. Synthesis, singlet-oxygen photogeneration, two-photon absorption, photo-induced DNA cleavage and cytotoxic properties of an amphiphilic β-Schiff-base linked Ru(II) polypyridyl–porphyrin conjugate

    International Nuclear Information System (INIS)

    Ke, Hanzhong; Ma, Wanpeng; Wang, Hongda; Cheng, Guoe; Yuan, Han; Wong, Wai-Kwok; Kwong, Daniel W.J.; Tam, Hoi-Lam; Cheah, Kok-Wai; Chan, Chi-Fai; Wong, Ka-Leung

    2014-01-01

    A novel porphyrin–polypyridyl ruthenium(II) conjugate (TPP–Ru), in which the ruthenium(II) polypyridyl moiety is linked to the β-position of the tetraphenylporphyrin via a Schiff base linkage, has been synthesized and characterized by 1 H NMR, HRMS and UV–visible spectroscopy. The relative singlet oxygen quantum yield and two-photon absorption cross-section of this conjugate, together with its photo-induced DNA cleavage and cytotoxic activities were measured. The results show that the amphiphilic ruthenium(II) polypyridyl–porphyrin conjugate is an effective DNA photocleavage agent, with potential application in one- and two-photon absorption anti-cancer photodynamic therapy. - Highlights: • New porphyrin–ruthenium(II) polypyridyl complexes (TTP–Ru) have been synthesized. • The TTP–Ru shows substantial two-photon absorption cross-section (σ 2 =391 GM). • The TTP–Ru exhibits a substantial 1 O 2 quantum yield (0.64±0.13). • The TTP–Ru exhibits a strong DNA cleavage activity upon photo-excitation. • The TTP–Ru is available for in vitro imaging and as a photodynamic therapy agent

  7. The Triruthenium Complex [{(acac)(2)Ru-II}(3)(L)] Containing a Conjugated Diquinoxaline[2,3-a : 2 '',3 ''-c]phenazine (L) Bridge and Acetylacetonate (acac) as Ancillary Ligands. Synthesis, Spectroelectrochemical and EPR Investigation

    Czech Academy of Sciences Publication Activity Database

    Patra, S.; Sarkar, B.; Ghumaan, S.; Fiedler, Jan; Kaim, W.; Lahiri, G. K.

    -, č. 5 (2004), s. 754-758 ISSN 1477-9226 R&D Projects: GA MŠk OC D14.20; GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : nonlinear-optical properties * electrochemical properties * spectroelectrochemistry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.926, year: 2004

  8. Several novel Ru(II) and Ru(III) complexes formed by reduction of (RuO4bipy) and (RuO3phen)2O with hydroquinone and methanol

    International Nuclear Information System (INIS)

    Ishiyama, Toshio

    1975-01-01

    The geometrical isomers, cis-dichloro-trans-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II) and cis-dichloro-cis-(methanol)(hydroquinone)(2,2'-bipyridine)ruthenium(II), [RuCl 2 (MeOH)(QH 2 )bipy] (complex I and II), were synthesized by reduction and substitution reactions of [RuO 4 bipy] and [RuO 2 (OH) 2 bipy] with hydroquinone in hydrochloric acid solution, and methanol. cis-Chloro(hydroquinonato)bis(2,2'-bipyridine)ruthenium(II), cis-[RuCl(QH)(bipy) 2 ], was obtained from the substitution reaction of complex I or II with 2,2'-bipyridine in methanol, and cis-chloro(hydroquinone)bis(2,2'-bipyridine)ruthenium(II) chloride, cis-[RuCl(QH 2 )(bipy) 2 ]Cl, was also obtained from the substitution of cis-trans-[RuCl 2 (MeOH)(QH 2 )bipy] in methanol containing hydrochloric acid. cis-Dihydroxobis(2,2'-bipyridine)ruthenium(II), cis-[Ru(OH) 2 (bipy) 2 ], was obtained by heating an aqueous solution of cis-[RuCl(QH)(bipy) 2 ]. Trihydroxoaquo(1,10-phenanthroline)ruthenium(III), [Ru(OH) 3 (H 2 O)phen] was also synthesized from [RuO 3 phen] 2 O and [Ru(OH) 3 phen] 2 O by reduction reactions similar to those used for [RuCl 2 (MeOH)(QH 2 )bipy]. These complexes were characterized by the infrared, visible and ultraviolet absorption spectra, and also by polarographic and magnetic measurements. The structures are discussed. (auth.)

  9. A novel photo-active Cd:1,4-benzene dicarboxylate metal organic framework templated using [Ru(ii)(2,2'-bipyridine)3]2+: synthesis and photophysics of RWLC-5.

    Science.gov (United States)

    Larsen, Randy W; Mayers, Jacob M; Wojtas, Lukasz

    2017-09-26

    The development of photoactive porous materials is of significant importance for applications ranging from sustainable energy to pharmaceutical development and catalysis. A particularly attractive class of photo-active materials is the metal-organic framework (MOF)-based platform in which the photo-active elements are components of the framework itself or photo-active guests encapsulated within the MOF cavities. It has now been demonstrated that the photo-active [Ru(2,2'-bipyridine) 3 ] 2+ (RuBpy) complex can template the formation of MOFs with varying three dimensional structures. Here we report the synthesis and structural and photo-physical characterization of a new RuBpy-templated MOF composed of Cd 2+ ions with 1,4-benzenedicarboxylate ligands (RWLC-5) that contains crystallographically resolved RuBpy complexes. The new material displays a biphasic emission decay (130 ns and 1180 ns, T = 20 °C) and a bathochromically shifted emission maximum, relative to RuBpy in solution (603 nm for RuBpy in ethanol vs. 630 nm for RWLC-5). The emission lifetimes also do not display temperature-dependent decays which are characteristic of RuBpy type complexes as well as other RuBpy templated MOFs. The lack of temperature dependence is consistent with the complete deactivation of the 3 LF state of the encapsulated RuBpy complex due to a constrained environment. The fast phase decay is attributed to a water molecule hydrogen bonded to a bipyridine ligand associated with ∼38% of the encapsulated RuBpy complexes resulting in the nonradiative deactivation of the 3 MLCT state.

  10. Synthesis, singlet-oxygen photogeneration, two-photon absorption, photo-induced DNA cleavage and cytotoxic properties of an amphiphilic β-Schiff-base linked Ru(II) polypyridyl–porphyrin conjugate

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Hanzhong, E-mail: kehanz@163.com [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074 (China); Ma, Wanpeng; Wang, Hongda; Cheng, Guoe [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074 (China); Yuan, Han [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Institute of Advanced Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Tam, Hoi-Lam; Cheah, Kok-Wai [Department of Physics, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Institute of Advanced Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Chan, Chi-Fai; Wong, Ka-Leung [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China)

    2014-10-15

    A novel porphyrin–polypyridyl ruthenium(II) conjugate (TPP–Ru), in which the ruthenium(II) polypyridyl moiety is linked to the β-position of the tetraphenylporphyrin via a Schiff base linkage, has been synthesized and characterized by {sup 1}H NMR, HRMS and UV–visible spectroscopy. The relative singlet oxygen quantum yield and two-photon absorption cross-section of this conjugate, together with its photo-induced DNA cleavage and cytotoxic activities were measured. The results show that the amphiphilic ruthenium(II) polypyridyl–porphyrin conjugate is an effective DNA photocleavage agent, with potential application in one- and two-photon absorption anti-cancer photodynamic therapy. - Highlights: • New porphyrin–ruthenium(II) polypyridyl complexes (TTP–Ru) have been synthesized. • The TTP–Ru shows substantial two-photon absorption cross-section (σ{sub 2}=391 GM). • The TTP–Ru exhibits a substantial {sup 1}O{sub 2} quantum yield (0.64±0.13). • The TTP–Ru exhibits a strong DNA cleavage activity upon photo-excitation. • The TTP–Ru is available for in vitro imaging and as a photodynamic therapy agent.

  11. A importância do estado excitado 3MLCT de compostos de Ru(II, Re(I e Ir(III no desenvolvimento de fotossensores, oleds e fotorredução de CO2

    Directory of Open Access Journals (Sweden)

    Andressa V. Müller

    Full Text Available The photochemistry and photophysics of coordination compounds have been extensively investigated not only because their structure, stability, reactivity dependence on the metal center oxidation state and the coordinated ligand; but also for their electronic transitions in a wide range of visible radiation. The knowledge of light absorption, excited state deactivation, sensitization and quenching processes are crucial to their manipulation aiming the development of systems capable of execute useful functions such as photosensors and/or probes, luminescent devices and molecular systems to convert sunlight into other types of energy. In this review, the progresses and challenges of biomolecules photosensors, organic light emitting diodes and CO2 photoreduction catalysts based on ruthenium(II, rhenium(I or iridium(III coordination compounds are discussed based on their photochemical and photophysical processes.

  12. Identification and Overexpression of a Bifunctional Aldehyde/Alcohol Dehydrogenase Responsible for Ethanol Production in Thermoanaerobacter mathranii

    DEFF Research Database (Denmark)

    Yao, Shuo; Just Mikkelsen, Marie

    2010-01-01

    Thermoanaerobacter mathranii contains four genes, adhA, adhB, bdhA and adhE, predicted to code for alcohol dehydrogenases involved in ethanol metabolism. These alcohol dehydrogenases were characterized as NADP(H)-dependent primary alcohol dehydrogenase (AdhA), secondary alcohol dehydrogenase (Adh....... Overexpressions of AdhE in strain BG1E1 with xylose as a substrate facilitate the production of ethanol at an increased yield. Copyright © 2010 S. Karger AG, Basel...

  13. Comparative studies of 111In-labeled monoclonal antibody using spacer-containing and non-spacer bifunctional chelates. 2

    International Nuclear Information System (INIS)

    Sun, Baofu

    1994-01-01

    Indium-111-labeled A7 monoclonal antibodies using two spacer-containing chelates, succinimido-EGS-DTPA (EGS-DTPA: diester spacer) and maleimido-C10-Bz-EDTA (C10-Bz-EDTA: hydrocarbon spacer) were investigated in human LS180 colon tumor bearing nude mice and were compared with two non-spacer chelates, cyclic DTPA dianhydride (cDTPAA) and isothiocyanatobenzyl-EDTA (SCN-Bz-EDTA). Compared with immunoconjugates using non-spacer chelates, immunoconjugates using spacer-containing chelates, especially C10-Bz-EDTA-A7 showed lower 111 In activity in normal organs. The radioactivity in the liver for C10-Bz-EDTA-A7 decreased continuously till 96 hrs postinjection, however, this liver radioactivity for EGS-DTPA-A7 showed little change after 24 hrs. Moreover, in liver subcellular distribution study, EGS-DTPA-A7 showed a higher activity retention in mitochondrial fraction which contained lysosome, a place for metabolizing and storing of 111 In labeled antibody, than that of C10-Bz-EDTA-A7. The C10-Bz-EDTA-A7 conjugate demonstrated more preferable tumor-to-non tumor contrast on the scintigrams than that found with other three immunoconjugates. Up to 96 hrs postinjection, tumor bearing nude mice injecting with immunoconjugates using spacer-containing chelates exreted twice radioactivity from whole body than that excreted by using non-spacer chelates. Interestingly, different from other three chelates, C10-Bz-EDTA-A7 were mainly excreted via feces. We conclude that the decrease of radioactivity in normal tissues in the case of EGS-DTPA-A7 was due to the rapid decrease of activity in the blood, while in the case of C10-Bz-EDTA-A7 it was due to the quickly excreted small metabolite through faces. 111 In labeled C10-Bz-EDTA conjugate is superior, at least when conjugated with A7, to other three chelate conjugates used in this study. (author)

  14. Crystal structure of CbpF, a bifunctional choline-binding protein and autolysis regulator from Streptococcus pneumoniae.

    Science.gov (United States)

    Molina, Rafael; González, Ana; Stelter, Meike; Pérez-Dorado, Inmaculada; Kahn, Richard; Morales, María; Moscoso, Miriam; Campuzano, Susana; Campillo, Nuria E; Mobashery, Shahriar; García, José L; García, Pedro; Hermoso, Juan A

    2009-03-01

    Phosphorylcholine, a crucial component of the pneumococcal cell wall, is essential in bacterial physiology and in human pathogenesis because it binds to serum components of the immune system and acts as a docking station for the family of surface choline-binding proteins. The three-dimensional structure of choline-binding protein F (CbpF), one of the most abundant proteins in the pneumococcal cell wall, has been solved in complex with choline. CbpF shows a new modular structure composed both of consensus and non-consensus choline-binding repeats, distributed along its length, which markedly alter its shape, charge distribution and binding ability, and organizing the protein into two well-defined modules. The carboxy-terminal module is involved in cell wall binding and the amino-terminal module is crucial for inhibition of the autolytic LytC muramidase, providing a regulatory function for pneumococcal autolysis.

  15. Comparative study of Hg(II) adsorption by thiol- and hydroxyl-containing bifunctional montmorillonite and vermiculite

    Energy Technology Data Exchange (ETDEWEB)

    Tran, Lytuong [College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); QuangBinh University, QuangBinh (Viet Nam); Wu, Pingxiao, E-mail: pppxwu@scut.edu.cn [College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China); The Key Laboratory of Environmental Protection and Eco-Remediation of Guangdong Regular Higher Education Institutions (China); Zhu, Yajie; Liu, Shuai; Zhu, Nengwu [College of Environment and Energy, South China University of Technology, Guangzhou 510006 (China); The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, Guangzhou 510006 (China)

    2015-11-30

    Graphical abstract: - Highlights: • Novel adsorbents were prepared by functionalization with BAL to remove Hg(II). • Thiol and hydroxyl groups contributed to the enhancement of Hg(II) removal. • BAL-Vm showed the most adsorption capacity of Hg(II). • The adsorption mechanism was discussed based on the adsorption behaviors. - Abstract: A novel approach to prepare adsorbents for Hg(II) uptake from aqueous media based on the grafting of dimercaprol (BAL), containing thiol and hydroxyl groups, onto the natural montmorillonite and vermiculite was investigated concerning the evaluation of the adsorption capacity. The kinetic study showed that the adsorption process abided by pseudo-second-order model. The adsorption behavior of Hg(II) onto the obtained samples fitted well with Langmuir isotherm model, exhibiting an enhanced maximum adsorption capacity of 8.57 and 3.21 mg g{sup −1} for BAL-Vm and BAL-Mt, respectively. The feasibility of Hg(II) uptake onto the the samples was studied thermodynamically and the calculated coefficients such as ΔH, ΔS and ΔG indicated a physical and spontaneous process. The pH values and coexisting cations had a great influence on Hg(II) removal, confirming the optimal pH value of 4.0–5.0 and the negative correlation between the ionic strength and the adsorption capacity of Hg(II). In general, BAL-Vm possessed a higher efficiency of Hg(II) uptake than BAL-Mt, contrary to that of the pristine clays. The pristine and functionalized materials were investigated by XRD, FTIR, BET, SEM and zeta potential analysis to gain in-depth insight into the structure and surface morphology. The results showed that BAL was successful grafted on montmorillonite and vermiculite surface, providing plentiful adsorption sites as chelating ligands. The mechanisms of Hg(II) adsorption on these samples could be further explained as ion exchange and electrostatic attraction for Vm and Mt, and formation of complexes for BAL-Vm and BAL-Mt.

  16. Efficient synthesis of tungsten oxide hydrate-based nanocomposites for applications in bifunctional electrochromic-energy storage devices

    Science.gov (United States)

    Chang, Xueting; Hu, Ruirui; Sun, Shibin; Lu, Tong; Liu, Tao; Lei, Yanhua; Dong, Lihua; Yin, Yansheng; Zhu, Yanqiu

    2018-05-01

    In this work, we realized the large-scale synthesis of WO3 · H2O nanoflakes (NFs), g-C3N4/WO3 · H2O nanocomposite (NC) and graphene (G)/WO3 · H2O NC via a sonochemical process with tungsten salt as the precursor, g-C3N4 or G sheets as the supports, and distilled water as the solvent. Both the g-C3N4/WO3 · H2O NC and G/WO3 · H2O NC exhibited much better electrochromic (EC) performance (higher coloration efficiencies and faster response times) than that of the WO3 · H2O NFs. Using the WO3 · H2O-based materials as electrode materials, EC batteries that integrate the energy storage and EC functions in one device have been assembled. The energy status of the EC batteries could be visually indicated by the reversible color variations. Compared with the plain WO3 · H2O-based EC batteries, the NC-based EC batteries possessed a lower color contrast between the charged and discharged conditions but much longer discharge durations. The EC batteries could be quickly charged in a few seconds by adding H2O2, and the charged batteries exhibited significantly-enhanced discharging durations in comparison with the initial ones. The g-C3N4/WO3 · H2O NC-EC batteries charged by a small amount of H2O2 could produce a long discharging duration up to 760 min.

  17. Bifunctional Characteristics of Al2O3 supported Ni in the HI Decomposition of Sulfur-Iodine Process

    Directory of Open Access Journals (Sweden)

    Park Chu-Sik

    2016-01-01

    Full Text Available The Sulfur-Iodine process is in need of catalytic reactor for HI decomposition because the HI decomposition reaction rate is very slow. Nickel as an alternative catalyst for platinum was investigated in this study. Al2O3 supported Ni catalysts were prepared by impregnation method. Ni amounts loaded over Al2O3 were in the range of 0.1~20 wt. %. HI decompositions were carried out in the temperature range of 573 ~ 773 K using the fixed-bed quartz reactor. The difference of catalysts before and after the reaction was analyzed using BET, CO/H2 chemisorption, XRD, XRF and SEM. It was confirmed by XRD and SEM-EDX analysis that Ni was converted to NiI2 during the HI decomposition. Catalyst deactivation due to the formation of NiI2 leads to a reduction of HI conversion. Although Ni of catalyst converted to NiI2, HI decomposition with low loading (up to 3 wt. % catalyst showed a little decrease of HI conversion. However, with more than 5 wt. % catalyst, the initial HI conversion was considerably decreased. In the particular case of 20 wt. %, the initial conversion was increased close to 60 %, which is higher than 20 % as an equilibrium conversion at 723 K. These results showed that Ni had not only a catalytic function for HI decomposition, but also function as a sorbent to absorb I2 produced from HI.

  18. Identification of a Plastid-Localized Bifunctional Nerolidol/Linalool Synthase in Relation to Linalool Biosynthesis in Young Grape Berries

    Directory of Open Access Journals (Sweden)

    Bao-Qing Zhu

    2014-12-01

    Full Text Available Monoterpenoids are a diverse class of natural products and contribute to the important varietal aroma of certain Vitis vinifera grape cultivars. Among the typical monoterpenoids, linalool exists in almost all grape varieties. A gene coding for a nerolidol/linalool (NES/LINS synthase was evaluated in the role of linalool biosynthesis in grape berries. Enzyme activity assay of this recombinant protein revealed that it could convert geranyl diphosphate and farnesyl diphosphate into linalool and nerolidol in vitro, respectively, and thus it was named VvRILinNer. However, localization experiment showed that this enzyme was only localized to chloroplasts, which indicates that VvRILinNer functions in the linalool production in vivo. The patterns of gene expression and linalool accumulation were analyzed in the berries of three grape cultivars (“Riesling”, “Cabernet Sauvignon”, “Gewurztraminer” with significantly different levels of monoterpenoids. The VvRILinNer was considered to be mainly responsible for the synthesis of linalool at the early developmental stage. This finding has provided us with new knowledge to uncover the complex monoterpene biosynthesis in grapes.

  19. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    OpenAIRE

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanof...

  20. Highly substituted zirconium and hafnium cyclopentadienyl bifunctional β-diketiminate complexes – Synthesis, structure, and catalytic activity towards ethylene polymerization

    Czech Academy of Sciences Publication Activity Database

    Havlík, A.; Lamač, Martin; Pinkas, Jiří; Varga, Vojtěch; Růžička, A.; Olejník, R.; Horáček, Michal

    2015-01-01

    Roč. 786, JUN 2015 (2015), s. 71-80 ISSN 0022-328X R&D Projects: GA ČR GAP106/10/0924 Institutional support: RVO:61388955 Keywords : Zirconium * Hafnium * Cyclopentadienyl Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.336, year: 2015