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Sample records for bifunctional trypanothione synthetase-amidase

  1. Protein S-Thiolation by Glutathionylspermidine (Gsp): THE ROLE OF ESCHERICHIA COLI Gsp SYNTHETASE/AMIDASE IN REDOX REGULATION*

    OpenAIRE

    Chiang, Bing-Yu; Chen, Tzu-Chieh; Pai, Chien-Hua; Chou, Chi-Chi; Chen, Hsuan-He; Ko, Tzu-Ping; Hsu, Wen-Hung; Chang, Chun-Yang; Wu, Whei-Fen; Wang, Andrew H.-J.; Lin, Chun-Hung

    2010-01-01

    Certain bacteria synthesize glutathionylspermidine (Gsp), from GSH and spermidine. Escherichia coli Gsp synthetase/amidase (GspSA) catalyzes both the synthesis and hydrolysis of Gsp. Prior to the work reported herein, the physiological role(s) of Gsp or how the two opposing GspSA activities are regulated had not been elucidated. We report that Gsp-modified proteins from E. coli contain mixed disulfides of Gsp and protein thiols, representing a new type of post-translational modification forme...

  2. Bifunctional antibodies for radioimmunotherapy.

    Science.gov (United States)

    Chatal, J F; Faivre-Chauvet, A; Bardies, M; Peltier, P; Gautherot, E; Barbet, J

    1995-04-01

    In two-step targeting technique using bifunctional antibodies, a nonradiolabeled immunoconjugate with slow uptake kinetics (several days) is initially injected, followed by a small radiolabeled hapten with fast kinetics (several hours) that binds to the bispecific immunoconjugate already taken up by the tumor target. In patients with colorectal or medullary thyroid cancer, clinical studies performed with an anti-CEA/anti-DTPA-indium bifunctional antibody and an indium-111-labeled di-DTPA-TL bivalent hapten showed that tumor uptake was not modified compared to results for F(ab')2 fragments of the same anti-CEA antibody directly labeled with indium-111, whereas the radioactivity of normal tissues was significantly reduced (3- to 6-fold). The fast tumor uptake kinetics (several hours) and high or very high tumor-to-normal tissue ratios obtained with the bifunctional antibody technique are favorable parameters for efficient radioimmunotherapy.

  3. Buthionine sulfoximine is a multitarget inhibitor of trypanothione synthesis in Trypanosoma cruzi.

    Science.gov (United States)

    Vázquez, Citlali; Mejia-Tlachi, Marlen; González-Chávez, Zabdi; Silva, Aketzalli; Rodríguez-Zavala, José Salud; Moreno-Sánchez, Rafael; Saavedra, Emma

    2017-12-01

    Buthionine sulfoximine (BSO) induces decreased glutathione (GSH) and trypanothione [T(SH) 2 ] pools in trypanosomatids, presumably because only gamma-glutamylcysteine synthetase (γECS) is blocked. However, some BSO effects cannot be explained by exclusive γECS inhibition; therefore, its effect on the T(SH) 2 metabolism pathway in Trypanosoma cruzi was re-examined. Parasites exposed to BSO did not synthesize T(SH) 2 even when supplemented with cysteine or GSH, suggesting trypanothione synthetase (TryS) inhibition by BSO. Indeed, recombinant γECS and TryS, but not GSH synthetase, were inhibited by BSO and kinetics and docking analyses on a TcTryS 3D model suggested BSO binding at the GSH site. Furthermore, parasites overexpressing γECS and TryS showed ~ 50% decreased activities after BSO treatment. These results indicated that BSO is also an inhibitor of TryS. © 2017 Federation of European Biochemical Societies.

  4. Effects of buthionine sulfoximine nifurtimox and benznidazole upon trypanothione and metallothionein proteins in Trypanosoma cruzi.

    Directory of Open Access Journals (Sweden)

    JUAN DIEGO MAYA

    2004-01-01

    Full Text Available Proteins rich in sulfhydryl groups, such as metallothionein, are present in several strains of the parasite Trypanosoma cruzi, the etiological agent of Chagas' disease. Metallothionein-like protein concentrations ranged from 5.1 to 13.2 pmol/mg protein depending on the parasite strain and growth phase. Nifurtimox and benznidazole, used in the treatment of Chagas' disease, decreased metallothionein activity by approximately 70%. T. cruzi metallothionein was induced by ZnCl2. Metallothionein from T. cruzi was partially purified and its monobromobimane derivative showed a molecular weight of approximately 10,000 Da by SDS-PAGE analysis. The concentration of trypanothione, the major glutathione conjugate in T. cruzi, ranged from 3.8 to 10.8 nmol/mg protein, depending on the culture phase. The addition of buthionine sulfoximine to the protozoal culture considerably reduced the concentration of trypanothione and had no effect upon the metallothionein concentration. The possible contribution of metallothionein-like proteins to drug resistance in T. cruzi is discussed.

  5. Dataset generated for Dissection of mechanisms of Trypanothione Reductase and Tryparedoxin Peroxidase through dynamic network analysis and simulations in leishmaniasis

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    Anurag Kumar

    2017-12-01

    Full Text Available Leishmaniasis is the second largest parasitic killer disease caused by the protozoan parasite Leishmania, transmitted by the bite of sand flies. It's endemic in the eastern India with 165.4 million populations at risk with the current drug regimen. Three forms of leishmaniasis exist in which cutaneous is the most common form caused by Leishmania major. Trypanothione Reductase (TryR, a flavoprotein oxidoreductase, unique to thiol redox system, is considered as a potential target for chemotherapy for trypanosomatids infection. It is involved in the NADPH dependent reduction of Trypanothione disulphide to Trypanothione. Similarly, is Tryparedoxin Peroxidase (Txnpx, for detoxification of peroxides, an event pivotal for survival of Leishmania in two disparate biological environment. Fe-S plays a major role in regulating redox balance. To check for the closeness between human homologs of these proteins, we have carried the molecular clock analysis followed by molecular modeling of 3D structure of this protein, enabling us to design and test the novel drug like molecules. Molecular clock analysis suggests that human homologs of TryR i.e. Glutathione Reductase and Txnpx respectively are highly diverged in phylogenetic tree, thus, they serve as good candidates for chemotherapy of leishmaniasis. Furthermore, we have done the homology modeling of TryR using template of same protein from Leishmania infantum (PDB ID: 2JK6. This was done using Modeller 9.18 and the resultant models were validated. To inhibit this target, molecular docking was done with various screened inhibitors in which we found Taxifolin acts as common inhibitors for both TryR and Txnpx. We constructed the protein-protein interaction network for the proteins that are involved in the redox metabolism from various Interaction databases and the network was statistically analysed. Keywords: Trypanothione Reductase, Tryparedoxin Peroxidase, L.major, Homology modeling, Molecular clock analysis

  6. A potent trypanocidal component from the fungus Lentinus strigosus inhibits trypanothione reductase and modulates PBMC proliferation

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    Betania Barros Cota

    2008-05-01

    Full Text Available The fungus Lentinus strigosus (Pegler 1983 (Polyporaceae, basidiomycete was selected in a screen for inhibitory activity on Trypanosoma cruzi trypanothione reductase (TR. The crude extract of L. strigosus was able to completely inhibit TR at 20 µg/ml. Two triquinane sesquiterpenoids (dihydrohypnophilin and hypnophilin, in addition to two panepoxydol derivatives (neopanepoxydol and panepoxydone, were isolated using a bioassay-guided fractionation protocol. Hypnophilin and panepoxydone displayed IC50 values of 0.8 and 38.9 µM in the TR assay, respectively, while the other two compounds were inactive. The activity of hypnophilin was confirmed in a secondary assay with the intracellular amastigote forms of T. cruzi, in which it presented an IC50 value of 2.5 µ M. Quantitative flow cytometry experiments demonstrated that hypnophilin at 4 µM also reduced the proliferation of human peripheral blood monocluear cells (PBMC stimulated with phytohemaglutinin, without any apparent interference on the viability of lymphocytes and monocytes. As the host immune response plays a pivotal role in the adverse events triggered by antigen release during treatment with trypanocidal drugs, the ability of hypnophilin to kill the intracellular forms of T. cruzi while modulating human PBMC proliferation suggests that this terpenoid may be a promising prototype for the development of new chemotherapeutical agents for Chagas disease.

  7. Stage-dependent expression and up-regulation of trypanothione synthetase in amphotericin B resistant Leishmania donovani.

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    Asif Equbal

    Full Text Available Kinetoplastids differ from other organisms in their ability to conjugate glutathione and spermidine to form trypanothione which is involved in maintaining redox homeostasis and removal of toxic metabolites. It is also involved in drug resistance, antioxidant mechanism, and defense against cellular oxidants. Trypanothione synthetase (TryS of thiol metabolic pathway is the sole enzyme responsible for the biosynthesis of trypanothione in Leishmania donovani. In this study, TryS gene of L. donovani (LdTryS was cloned, expressed, and fusion protein purified with affinity column chromatography. The purified protein showed optimum enzymatic activity at pH 8.0-8.5. The TryS amino acids sequences alignment showed that all amino acids involved in catalytic and ligands binding of L. major are conserved in L. donovani. Subcellular localization using digitonin fractionation and immunoblot analysis showed that LdTryS is localized in the cytoplasm. Furthermore, RT-PCR coupled with immunoblot analysis showed that LdTryS is overexpressed in Amp B resistant and stationary phase promastigotes (∼ 2.0-folds than in sensitive strain and logarithmic phase, respectively, which suggests its involvement in Amp B resistance. Also, H2O2 treatment upto 150 µM for 8 hrs leads to 2-fold increased expression of LdTryS probably to cope up with oxidative stress generated by H2O2. Therefore, this study demonstrates stage- and Amp B sensitivity-dependent expression of LdTryS in L. donovani and involvement of TryS during oxidative stress to help the parasites survival.

  8. 8-Methoxy-naphtho[2,3-b]thiophen-4,9-quinone, a non-competitive inhibitor of trypanothione reductase

    Directory of Open Access Journals (Sweden)

    Zani Carlos L

    2003-01-01

    Full Text Available The enzyme trypanothione reductase is a recognised drug target in trypanosomatids and has been used in the search of new compounds with potential activity against diseases such as leishmaniasis, Chagas disease and African trypanosomiasis. 8-Methoxy-naphtho [2,3-b] thiophen-4,9-quinone was selected in a screening of natural and synthetic compounds using an in vitro assay with the recombinant enzyme from Trypanosoma cruzi. Its mode of inhibition fits a non-competitive model with respect to the substrate (trypanothione and to the co-factor (NADPH, with Ki-values of 5 and 3.6 µM, respectively. When tested against human glutathione reductase, this compound did not display any significant inhibition at 100 µM, indicating a good selectivity against the parasite enzyme.

  9. 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.

  10. 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.

  11. Bifunctional electrocatalyst for oxygen/air electrodes

    International Nuclear Information System (INIS)

    Sasikala, N.; Ramya, K.; Dhathathreyan, K.S.

    2014-01-01

    Highlights: • Nano-Silver powder was prepared by chemical method. • Ag catalyst was characterized by SEM and XRD studies. • Ag was investigated as bi-functional electrocatalyst for oxygen/air electrodes. • Ag shows good electrochemical activity towards OER and ORR reactions. - Abstract: Nano-Silver powder has been studied as bi-functional electrocatalyst for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline medium. Ag nano-powder has been prepared by a simple wet chemical method with Silver nitrate as precursor and Glucose as reducing agent. X-ray Diffraction and Scanning Electron Microscopy studies were carried out to characterize the Silver catalyst. Electrochemical oxygen evolution characterization shows anodic peak typically at the range between 0.350 and 0.514 V Vs Hg/HgO corresponding to Silver oxidation followed by the onset of oxygen evolution at 0.706 V. Oxygen reduction reaction studies carried out using Rotating Disc Electrode (RDE) confirm the four electron reaction mechanism. Ag catalyst shows promising characteristics for oxygen evolution and oxygen reduction

  12. Crassiflorone derivatives that inhibit Trypanosoma brucei glyceraldehyde-3-phosphate dehydrogenase (TbGAPDH) and Trypanosoma cruzi trypanothione reductase (TcTR) and display trypanocidal activity.

    Science.gov (United States)

    Uliassi, Elisa; Fiorani, Giulia; Krauth-Siegel, R Luise; Bergamini, Christian; Fato, Romana; Bianchini, Giulia; Carlos Menéndez, J; Molina, Maria Teresa; López-Montero, Eulogio; Falchi, Federico; Cavalli, Andrea; Gul, Sheraz; Kuzikov, Maria; Ellinger, Bernhard; Witt, Gesa; Moraes, Carolina B; Freitas-Junior, Lucio H; Borsari, Chiara; Costi, Maria Paola; Bolognesi, Maria Laura

    2017-12-01

    Crassiflorone is a natural product with anti-mycobacterial and anti-gonorrhoeal properties, isolated from the stem bark of the African ebony tree Diospyros crassiflora. We noticed that its pentacyclic core possesses structural resemblance to the quinone-coumarin hybrid 3, which we reported to exhibit a dual-targeted inhibitory profile towards Trypanosoma brucei glyceraldehyde-3-phosphate dehydrogenase (TbGAPDH) and Trypanosoma cruzi trypanothione reductase (TcTR). Following this basic idea, we synthesized a small library of crassiflorone derivatives 15-23 and investigated their potential as anti-trypanosomatid agents. 19 is the only compound of the series showing a balanced dual profile at 10 μM (% inhibition TbGAPDH  = 64% and % inhibition TcTR  = 65%). In phenotypic assay, the most active compounds were 18 and 21, which at 5 μM inhibited Tb bloodstream-form growth by 29% and 38%, respectively. Notably, all the newly synthesized compounds at 10 μM did not affect viability and the status of mitochondria in human A549 and 786-O cell lines, respectively. However, further optimization that addresses metabolic liabilities including solubility, as well as cytochromes P450 (CYP1A2, CYP2C9, CYP2C19, and CYP2D6) inhibition, is required before this class of natural product-derived compounds can be further progressed. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  13. Molecular Docking and Binding Mode Analysis of Plant Alkaloids as in vitro and in silico Inhibitors of Trypanothione Reductase from Trypanosoma cruzi.

    Science.gov (United States)

    Argüelles, Alonso J; Cordell, Geoffrey A; Maruenda, Helena

    2016-01-01

    Trypanothione reductase (TryR) is a key enzyme in the metabolism of Trypanosoma cruzi, the parasite responsible for Chagas disease. The available repertoire of TryR inhibitors relies heavily on synthetic substrates of limited structural diversity, and less on plant-derived natural products. In this study, a molecular docking procedure using a Lamarckian Genetic Algorithm was implemented to examine the protein-ligand binding interactions of strong in vitro inhibitors for which no X-ray data is available. In addition, a small, skeletally diverse, set of natural alkaloids was assessed computationally against T. cruzi TryR in search of new scaffolds for lead development. The preferential binding mode (low number of clusters, high cluster population), together with the deduced binding interactions were used to discriminate among the virtual inhibitors. This study confirms the prior in vitro data and proposes quebrachamine, cephalotaxine, cryptolepine, (22S,25S)-tomatidine, (22R,25S)-solanidine, and (22R,25R)-solasodine as new alkaloid scaffold leads in the search for more potent and selective TryR inhibitors.

  14. Trypanothione Reductase and Superoxide Dismutase as Current Drug Targets for Trypanosoma cruzi: An Overview of Compounds with Activity against Chagas Disease.

    Science.gov (United States)

    Beltran-Hortelano, Ivan; Perez-Silanes, Silvia; Galiano, Silvia

    2017-05-31

    It has been over a century since Carlos Chagas discovered the Trypanosoma cruzi (T. cruzi) as the causative agent of Chagas disease (CD), a neglected tropical disease with several socioeconomic, epidemiological and human health repercussions. Currently, there are only two commercialized drugs to treat CD in acute phase, nifurtimox and benznidazol, with several adverse side effects. Thus, new orally available and safe drugs for this parasitic infection are urgently required. One strategy of great importance in new drug discovery programmes is based on the search of molecules enabling to interfere with enzymes involved in T. cruzi metabolism. This review will focus on two of the most promising targets for the therapy of CD: trypanothione reductase (TR) and the iron-containing superoxide dismutase (Fe- SOD), which protect the parasite against oxidative damage by reactive oxygen species. A brief comparison of the function, mechanism of action and the active sites between T. cruzi TR and Fe-SOD with their analogues enzymes in human, glutathione reductase (GR) and the corresponding SODs, will be discussed. This review will also summarize the recent development and structure-activity relationships of novel compounds reported for their ability to selectively inhibit these targets, aiming to define molecular bases in the search for new effective treatment of CD. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  15. Improved proteolytic stability and potent activity against Leishmania infantum trypanothione reductase of α/β-peptide foldamers conjugated to cell-penetrating peptides.

    Science.gov (United States)

    de Lucio, Héctor; Gamo, Ana María; Ruiz-Santaquiteria, Marta; de Castro, Sonia; Sánchez-Murcia, Pedro A; Toro, Miguel A; Gutiérrez, Kilian Jesús; Gago, Federico; Jiménez-Ruiz, Antonio; Camarasa, María-José; Velázquez, Sonsoles

    2017-11-10

    The objective of the current study was to enhance the proteolytic stability of peptide-based inhibitors that target critical protein-protein interactions at the dimerization interface of Leishmania infantum trypanothione reductase (Li-TryR) using a backbone modification strategy. To achieve this goal we carried out the synthesis, proteolytic stability studies and biological evaluation of a small library of α/β 3 -peptide foldamers of different length (from 9-mers to 13-mers) and different α→β substitution patterns related to prototype linear α-peptides. We show that several 13-residue α/β 3 -peptide foldamers retain inhibitory potency against the enzyme (in both activity and dimerization assays) while they are far less susceptible to proteolytic degradation than an analogous α-peptide. The strong dependence of the binding affinities for Li-TryR on the length of the α,β-peptides is supported by theoretical calculations on conformational ensembles of the resulting complexes. The conjugation of the most proteolytically stable α/β-peptide with oligoarginines results in a molecule with potent activity against L. infantum promastigotes and amastigotes. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  16. Cooperative CO2 Absorption Isotherms from a Bifunctional Guanidine and Bifunctional Alcohol.

    Science.gov (United States)

    Steinhardt, Rachel; Hiew, Stanley C; Mohapatra, Hemakesh; Nguyen, Du; Oh, Zachary; Truong, Richard; Esser-Kahn, Aaron

    2017-12-27

    Designing new liquids for CO 2 absorption is a challenge in CO 2 removal. Here, achieving low regeneration energies while keeping high selectivity and large capacity are current challenges. Recent cooperative metal-organic frameworks have shown the potential to address many of these challenges. However, many absorbent systems and designs rely on liquid capture agents. We present herein a liquid absorption system which exhibits cooperative CO 2 absorption isotherms. Upon introduction, CO 2 uptake is initially suppressed, followed by an abrupt increase in absorption. The liquid consists of a bifunctional guanidine and bifunctional alcohol, which, when dissolved in bis(2-methoxyethyl) ether, forms a secondary viscous phase within seconds in response to increases in CO 2 . The precipitation of this second viscous phase drives CO 2 absorption from the gas phase. The isotherm of the bifunctional system differs starkly from the analogous monofunctional system, which exhibits limited CO 2 uptake across the same pressure range. In our system, CO 2 absorption is strongly solvent dependent. In DMSO, both systems exhibit hyperbolic isotherms and no precipitation occurs. Subsequent 1 H NMR experiments confirmed the formation of distinct alkylcarbonate species having either one or two molecules of CO 2 bound. The solvent and structure relationships derived from these results can be used to tailor new liquid absorption systems to the conditions of a given CO 2 separation process.

  17. Structure and mechanism of Escherichia coli glutathionylspermidine amidase belonging to the family of cysteine; histidine-dependent amidohydrolases/peptidases

    OpenAIRE

    Pai, Chien-Hua; Wu, Hsing-Ju; Lin, Chun-Hung; Wang, Andrew H-J

    2011-01-01

    The bifunctional Escherichia coli glutathionylspermidine synthetase/amidase (GspSA) catalyzes both the synthesis and hydrolysis of Gsp. Its amidase domain (GspA), which catalyzes the hydrolysis of Gsp into glutathione and spermidine, plays an important role in redox sensing and protein S-thiolation. To gain insight of the regulation and catalytic mechanism of and further understand the recycling of the Gsp dimer and Gsp-S-protein adducts, we solved two crystal structures of GspA and GspSA bot...

  18. 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.

  19. 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

  20. 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)

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

    NARCIS (Netherlands)

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

    2015-01-01

    The ability to control nanoscale features precisely is increasingly being exploited to develop and improve monofunctional catalysts(1-4). Striking effects might also be expected in the case of bifunctional catalysts, which are important in the hydrocracking of fossil and renewable hydrocarbon

  2. Synthesis and characterization of bi-functional magneto-luminescent ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 7. Synthesis and characterization of bi-functional magneto-luminescent Fe₃O₄ @ SiO₂ @ NaLuF₄ :Eu³⁺ hybrid core / shell nanospheres. JIGMET LADOL HEENA KHAJURIA HAQ NAWAZ SHEIKH YUGAL KHAJURIA. Regular Article Volume 128 Issue ...

  3. 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

  4. (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).

  5. [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).

  6. 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.

  7. 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.

  8. Targeting Prostate Cancer with Bifunctional Modulators of the Androgen Receptor

    Science.gov (United States)

    2015-06-01

    References 1. Ramamoorthy S, Cidlowski JA. Exploring the molecular mecha- nisms of glucocorticoid receptor action from sensitivity to resis- tance. Endocr... actions of glucocorti- coids. Proc Natl Acad Sci USA. 2012;109:11776–11781. 16. van Rossum EF, van den Akker EL. Glucocorticoid resistance. En- docr Dev...we continued the use of glucocorticoid receptor (GR) as the model in which to test the bifunctional recruitment model. Given the modular nature of om

  9. Is Root Catalase a Bifunctional Catalase-Peroxidase?

    Science.gov (United States)

    Chioti, Vasileia; Zervoudakis, George

    2017-05-25

    Plant catalases exhibit spatial and temporal distribution of their activity. Moreover, except from the typical monofunctional catalase, a bifunctional catalase-peroxidase has been reported. The aim of this study was to investigate whether the leaf and root catalases from six different plant species ( Lactuca sativa , Cichorium endivia , Apium graveolens , Petroselinum crispum, Lycopersicon esculentum , and Solanum melongena ) correspond to the monofunctional or the bifunctional type based on their sensitivity to the inhibitor 3-amino-1,2,4-triazole (3-AT). The leaf catalases from all species seem to be monofunctional since they are very sensitive to 3-AT. On the other hand, the root enzymes from Lactuca sativa , Cichorium endivia , Lycopersicon esculentum , and Solanum melongena seem to be bifunctional catalase-peroxidases, considering that they are relatively insensitive to 3-AT, whereas the catalases from Apium graveolens and Petroselinum crispum display the same monofunctional characteristics as the leaves' enzymes. The leaf catalase activity is usually higher ( Lactuca sativa , Petroselinum crispum , and Solanum melongena ) or similar ( Cichorium endivia and Apium graveolens ) to the root one, except for the enzyme from Lycopersicon esculentum , while in all plant species the leaf protein concentration is significantly higher than the root protein concentration. These results suggest that there are differences between leaf and root catalases-differences that may correspond to their physiological role.

  10. Microwave assisted bi-functional activation of -bromo-tert-alcohols

    Indian Academy of Sciences (India)

    -Bromo-tert-alcohols; microwave; bi-functional activation; ZnS; flavour compounds. ... A concurrent bi-functional activation of trans-vicinal bromo- and hydroxyl groups with ZnS is elucidated. This is a new ... Spice and Flavour Science Department, CSIR-Central Food Technological Research Institute, Mysore 570 020, India ...

  11. 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.

  12. Novel magnetic-fluorescent bifunctional Janus nanofiber membrane

    Science.gov (United States)

    Wang, Qiutong; Geng, Yuting; Li, Jianhao; Yin, Meizhen; Hu, Yiseng; Liu, Yangxiu; Pan, Kai

    2018-04-01

    Magnetic-fluorescent bifunctional materials have received global attention owing to their potential in many fields. Herein, we reported a novel magnetic-fluorescent bifunctional Janus nanofiber membrane (NFM) by adding the as-prepared magnetic CoFe2O4 nanoparticles into the polyacrylonitrile (PAN) side (m-PAN) and the fluorescent molecules of 1,8-naphthalene anhydride (1,8-NAD) into the polyvinylpyrrolidone (PVP) side (f-PVP) via electrospinning method. The obtained m-PAN/f-PVP Janus NFM exhibited excellent magnetic performance and high fluorescent properties due to the unique structure. Compared with the m-PAN/f-PVP composite NFM, the Janus NFM showed higher fluorescent performance because the fluorescent molecules were isolated from the magnetic nanoparticles. In addition, the Janus NFM not only maintain the good self-supporting state in water but also realize a directional movement attracted by a magnet. The unique structure of Janus nanofiber is of great importance and demonstrates great potential applications.

  13. 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...

  14. Bifunctional chelates of RH-105 and AU199 as potential radiotherapeutic agents

    Energy Technology Data Exchange (ETDEWEB)

    Droege, P.

    1997-03-01

    Research is presented on new bifunctional chelating ligand systems with stability on the macroscopic and radiochemical levels. The synthesis of the following complexes are described: rhodium 105, palladium 109, and gold 198.

  15. Synthesis and 2D-QSAR studies of neolignan-based diaryl-tetrahydrofuran and -furan analogues with remarkable activity against Trypanosoma cruzi and assessment of the trypanothione reductase activity.

    Science.gov (United States)

    Hartmann, Ana Paula; de Carvalho, Marcelo Rodrigues; Bernardes, Lilian Sibelle Campos; Moraes, Milena Hoehr de; de Melo, Eduardo Borges; Lopes, Carla Duque; Steindel, Mario; da Silva, João Santana; Carvalho, Ivone

    2017-11-10

    Two series of diaryl-tetrahydrofuran and -furan were synthesised and screened for anti-trypanosomal activity against trypomastigote and amastigote forms of Trypanosoma cruzi, the causative agent of Chagas disease. Based on evidence that modification of a natural product may result in a more effective drug than the natural product itself, and using known neolignan inhibitors veraguensin 1 and grandisin 2 as templates to synthesise simpler analogues, remarkable anti-trypanosomal activity and selectivity were found for 3,5-dimethoxylated diaryl-furan 5c and 2,4-dimethoxylated diaryl-tetrahydrofuran 4e analogues with EC 50 0.01 μM and EC 50 0.75 μM, respectively, the former being 260-fold more potent than veraguensin 1 and 150-fold better than benznidazole, the current available drugs for Chagas disease treatment. The ability of the most potent anti-trypanosomal compounds to penetrate LLC-MK2 cells infected with T. cruzi amastigotes parasite was tested, which revealed 4e and 5e analogues as the most effective, causing no damage to mammalian cells. In particular, the majority of the derivatives were non-toxic against mice spleen cells. 2D-QSAR studies show the rigid central core and the position of dimethoxy-aryl substituents dramatically affect the anti-trypanosomal activity. The mode of action of the most active anti-trypanosomal derivatives was investigated by exploring the anti-oxidant functions of Trypanothione reductase (TR). As a result, diarylfuran series displayed the strongest inhibition, highlighting compounds 5d-e (IC 50 19.2 and 17.7 μM) and 5f-g (IC 50 8.9 and 7.4 μM), respectively, with similar or 2-fold higher than the reference inhibitor clomipramine (IC 50 15.2 μM). Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  16. 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...

  17. 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...

  18. 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.

  19. 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.

  20. From Food Waste to Efficient Bifunctional Nonprecious Electrocatalyst.

    Science.gov (United States)

    Hof, Ferdinand; Boni, Alessandro; Valenti, Giovanni; Huang, Kai; Paolucci, Francesco; Pénicaud, Alain

    2017-11-02

    Synergy between graphitic nanocarbon, obtainable from food waste through cracking of biomethane, and iron oxide nanoparticles provides access to efficient bifunctional electro catalysts. Dissolution of potassium-intercalated graphitic nanocarbons yields graphenide solutions with calibrated, small lateral size-reduced graphenes that are used subsequently as reducing agents of iron metal salts. This results in the strong binding of small size (2-5 nm) nanoparticles on the carbon framework homogeneously within the composite material, accessibility of the catalytic centers, and good conductivity provided by the underlying carbon framework. The iron oxide nanocarbon electrocatalyst performances are highlighted by the overall overpotential of approximately 1 V needed to reach the benchmark threshold of 10 mA cm -2 for the oxygen reduction reaction and the particular activity towards oxygen evolution reaction (η≈0.4 V at 10 mA cm -2 ), comparable to that of the precious RuO 2 and IrO 2 catalysts. This iron oxide/nanocarbon electrocatalyst is versatile, remarkably active, stable, and truly sustainable. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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.

  2. 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.

  3. Polymer-Supported Reagents: The Role of Bifunctionality in the Design of Ion-Selective Complexants

    Energy Technology Data Exchange (ETDEWEB)

    Alexandratos, S. D.

    2001-06-01

    The importance of multi-functionality in the preparation of ion-selective polymers is evident from the structure of enzymes where specific metal ions are bound through cooperative interactions among different amino acids. In synthetic polymers, ionic selectivity is enhanced when a chemical reaction is superimposed on an ion-exchange process. The concept of reactive ion exchange has been extended through the synthesis of crosslinked polymers whose metal ion selectivity is a function of reduction, coordination or precipitation reactions as determined by various covalently bound ligands. Development of three classes of dual mechanism bifunctional polymers, a new series of bifunctional diphosphonate polymers, and novel bifunctional ion-selective polymers with enhanced ionic accessibility has been accomplished.

  4. 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...... bifunctional requirement, which demands both adsorption and water oxidation sites. In this contribution, we explore the possibility of using Pt-Si alloys to fulfill this bifunctional requirement. Silicon, a highly oxophillic element, is alloyed into Pt as a site for water oxidation, while Pt serves as a CO...

  5. Janus nanobelts: fabrication, structure and enhanced magnetic-fluorescent bifunctional performance

    Science.gov (United States)

    Ma, Qianli; Yu, Wensheng; Dong, Xiangting; Wang, Jinxian; Liu, Guixia

    2014-02-01

    A new nanostructure of magnetic-fluorescent bifunctional Janus nanobelts with Fe3O4/PMMA as one half and Tb(BA)3phen/PMMA as the other half has been successfully fabricated by a specially designed parallel spinneret electrospinning technology. The morphology and properties of the final products were investigated in detail by X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), biological microscopy (BM), vibrating sample magnetometry (VSM) and fluorescence spectroscopy. The results revealed that the [Fe3O4/PMMA]//[Tb(BA)3phen/PMMA] magnetic-fluorescent bifunctional Janus nanobelts possess superior magnetic and fluorescent properties due to their special nanostructure. Compared with Fe3O4/Tb(BA)3phen/PMMA composite nanobelts, the magnetic-fluorescent bifunctional Janus nanobelts provided better performance. The new magnetic-fluorescent bifunctional Janus nanobelts have potential applications in novel nano-bio-label materials, drug target delivery materials and future nanodevices due to their excellent magnetic-fluorescent properties, flexibility and insolubility. Moreover, the construction technique for the Janus nanobelts is of universal significance for the fabrication of other multifunctional Janus nanobelts.A new nanostructure of magnetic-fluorescent bifunctional Janus nanobelts with Fe3O4/PMMA as one half and Tb(BA)3phen/PMMA as the other half has been successfully fabricated by a specially designed parallel spinneret electrospinning technology. The morphology and properties of the final products were investigated in detail by X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), biological microscopy (BM), vibrating sample magnetometry (VSM) and fluorescence spectroscopy. The results revealed that the [Fe3O4/PMMA]//[Tb(BA)3phen/PMMA] magnetic-fluorescent bifunctional Janus nanobelts possess superior magnetic and fluorescent properties due to their special

  6. 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

  7. Physical properties of bifunctional BST/LSMO nanocomposites

    Science.gov (United States)

    Beltran-Huarac, Juan; Martinez, Ricardo; Morell, Gerardo

    2014-02-01

    We report the fabrication of bifunctional nanocomposites consisting of ferroelectric Ba0.7Sr0.3TiO3 (BST) and ferromagnetic La0.67Sr0.33MnO3 (LSMO) at different concentrations via a high-temperature solid state route. The structural, dielectric, electrical, magnetodielectric (MD), magnetoelectric (ME) and magnetic properties of BST/LSMO nanocomposites were systematically investigated over a wide range of temperatures and frequencies. The X-Ray Diffraction analyses reveal the nanocrystalline nature of the heterostructures, wherein both perovskite phases co-exist. No parasitic phases were observed. The study of the dielectric properties shows that the nanocomposites exhibit relaxor ferroelectric character, with ferroelectric-paraelectric phase transition temperatures around 287-292 K that do not follow the Curie-Weiss law. The electrical measurements indicate that ac conductivities of the nanocomposites follow the Jonscher's universal power law, with activation energies of 0.42-0.63 eV based on Arrhenius-type behavior at high temperatures. The nanocomposites exhibit well-defined ferromagnetic hysteresis loops at room temperature (RT). The MD and ME measurements at RT indicate that BST/LSMO exhibits a nonlinear ME effect at low frequencies, with a threshold near 0.5 T. The magnetocapacitance (MCp) measurements evidence a quadratic dependence on magnetic field, further confirming the multiferroic nature of BST/LSMO. The order of MCp was found to be ˜7% per Tesla. The analysis of the MCp measurements indicates that one of the BST/LSMO compositions studied can be considered as a new multiferroic compound.

  8. 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...

  9. 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

  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. 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.

  13. 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)

  14. 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

  15. 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

    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...

  16. 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.

  17. Synthesis, characterization and performance of bifunctional catalysts for the synthesis of menthol from citronellal

    NARCIS (Netherlands)

    ten Dam, J.; Ramanathan, A; Djanashvili, K.; Kapteijn, F.; Hanefeld, U.

    2017-01-01

    The synthesis of a series of bifunctional catalysts (1 wt% Pt/W-TUD-1 (Technische Universiteit Delft-1) and 1 wt% Pt/WO3/TUD-1) with different tungsten loadings (5-30 wt% WO3) is described. They were characterized using ICP-OES, INAA, N2 physisorption, XRD and

  18. Metagenomic Analysis of Apple Orchard Soil Reveals Antibiotic Resistance Genes Encoding Predicted Bifunctional Proteins▿

    Science.gov (United States)

    Donato, Justin J.; Moe, Luke A.; Converse, Brandon J.; Smart, Keith D.; Berklein, Flora C.; McManus, Patricia S.; Handelsman, Jo

    2010-01-01

    To gain insight into the diversity and origins of antibiotic resistance genes, we identified resistance genes in the soil in an apple orchard using functional metagenomics, which involves inserting large fragments of foreign DNA into Escherichia coli and assaying the resulting clones for expressed functions. Among 13 antibiotic-resistant clones, we found two genes that encode bifunctional proteins. One predicted bifunctional protein confers resistance to ceftazidime and contains a natural fusion between a predicted transcriptional regulator and a β-lactamase. Sequence analysis of the entire metagenomic clone encoding the predicted bifunctional β-lactamase revealed a gene potentially involved in chloramphenicol resistance as well as a predicted transposase. A second clone that encodes a predicted bifunctional protein confers resistance to kanamycin and contains an aminoglycoside acetyltransferase domain fused to a second acetyltransferase domain that, based on nucleotide sequence, was predicted not to be involved in antibiotic resistance. This is the first report of a transcriptional regulator fused to a β-lactamase and of an aminoglycoside acetyltransferase fused to an acetyltransferase not involved in antibiotic resistance. PMID:20453147

  19. Microwave assisted bi-functional activation of -bromo-tert-alcohols

    Indian Academy of Sciences (India)

    unsaturated ketones in good yield is reported. The reaction of substrates with DMSO in 1:1 ratio (w/v) is promoted by ZnS in a solvent-free condition. A concurrent bi-functional activation of trans-vicinal bromo- and hydroxyl groups with ZnS is ...

  20. Highly Enantioselective Three-Component Direct Mannich Reactions of Unfunctionalized Ketones Catalyzed by Bifunctional Organocatalysts

    Science.gov (United States)

    Guo, Qunsheng; Zhao, John Cong-Gui

    2013-01-01

    A highly stereoselective three-component direct Mannich reaction between aromatic aldehydes, p-toluenesulfonamide, and unfunctionalized ketones was achieved through an enolate mechanism for the first time with a bifunctional quinidine thiourea catalyst. The corresponding N-tosylated β-aminoketones were obtained in high yields and excellent diastereo- and enantioselectivities (up to >99:1 dr and >99% ee). PMID:23343472

  1. 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

  2. A Metal-Amino Acid Complex-Derived Bifunctional Oxygen Electrocatalyst for Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Ding, Yanjun; Niu, Yuchen; Yang, Jia; Ma, Liang; Liu, Jianguo; Xiong, Yujie; Xu, Hangxun

    2016-10-01

    Bifunctional oxygen electrocatalyst: A metal-amino acid complex is developed to prepare high-performance mesoporous carbon electrocatalyst for both oxygen reduction and oxygen evolution reactions. Such prepared catalyst can be used to assemble rechargeable zinc-air batteries with excellent durability. This work represents a new route toward low-cost, highly active, and durable bifunctional electrocatalysts for cutting-edge energy conversion devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 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.

  4. 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

  5. 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

    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...... of information that is inaccessible by purely experimental means, and these structures, in turn, strongly suggest that a bifunctional reaction mechanism for alkaline HER will be operative at the interface between the films, the metal substrates, and the surrounding aqueous medium. This bifunctionality produces...... important changes in the calculated barriers of key elementary reaction steps, including water activation and dissociation, as compared to traditional monofunctional Pt surfaces. The successful identification of the structures of thin metal films and three-phase boundary catalysts is not only an important...

  6. Preparations of bifunctional polymeric beads simultaneously incorporated with fluorescent quantum dots and magnetic nanocrystals

    International Nuclear Information System (INIS)

    Tu Chifeng; Yang Yunhua; Gao Mingyuan

    2008-01-01

    Bifunctional polystyrene beads simultaneously incorporated with fluorescent CdTe quantum dots (Q-dots) and superparamagnetic Fe 3 O 4 nanocrystals were prepared by a modified mini-emulsion polymerization method, in which polymerizable surfactants were used as both phase transfer agent for aqueous colloidal nanoparticles and emulsifier. In addition, silica coating was also introduced to Fe 3 O 4 nanocrystals for regulating the internal structure of the composite beads. Transmission electron microscopy, confocal fluorescence microscopy and conventional spectroscopy were used to characterize the composite beads, as well as the polymerizable surfactant-coated CdTe Q-dots and silica-coated Fe 3 O 4 nanoparticles. Different mixing methods were also attempted in order to vary the size of the resultant bifunctional beads

  7. 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

    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...... of information that is inaccessible by purely experimental means, and these structures, in turn, strongly suggest that a bifunctional reaction mechanism for alkaline HER will be operative at the interface between the films, the metal substrates, and the surrounding aqueous medium. This bifunctionality produces...... important changes in the calculated barriers of key elementary reaction steps, including water activation and dissociation, as compared to traditional monofunctional Pt surfaces. The successful identification of the structures of thin metal films and three-phase boundary catalysts is not only an important...

  8. 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.

  9. 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)

  10. 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

    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 carbo...... 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...

  11. 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....

  12. 3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Park, Moon Gyu; Lee, Dong Un; Seo, Min Ho; Cano, Zachary Paul; Chen, Zhongwei

    2016-05-01

    To enhance energy efficiency and durability, a highly active and durable 3D ordered mesoporous cobalt oxide framework has been developed for rechargeable zinc-air batteries. The bifunctional air electrode consisting of 3DOM Co3 O4 having high active surface area and robust structure, results in superior charge and discharge battery voltages, and durable performance for electrically rechargeable zinc-air batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    Science.gov (United States)

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 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

  16. Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution.

    Science.gov (United States)

    Zhan, Yi; Du, Guojun; Yang, Shiliu; Xu, Chaohe; Lu, Meihua; Liu, Zhaolin; Lee, Jim Yang

    2015-06-17

    Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER-ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO). The good performance was attributed to the nanosizing of Co(OH)2 and the synergistic interaction between Co(OH)2 and N-rGO. A zinc-air cell assembled with a Co(OH)2-air electrode also showed a performance comparable to that of the state-of-the-art zinc-air cells. The combination of bifunctional activity and operational stability establishes Co(OH)2 as an effective low-cost alternative to the platinum group metal catalysts.

  17. 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.

  18. Preparation and characteristics of Fe3O4-YVO4:Eu3+ bifunctional magnetic-luminescent nanocomposites

    International Nuclear Information System (INIS)

    Peng Hongxia; Liu Guixia; Dong Xiangting; Wang Jinxian; Xu Jia; Yu Wensheng

    2011-01-01

    Graphical abstract: Highlights: → Bifunctional magnetic-luminescent nanocomposites with Fe 3 O 4 nanoparticles as the core and YVO 4 :Eu 3+ as the shell. → A cubic spinel structrue of Fe 3 O 4 core and a tetragonal phase of YVO 4 shell were obtained. → The nanocomposites displayed a strong red emission and superparamagnetic behavior at room temperature. - Abstract: A facile direct precipitation method has been developed for the synthesis of bifunctional magnetic-luminescent nanocomposites with Fe 3 O 4 nanoparticles as the core and YVO 4 :Eu 3+ as the shell. Transmission electron microscopy (TEM) images revealed that the obtained bifunctional nanocomposites had a core-shell structure and a spherical morphology. The average size was ∼150 nm, and the thickness of the shell was ∼15 nm. The X-ray diffraction (XRD) patterns showed that a cubic spinel structure of Fe 3 O 4 core and a tetragonal phase of YVO 4 shell were obtained. Fourier transform infrared (FT-IR) spectra confirmed that the YVO 4 :Eu 3+ had been successfully deposited on the surface of Fe 3 O 4 nanoparticles. Photoluminescence (PL) spectra indicated that the nanocomposites displayed a strong red characteristic emission of Eu 3+ . Magnetic measurements showed that the obtained bifunctional nanocomposites exhibited superparamagnetic behavior at room temperature. Therefore, the bifunctional nanocomposites are expected to develop many potential applications in biomedical fields.

  19. Unusual non-bifunctional mechanism for Co-PNP complex catalyzed transfer hydrogenation governed by the electronic configuration of metal center.

    Science.gov (United States)

    Hou, Cheng; Jiang, Jingxing; Li, Yinwu; Zhang, Zhihan; Zhao, Cunyuan; Ke, Zhuofeng

    2015-10-07

    The mimic of hydrogenases has unleashed a myriad of bifunctional catalysts, which are widely used in the catalytic hydrogenation of polar multiple bonds. With respect to ancillary ligands, the bifunctional mechanism is generally considered to proceed via the metal-ligand cooperation transition state. Inspired by the interesting study conducted by Hanson et al. (Chem Commun., 2013, 49, 10151), we present a computational study of a distinctive example, where a Co(II)-PNP catalyst with an ancillary ligand exhibits efficient transfer hydrogenation through a non-bifunctional mechanism. Both the bifunctional and non-bifunctional mechanisms are discussed. The calculated results, which are based on a full model of the catalyst, suggest that the inner-sphere non-bifunctional mechanism is more favorable (by ∼11 kcal mol(-1)) than the outer-sphere bifunctional mechanism, which is in agreement with the experimental observations. The origin of this mechanistic preference of the Co(II)-PNP catalyst can be attributed to its preference for the square planar geometry. A traditional bifunctional mechanism is less plausible for Co(II)-PNP due to the high distortion energy caused by the change in electronic configuration with the varied ligand field. Considering previous studies that focus on the development of ligands more often, this computational study indicates that the catalytic hydrogenation mechanism is controlled not only by the structure of the ligand but also by the electronic configuration of the metal center.

  20. Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

    Science.gov (United States)

    Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

    2015-09-01

    Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

  1. Combining conformational sampling and selection to identify the binding mode of zinc-bound amyloid peptides with bifunctional molecules

    Science.gov (United States)

    Xu, Liang; Gao, Ke; Bao, Chunyu; Wang, Xicheng

    2012-08-01

    The pathogenesis of Alzheimer's disease (AD) has been suggested to be related with the aggregation of amyloid β (Aβ) peptides. Metal ions (e.g. Cu, Fe, and Zn) are supposed to induce the aggregation of Aβ. Recent development of bifunctional molecules that are capable of interacting with Aβ and chelating biometal ions provides promising therapeutics to AD. However, the molecular mechanism for how Aβ, metal ions, and bifunctional molecules interact with each other is still elusive. In this study, the binding mode of Zn2+-bound Aβ with bifunctional molecules was investigated by the combination of conformational sampling of full-length Aβ peptides using replica exchange molecular dynamics simulations (REMD) and conformational selection using molecular docking and classical MD simulations. We demonstrate that Zn2+-bound Aβ(1-40) and Aβ(1-42) exhibit different conformational ensemble. Both Aβ peptides can adopt various conformations to recognize typical bifunctional molecules with different binding affinities. The bifunctional molecules exhibit their dual functions by first preferentially interfering with hydrophobic residues 17-21 and/or 30-35 of Zn2+-bound Aβ. Additional interactions with residues surrounding Zn2+ could possibly disrupt interactions between Zn2+ and Aβ, which then facilitate these small molecules to chelate Zn2+. The binding free energy calculations further demonstrate that the association of Aβ with bifunctional molecules is driven by enthalpy. Our results provide a feasible approach to understand the recognition mechanism of disordered proteins with small molecules, which could be helpful to the design of novel AD drugs.

  2. Further Characterization of the Bifunctional HIV Entry Inhibitor sCD4-FIT45

    Directory of Open Access Journals (Sweden)

    Alexander Falkenhagen

    2017-06-01

    Full Text Available HIV entry into target cells is a highly sequential and time-sensitive process. In recent years, potent HIV Env-targeting antibodies, such as VRC01, have been identified. However, antibodies bind only to a single epitope, and mutations that confer resistance to antibody-mediated inhibition of HIV entry have been detected. In contrast, HIV cannot escape from binding to soluble CD4 (sCD4 without a fitness disadvantage. sCD4 has the unique ability to induce conformational changes within the HIV envelope glycoproteins (Env that allow fusion inhibitors to bind. We have previously linked sCD4 to the fusion inhibitor FIT45 (sCD4-FIT45 and examined delivery of the bifunctional entry inhibitor via gene therapy. Here, we extend our studies and analyze the ability of sCD4-FIT45 to inhibit HIV Env-mediated cell fusion and HIV entry of several primary isolates. sCD4-FIT45 inhibited both cell fusion and HIV entry with remarkable antiviral activity. The mean 50% inhibitory concentrations (IC50 for sCD4-FIT45 were <0.2 μg/mL in both assays. Importantly, inhibition by sCD4-FIT45 was more potent than by VRC01, sCD4, or the previously described bifunctional protein sCD4-scFv17b. In contrast to sCD4, sCD4-FIT45 as well as VRC01 and sCD4-scFv17b did not mediate cell fusion between HIV Env+ and CD4−CCR5+ cells. The results presented here provide further evidence for the testing of sCD4-FIT45 and development of bifunctional proteins based on the sCD4-fusion inhibitor architecture.

  3. Further Characterization of the Bifunctional HIV Entry Inhibitor sCD4-FIT45.

    Science.gov (United States)

    Falkenhagen, Alexander; Joshi, Sadhna

    2017-06-16

    HIV entry into target cells is a highly sequential and time-sensitive process. In recent years, potent HIV Env-targeting antibodies, such as VRC01, have been identified. However, antibodies bind only to a single epitope, and mutations that confer resistance to antibody-mediated inhibition of HIV entry have been detected. In contrast, HIV cannot escape from binding to soluble CD4 (sCD4) without a fitness disadvantage. sCD4 has the unique ability to induce conformational changes within the HIV envelope glycoproteins (Env) that allow fusion inhibitors to bind. We have previously linked sCD4 to the fusion inhibitor FI T45 (sCD4-FI T45 ) and examined delivery of the bifunctional entry inhibitor via gene therapy. Here, we extend our studies and analyze the ability of sCD4-FI T45 to inhibit HIV Env-mediated cell fusion and HIV entry of several primary isolates. sCD4-FI T45 inhibited both cell fusion and HIV entry with remarkable antiviral activity. The mean 50% inhibitory concentrations (IC 50 ) for sCD4-FI T45 were <0.2 μg/mL in both assays. Importantly, inhibition by sCD4-FI T45 was more potent than by VRC01, sCD4, or the previously described bifunctional protein sCD4-scFv 17b . In contrast to sCD4, sCD4-FI T45 as well as VRC01 and sCD4-scFv 17b did not mediate cell fusion between HIV Env + and CD4 - CCR5 + cells. The results presented here provide further evidence for the testing of sCD4-FI T45 and development of bifunctional proteins based on the sCD4-fusion inhibitor architecture. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  4. 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.)

  5. Conversion of microalgal oil to biodiesel using bi-functional heterogenous catalysts MCS

    International Nuclear Information System (INIS)

    Nguyen Dang Toan; Nguyen Khanh Dieu Hong

    2015-01-01

    Biodiesel was synthesized from microalgal oil typed Botryococcus using a bi-functional heterogeneous catalyst mesoporous calcium containing silicate (MCS). The microalgal oil owned a very large amount of free fatty acid. The conditions for the reactions were controlled such as temperature, time, catalyst dosage, methanol/oil molar ratio and agitation speed. The results revealed that the optimum conditions should be temperature of 63 o C, reaction of 24 hours, catalyst dosage of 5 %wt, methanol/oil molar ratio of 45/1 and stirring speed of 450 rpm. The conversion of the reactions was 95.3 %. (author)

  6. 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

  7. 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.

  8. 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)

  9. Modifying the size and shape of monodisperse bifunctional alkaline-earth fluoride nanocrystals through lanthanide doping.

    Science.gov (United States)

    Chen, Daqin; Yu, Yunlong; Huang, Feng; Huang, Ping; Yang, Anping; Wang, Yuansheng

    2010-07-28

    In this communication, a simple route for modifying the uneven size and shape of alkaline-earth fluoride nanophases to monodisperse ultrasmall nanospheres through lanthanide doping is offered. These nanospheres are found to exhibit bifunctionality, i.e., tunable upconversion emissions as well as proper paramagnetism, making them potentially applicable in the biological field. The synthesis strategy, which involves doping of an impurity with a different valence than the cation in the nanophase, might be useful for controlling the solution growth of some technologically important nanomaterials.

  10. Orderly Layered Zr-Benzylphosphonate Nanohybrids for Efficient Acid-Base-Mediated Bifunctional/Cascade Catalysis.

    Science.gov (United States)

    Li, Hu; Fang, Zhen; He, Jian; Yang, Song

    2017-02-22

    The development of functional metal-organic materials that are robust and active for bifunctional/cascade catalysis is of great significance. Herein, a series of mesoporous and orderly layered nanohybrids were synthesized for the first time through simple and template-free assembly of ortho-, meta-, or para-xylylenediphosphonates (o-, p-, or m-PhP) containing zirconium. It was found that m-PhPZr nanoparticles (20-50 nm) with mesopores centered at 7.9 nm and high Lewis acid-base site ratio (1:0.7) showed excellent performance under mild conditions (as low as 82 °C) in transfer hydrogenation of carbonyl compounds, including bioaldehydes and alcohols, with near quantitative yields and little Zr leaching. Isotopic labeling studies indicated the occurrence of direct hydrogen transfer rather than metal hydride route by bifunctional catalysis. Lewis acidic (Zr) and basic (PO 3 ) centers of the heterogeneous catalyst were further revealed to play a synergistic role in one-pot cascade transformations, for example, of ethyl levulinate to γ-valerolactone and glucose to 5-hydroxymethylfurfural. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate.

    Science.gov (United States)

    Sun, Peng; Long, Xiangdong; He, Hao; Xia, Chungu; Li, Fuwei

    2013-11-01

    Considerable effort has been applied to the development of new processes and catalysts for cellulose conversion to valuable platform chemicals. Isosorbide is among the most interesting products as it can be applied as a monomer and building block for the future replacement of fossil resource-based products. A sustainable method of isosorbide production from cellulose is presented in this work. The strategy relies on a bifunctional Ru catalyst supported on mesoporous niobium phosphate in a H2 atmosphere under pressure without further addition of any soluble acid. Over 50 % yield of isosorbide with almost 100 % cellulose conversion can be obtained in 1 h. The large surface area, pore size, and strong acidity of mesoporous niobium phosphate promote the hydrolysis of cellulose and dehydration of sorbitol; additionally, the appropriate size of the supported Ru nanoparticles avoids unnecessary hydrogenolysis of sorbitol. Under a cellulose/catalyst mass ratio of 43.3, the present bifunctional catalyst could be stably used up to six times, with its mesoporous structure well preserved and without detectable Ru leaching into the reaction solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Porous NiFe-Oxide Nanocubes as Bifunctional Electrocatalysts for Efficient Water-Splitting.

    Science.gov (United States)

    Kumar, Ashwani; Bhattacharyya, Sayan

    2017-12-06

    Electrocatalytic water-splitting, a combination of oxygen and hydrogen evolution reactions (OER and HER), is highly attractive in clean energy technologies, especially for high-purity hydrogen production, whereas developing stable, earth-abundant, bifunctional catalysts has continued to pose major challenges. Herein, a mesoporous NiFe-oxide nanocube (NiFe-NC) system is developed from a NiFe Prussian blue analog metal-organic framework as an efficient bifunctional catalyst for overall water-splitting. The NiFe-NCs with ∼200 nm side length have a Ni/Fe molar ratio of 3:2 and is a composite of NiO and α/γ-Fe 2 O 3 . The NCs demonstrate overpotentials of 271 and 197 mV for OER and HER, respectively, in 1 M KOH at 10 mA cm -2 , which outperform those of 339 and 347 mV for the spherical NiFe-oxide nanoparticles having a similar composition. The electrolyzer constructed using NiFe-NCs requires an impressive cell voltage of 1.67 V to deliver a current density of 10 mA cm -2 . Along with a mesoporous structure with a broad pore size distribution, the NiFe-NCs demonstrate the qualities of a desired corrosion-resistant water-splitting catalyst with long-term stability. The exposure of active sites at the edges and vertices of the NCs was validated to play a crucial role in their overall catalytic performance.

  13. Strongly Coupled Molybdenum Carbide on Carbon Sheets as a Bifunctional Electrocatalyst for Overall Water Splitting.

    Science.gov (United States)

    Wang, Hao; Cao, Yingjie; Sun, Cheng; Zou, Guifu; Huang, Jianwen; Kuai, Xiaoxiao; Zhao, Jianqing; Gao, Lijun

    2017-09-22

    High-performance and affordable electrocatalysts from earth-abundant elements are desirably pursued for water splitting involving hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, a bifunctional electrocatalyst of highly crystalline Mo 2 C nanoparticles supported on carbon sheets (Mo 2 C/CS) was designed toward overall water splitting. Owing to the highly active catalytic nature of Mo 2 C nanoparticles, the high surface area of carbon sheets and efficient charge transfer in the strongly coupled composite, the designed catalysts show excellent bifunctional behavior with an onset potential of -60 mV for HER and an overpotential of 320 mV to achieve a current density of 10 mA cm -2 for OER in 1 m KOH while maintaining robust stability. Moreover, the electrolysis cell using the catalyst only requires a low cell voltage of 1.73 V to achieve a current density of 10 mA cm -2 and maintains the activity for more than 100 h when employing the Mo 2 C/CS catalyst as both anode and cathode electrodes. Such high performance makes Mo 2 C/CS a promising electrocatalyst for practical hydrogen production from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Proteolytic and partial sequencing studies of the bifunctional dihydrofolate reductase-thymidylate synthase from Daucus carota.

    Science.gov (United States)

    Cella, R; Carbonera, D; Orsi, R; Ferri, G; Iadarola, P

    1991-06-01

    The bifunctional dihydrofolate reductase-thymidylate synthase (DHFR-TS) of Daucus carota has been further characterized as regards molecular weight, amino acid composition, protease digestion and microsequencing of proteolytic peptides. Data reported in this paper demonstrate that the carrot protein has a calculated Mr of 124,000 thus indicating that, contrarily to what has previously been suggested, it occurs as a dimer of identical subunits. Results of partial amino acid microsequencing show the presence of sequences highly homologous with those of the active sites of both DHFR and TS from other organisms confirming, at the structural level, the bifunctional nature of the carrot protein. As in the case of Leishmania tropica DHFR-TS, incubation of the carrot protein with V8 protease led to a rapid loss of TS activity while retaining that of DHFR. However the pattern of proteolysis did not allow to establish whether the sequence of domains is DHFR-TS as in Leishmania, or vice versa. Low homology of other amino acid sequences, as judged by computer analysis, and absence of common epitopes indicate an apparent divergence between carrot and leishmanian proteins.

  15. Bifunctional metal-free catalysis of mesoporous noble carbons for oxygen reduction and evolution reactions.

    Science.gov (United States)

    Sakaushi, Ken; Fellinger, Tim-Patrick; Antonietti, Markus

    2015-04-13

    Electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key reactions in lithium-oxygen batteries (LOBs) being a promising candidate to store renewable energies due to their high specific energy. However current development on LOBs is suffering from unsuitable catalysts. In particular, carbon-based catalysts were found to perform poorly in this system. Here, we show that metal-free mesoporous nitrogen-doped carbons (meso-NdCs) offer highly promising performances in both ORR and OER; they act as bifunctional catalysts, and can be synthesized by a very simple method. The efficient electrocatalytic activity of ORR and OER was used in a LOB cell during discharge and charge, respectively, and the present system showed a lower overpotential comparable to metal-based catalysts in LOB system. Thus, we demonstrate that meso-NdCs act as a new and affordable candidate for the efficient bifunctional oxygen catalysis, therefore can be applied to many energy-related applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Unprecedented Activity of Bifunctional Electrocatalyst for High Power Density Aqueous Zinc-Air Batteries.

    Science.gov (United States)

    Wang, Mengfan; Qian, Tao; Liu, Sisi; Zhou, Jinqiu; Yan, Chenglin

    2017-06-28

    The development of nonprecious metal catalysts with desirable bifunctional activities to supersede noble metal catalysts is of vital importance for high performance aqueous zinc-air batteries. Here, an unprecedented activity of bifunctional electrocatalyst is reported by in situ growth of nitrogen-enriched carbon nanotubes with transition metal composite. The resultant catalyst delivers surprisingly high OER (potential@10 mA cm -2 of 1.58 V) and ORR (onset potential of 0.97 V, half-wave potential of 0.86 V) performance. The overall oxygen electrode activity (overvoltage between ORR and OER) of the catalyst is as low as 0.72 V. In aqueous Zn-air battery tests, primary batteries demonstrate high maximum power density and two-electrode rechargeable batteries also exhibit good cycle performance. The unprecedented electrocatalyst opens up new avenues for developing highly active nitrogen-doped carbon nanotube-supported electrocatalysts and offers prospects for the next generation of fuel cells, metal-air batteries, and photocatalysis applications.

  17. 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.

  18. A bifunctional spin label reports the structural topology of phospholamban in magnetically-aligned bicelles

    Science.gov (United States)

    McCaffrey, Jesse E.; James, Zachary M.; Svensson, Bengt; Binder, Benjamin P.; Thomas, David D.

    2016-01-01

    We have applied a bifunctional spin label and EPR spectroscopy to determine membrane protein structural topology in magnetically-aligned bicelles, using monomeric phospholamban (PLB) as a model system. Bicelles are a powerful tool for studying membrane proteins by NMR and EPR spectroscopies, where magnetic alignment yields topological constraints by resolving the anisotropic spectral properties of nuclear and electron spins. However, EPR bicelle studies are often hindered by the rotational mobility of monofunctional Cys-linked spin labels, which obscures their orientation relative to the protein backbone. The rigid and stereospecific TOAC label provides high orientational sensitivity but must be introduced via solid-phase peptide synthesis, precluding its use in large proteins. Here we show that a bifunctional methanethiosulfonate spin label attaches rigidly and stereospecifically to Cys residues at i and i + 4 positions along PLB's transmembrane helix, thus providing orientational resolution similar to that of TOAC, while being applicable to larger membrane proteins for which synthesis is impractical. Computational modeling and comparison with NMR data shows that these EPR experiments provide accurate information about helix tilt relative to the membrane normal, thus establishing a robust method for determining structural topology in large membrane proteins with a substantial advantage in sensitivity over NMR.

  19. Synthesis and characterization of ZnS@Fe3O4 fluorescent-magnetic bifunctional nanospheres

    Science.gov (United States)

    Koc, Kenan; Karakus, Baris; Rajar, Kausar; Alveroglu, Esra

    2017-10-01

    Herein, we synthesized and characterized fluorescent and super paramagnetic ZnS@Fe3O4 nanospheres. First, (3-mercaptopropyl) trimethoxysilane (MPS) capped ZnS quantum dots (QDs) and SiO2 coated Fe3O4 nanoparticles were synthesized separately by using solution growth and co-precipitation techniques. After synthesis and characterization of these two nanoparticles, they were conglutinated together in a nano sized sphere. The QDs were attached to the surface of the Fe3O4 nanoparticles by Sisbnd Osbnd Si bonds and so Sisbnd Osbnd Si bonds created a SiO2 network around the nanoparticles during the formation of the ZnS@Fe3O4 nanospheres. The synthesized MPS capped ZnS fluorescent QDs, SiO2 coated magnetite super paramagnetic nanoparticles and ZnS@Fe3O4 fluorescent-magnetic bifunctional nanospheres were characterized by using UV-Vis Absorption Spectroscopy, Fluorescence Spectroscopy, X-ray analysis, Vibrating Sample Magnetometer analysis, Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy, Scanning Electron Microscope and Energy-dispersive X-ray spectroscopy. ZnS@Fe3O4 bifunctional nanospheres were shown to retain the magnetic properties of magnetite, while exhibiting the luminescent optical properties of ZnS nanoparticles. The combination of fluorescent and magnetic behaviors of nano composites make them useful for potential applications in the field of bio-medical and environmental.

  20. Cell Growth on ("Janus") Density Gradients of Bifunctional Zeolite L Crystals.

    Science.gov (United States)

    Kehr, Nermin Seda; Motealleh, Andisheh; Schäfer, Andreas H

    2016-12-28

    Nanoparticle density gradients on surfaces have attracted interest as two-dimensional material surfaces that can mimic the complex nano-/microstructure of the native extracellular matrix, including its chemical and physical gradients, and can therefore be used to systematically study cell-material interactions. In this respect, we report the preparation of density gradients made of bifunctional zeolite L crystals on glass surfaces and the effects of the density gradient and biopolymer functionalization of zeolite L crystals on cell adhesion. We also describe how we created "Janus" density gradient surfaces by gradually depositing two different types of zeolite L crystals that were functionalized and loaded with different chemical groups and guest molecules onto the two distinct sides of the same glass substrate. Our results show that more cells adhered on the density gradient of biopolymer-coated zeolites than on uncoated ones. The number of adhered cells increased up to a certain surface coverage of the glass by the zeolite L crystals, but then it decreased beyond the zeolite density at which a higher surface coverage decreased fibroblast cell adhesion and spreading. Additionally, cell experiments showed that cells gradually internalized the guest-molecule-loaded zeolite L crystals from the underlying density gradient containing bifunctional zeolite L crystals.

  1. 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.

  2. 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

  3. 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

  4. 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

    "bifunctional" catalysts using Au-Cd based alloys inspired by theoretical modelling. Density functional theory calculations suggest more favourable thermodynamics for CO2 reduction to CO and methanol on mixed Au-Cd sites on Au3Cd relative to similar values on Au. We use various tools to test the bulk...

  5. Production of medium-chain, a, omega-bifunctional monomers from fatty acids and n-alkanes

    NARCIS (Netherlands)

    Nuland, Youri M.

    2017-01-01

    In chapter 1, we give an introduction to bifunctional monomers that play an important role in the chemical industry. Briefly, the conventional production processes of α,ω-dicarboxylic acids and α,ω-diols are discussed. Strategies for more sustainable

  6. A bifunctional curcumin analogue for two-photon imaging and inhibiting crosslinking of amyloid beta in Alzheimer's disease.

    Science.gov (United States)

    Zhang, Xueli; Tian, Yanli; Yuan, Peng; Li, Yuyan; Yaseen, Mohammad A; Grutzendler, Jaime; Moore, Anna; Ran, Chongzhao

    2014-10-09

    In this report, we designed a highly bright bifunctional curcumin analogue CRANAD-28. In vivo two-photon imaging suggested that CRANAD-28 could penetrate the blood brain barrier (BBB) and label plaques and cerebral amyloid angiopathies (CAAs). We also demonstrated that this imaging probe could inhibit the crosslinking of amyloid beta induced either by copper or by natural conditions.

  7. 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

  8. Typical cMRI Pattern as Diagnostic Clue for D-Bifunctional Protein Deficiency Without Apparent Biochemical Abnormalities in Plasma

    NARCIS (Netherlands)

    Grønborg, Sabine; Krätzner, Ralph; Spiegler, Juliane; Ferdinandusse, Sacha; Wanders, Ronald J. A.; Waterham, Hans R.; Gärtner, Jutta

    2010-01-01

    D-bifunctional protein deficiency (DBPD) is an autosomal recessive disease caused by a defect in peroxisomal beta-oxidation. The majority of patients suffer from a severe neurological disease with neonatal hypotonia and seizures and die within the first 2 years of life. Few patients show milder

  9. Bifunctional ferrocene-based squaramide-phosphine as an organocatalyst for highly enantioselective intramolecular Morita-Baylis-Hillman reaction.

    Science.gov (United States)

    Zhang, Xiaorui; Ma, Pengfei; Zhang, Dongxu; Lei, Yang; Zhang, Shengyong; Jiang, Ru; Chen, Weiping

    2014-04-21

    This work demonstrates that, in accord with metal catalysis, ferrocene could be an excellent scaffold for organocatalysts. The simple and easily accessible bifunctional ferrocene-based squaramide-phosphine shows high enantioselectivity in the intramolecular Morita-Baylis-Hillman reaction of 7-aryl-7-oxo-5-heptenals, giving a variety of 2-aroyl-2-cyclohexenols in up to 96% ee.

  10. Facile synthesis of 4-vinyl- and 4-fluorovinyl-1,2,3-triazoles via bifunctional “click-olefination” reagents

    Science.gov (United States)

    Kumar, Rakesh; Pradhan, Padmanava; Zajc, Barbara

    2011-01-01

    Modular synthesis of vinyl and fluorovinyl triazoles can be achieved from bifunctional propargyl and fluoropropargyl sulfones by Cu-catalyzed azide-alkyne ligation and Julia-Kocienski olefination. Competitive click reactions of the protio and fluoropropargyl sulfones show higher reactivity of the latter, and a preliminary DFT analysis was performed. PMID:21336351

  11. Asymmetric additions of thioglycolates and N-Boc aldimines catalyzed by a bifunctional tertiary-amine squaramide.

    Science.gov (United States)

    Feng, Bo-Xu; Wang, Bin; Li, Xin

    2016-10-21

    A highly enantioselective asymmetric addition reaction of thioglycolates and N-Boc aldimines was promoted by a bifunctional tertiary-amine squaramide catalyst. As a result, a number of chiral N,S-acetal derivatives were efficiently synthesized with good enantioselectivities.

  12. 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

  13. Oxygen electrode bifunctional electrocatalyst NiCo2O4 spinel

    Science.gov (United States)

    Fielder, William L.; Singer, Joseph

    1988-01-01

    A significant increase in energy density may be possible if a two-unit alkaline regenerative H2-O2 fuel cell is replaced with a single-unit system that uses passive means for H2O transfer and thermal control. For this single-unit system, new electrocatalysts for the O2 electrode will be required which are not only bifunctionally active but also chemically and electrochemically stable between the voltage range of about 0.7 and 1.5 V. NiCo2O4 spinel is reported to have certain characteristics that make it useful for a study of electrode fabrication techniques. High surface area NiCo2O4 powder was fabricated into unsupported, bifunctional, PTFE-bonded, porous gas fuel cell electrodes by commercial sources using varying PTFE contents and sintering temperatures. The object of this study is to measure the bifunctional activities of these electrodes and to observe what performance differences might result from different commercial electrode fabricators. O2 evolution and O2 reduction data were obtained at 80 C (31 percent KOH). An irreversible reaction (i.e., aging) occurred during O2 evolution at potentials greater than about 1.5 V. Anodic Tafel slopes of 0.06 and 0.12 V/decade were obtained for the aged electrodes. Within the range of 15 to 25 percent, the PTFE content was not a critical parameter for optimizing the electrode for O2 evolution activity. Sintering temperatures between 300 and 340 C may be adequate but heating at 275 C may not be sufficient to properly sinter the PTFE-NiCo2O4 mixture. Electrode disintegration was observed during O2 reduction. Transport of O2 to the NiCo2O4 surface became prohibitive at greater than about -0.02 A/sq cm. Cathodic Tafel slopes of -0.6 and -0.12 V/decade were assumed for the O2 reduction process. A PTFE content of 25 percent (or greater) appears to be preferable for sintering the PTFE-NiCo2O4 mixture.

  14. Eggplant-derived microporous carbon sheets: towards mass production of efficient bifunctional oxygen electrocatalysts at low cost for rechargeable Zn-air batteries.

    Science.gov (United States)

    Li, Bing; Geng, Dongsheng; Lee, Xinjing Shannon; Ge, Xiaoming; Chai, Jianwei; Wang, Zhijuan; Zhang, Jie; Liu, Zhaolin; Hor, T S Andy; Zong, Yun

    2015-05-25

    We report 2D microporous carbon sheets with high surface area, derived from eggplant via simple carbonization and KOH activation, as low cost yet efficient bifunctional catalysts for high performance rechargeable zinc-air batteries.

  15. Synthesis of acrylic and allylic bifunctional cross-linking monomers derived from PET waste

    International Nuclear Information System (INIS)

    Cruz-Aguilar, A; Herrera-González, A M; Vázquez-García, R A; Coreño, J; Navarro-Rodríguez, D

    2013-01-01

    An acrylic and two novel allylic monomers synthesized from bis (hydroxyethyl) terephthalate, BHET, are reported. This was obtained by glycolysis of post-consumer PET with boiling ethylene glycol. The bifunctional monomer bis(2-(acryloyloxy)ethyl) terephthalate was obtained from acryloyl chloride, while the allylic monomers 2-(((allyloxi)carbonyl)oxy) ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxi)carbonyl)oxy)ethyl) terephthalate, from allyl chloroformate. Cross-linking was studied in bulk polymerization using two different thermal initiators. Monomers were analyzed by means of 1 H NMR and the cross-linked polymers by infrared spectroscopy. Gel content higher than 90% was obtained for the acrylic monomer. In the case of the mixture of the allylic monomers, the cross-linked polymer was 80 % using BPO initiator, being this mixture 24 times less reactive than the acrylic monomer.

  16. The determination of the rate of conjugation of immunoglobulin with a bifunctional chelator

    International Nuclear Information System (INIS)

    Malek, Z.; Miler, V.; Budsky, F.

    2006-01-01

    Imaging of cell's antigens with the use of labelled immunoglobulins allows imaging of specific receptors on cell membrane and specific tumours. It is necessary to carry out the labelling of the immunoglobulins with radionuclides of suitable physical properties which form cations (e.g., 111 In, 90 Y, 177 Lu) that form very strong chelates of sufficiently high stability constant preventing the dissociation of complexes or the radionuclide under 'in-vivo' conditions. The immunoglobulin must be conjugated with the bifunctional chelator (BCH), which contains both chelating unit and reactive group for binding to the immunoglobulin. In our laboratory we have conjugated human IgG and monoclonal antibody CD20 with diethylenetriamine pentaacetic acid dianhydride (cDTPAA). Radionuclides 90 Y and 177 Lu prepared on the LVR-15 reactor were used for labelling. After conjugation and labelling the yields in relation to the amount of isotopic carrier have been determined

  17. Crystal structure of human leukotriene A(4) hydrolase, a bifunctional enzyme in inflammation.

    Science.gov (United States)

    Thunnissen, M M; Nordlund, P; Haeggström, J Z

    2001-02-01

    Leukotriene (LT) A(4) hydrolase/aminopeptidase (LTA4H) is a bifunctional zinc enzyme that catalyzes the biosynthesis of LTB4, a potent lipid chemoattractant involved in inflammation, immune responses, host defense against infection, and PAF-induced shock. The high resolution crystal structure of LTA4H in complex with the competitive inhibitor bestatin reveals a protein folded into three domains that together create a deep cleft harboring the catalytic Zn(2+) site. A bent and narrow pocket, shaped to accommodate the substrate LTA(4), constitutes a highly confined binding region that can be targeted in the design of specific anti-inflammatory agents. Moreover, the structure of the catalytic domain is very similar to that of thermolysin and provides detailed insight into mechanisms of catalysis, in particular the chemical strategy for the unique epoxide hydrolase reaction that generates LTB(4).

  18. Dyes as bifunctional markers of DNA hybridization on surfaces and mutation detection.

    Science.gov (United States)

    García-Mendiola, Tania; Cerro, María Ramos; López-Moreno, José María; Pariente, Félix; Lorenzo, Encarnación

    2016-10-01

    The interaction of small molecules with DNA has found diagnostic and therapeutic applications. In this work, we propose the use of two different dyes, in particular Azure A and Safranine, as bifunctional markers of on-surface DNA hybridization and potent tools for screening of specific gene mutations directly in real DNA PCR amplicons extracted from blood cells. By combining spectroscopic and electrochemical methods we demonstrate that both dyes can interact with single and double stranded DNA to a different extent, allowing reliable hybridization detection. From these data, we have also elucidated the nature of the interaction. We conclude that the binding mode is fundamentally intercalative with an electrostatic component. The dye fluorescence allows their use as nucleic acid stains for the detection of on-surfaces DNA hybridization. Its redox activity is exploited in the development of selective electrochemical DNA biosensors. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. New Tailor-Made Alkyl-Aldehyde Bifunctional Supports for Lipase Immobilization

    Directory of Open Access Journals (Sweden)

    Robson Carlos Alnoch

    2016-11-01

    Full Text Available Immobilized and stabilized lipases are important biocatalytic tools. In this paper, different tailor-made bifunctional supports were prepared for the immobilization of a new metagenomic lipase (LipC12. The new supports contained hydrophobic groups (different alkyl groups to promote interfacial adsorption of the lipase and aldehyde groups to react covalently with the amino groups of side chains of the adsorbed lipase. The best catalyst was 3.5-fold more active and 5000-fold more stable than the soluble enzyme. It was successfully used in the regioselective deacetylation of peracetylated d-glucal. The PEGylated immobilized lipase showed high regioselectivity, producing high yields of the C-3 monodeacetylated product at pH 5.0 and 4 °C.

  20. Synthesis of Bifunctional Azobenzene Glycoconjugates for Cysteine-Based Photosensitive Cross-Linking with Bioactive Peptides.

    Science.gov (United States)

    Müller, Anne; Kobarg, Hauke; Chandrasekaran, Vijayanand; Gronow, Joana; Sönnichsen, Frank D; Lindhorst, Thisbe K

    2015-09-21

    Azobenzene linker molecules can be utilized to control peptide/protein function when they are ligated to appropriately spaced amino acid side chains of the peptide. This is because the photochemical E/Z isomerization of the azobenzene N=N double bond allows to switch peptide conformation between folded and unfolded. In this context, we have introduced carbohydrate-functionalized azobenzene derivatives in order to advance the biocompatible properties of azobenzene peptide linkers. Chloroacetamide-functionalized and O-allylated carbohydrate derivatives were synthesized and conjugated with azobenzene to achieve new bifunctional cross-linkers, in order to allow ligation to cysteine side chains by nucleophilic substitution or thiol-ene reaction, respectively. The photochromic properties of the new linker glycoconjugates were determined and first ligation reactions performed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Bioinspired design of a hybrid bifunctional enzymatic/organic electrocatalyst for site selective alcohol oxidation.

    Science.gov (United States)

    Lancaster, Louis; Hickey, David P; Sigman, Matthew S; Minteer, Shelley D; Wheeldon, Ian

    2018-01-11

    This work combines the thermostable alcohol dehydrogenase D (AdhD) from Pyrococcus furiosus and the organic electrocatalyst TEMPO to create a bifunctional catalyst that selectively oxidizes primary and secondary alcohols. The active sites function independently, can be switched on by changing reaction conditions, and can selectively oxidize a mixture of 1- and 2-butanol. The NAD + -dependent enzyme catalyses the secondary alcohol oxidation at a rate 3-fold faster than the primary alcohol, while the covalently attached 4-glycidyl-TEMPO oxidizes 1-butanol and has negligible activity toward 2-butanol. This hybrid catalytic approach has potential value for selective alcohol oxidations as well as other electrochemical and enzymatic multistep processes in energy conversion and chemical synthesis.

  2. Recent Development of Bifunctional Small Molecules to Study Metal-Amyloid-β Species in Alzheimer's Disease

    Directory of Open Access Journals (Sweden)

    Joseph J. Braymer

    2011-01-01

    Full Text Available Alzheimer's disease (AD is a multifactorial neurodegenerative disease related to the deposition of aggregated amyloid-β (Aβ peptides in the brain. It has been proposed that metal ion dyshomeostasis and miscompartmentalization contribute to AD progression, especially as metal ions (e.g., Cu(II and Zn(II found in Aβ plaques of the diseased brain can bind to Aβ and be linked to aggregation and neurotoxicity. The role of metal ions in AD pathogenesis, however, is uncertain. To accelerate understanding in this area and contribute to therapeutic development, recent efforts to devise suitable chemical reagents that can target metal ions associated with Aβ have been made using rational structure-based design that combines two functions (metal chelation and Aβ interaction in the same molecule. This paper presents bifunctional compounds developed by two different design strategies (linkage or incorporation and discusses progress in their applications as chemical tools and/or potential therapeutics.

  3. Bifunctional Hydrogels Containing the Laminin Motif IKVAV Promote Neurogenesis

    Directory of Open Access Journals (Sweden)

    Aleeza Farrukh

    2017-11-01

    Full Text Available Engineering of biomaterials with specific biological properties has gained momentum as a means to control stem cell behavior. Here, we address the effect of bifunctionalized hydrogels comprising polylysine (PL and a 19-mer peptide containing the laminin motif IKVAV (IKVAV on embryonic and adult neuronal progenitor cells under different stiffness regimes. Neuronal differentiation of embryonic and adult neural progenitors was accelerated by adjusting the gel stiffness to 2 kPa and 20 kPa, respectively. While gels containing IKVAV or PL alone failed to support long-term cell adhesion, in bifunctional gels, IKVAV synergized with PL to promote differentiation and formation of focal adhesions containing β1-integrin in embryonic cortical neurons. Furthermore, in adult neural stem cell culture, bifunctionalized gels promoted neurogenesis via the expansion of neurogenic clones. These data highlight the potential of synthetic matrices to steer stem and progenitor cell behavior via defined mechano-adhesive properties.

  4. 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.

  5. 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.

  6. 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.

  7. Dimerization and Bifunctionality Confer Robustness to the Isocitrate Dehydrogenase Regulatory System in Escherichia coli*

    Science.gov (United States)

    Dexter, Joseph P.; Gunawardena, Jeremy

    2013-01-01

    An important goal of systems biology is to develop quantitative models that explain how specific molecular features give rise to systems-level properties. Metabolic and regulatory pathways that contain multifunctional proteins are especially interesting to study from this perspective because they have frequently been observed to exhibit robustness: the ability for a system to perform its proper function even as levels of its components change. In this study, we use extensive biochemical data and algebraic modeling to develop and analyze a model that shows how robust behavior arises in the isocitrate dehydrogenase (IDH) regulatory system of Escherichia coli, which was shown in 1985 to experimentally exhibit robustness. E. coli IDH is regulated by reversible phosphorylation catalyzed by the bifunctional isocitrate dehydrogenase kinase/phosphatase (IDHKP), and the level of IDH activity determines whether carbon flux is directed through the glyoxylate bypass (for growth on two-carbon substrates) or the full tricarboxylic acid cycle. Our model, which incorporates recent structural data on IDHKP, identifies several specific biochemical features of the system (including homodimerization of IDH and bifunctionality of IDHKP) that provide a potential explanation for robustness. Using algebraic techniques, we derive an invariant that summarizes the steady-state relationship between the phospho-forms of IDH. We use the invariant in combination with kinetic data on IDHKP to calculate IDH activity at a range of total IDH levels and find that our model predicts robustness. Our work unifies much of the known biochemistry of the IDH regulatory system into a single quantitative framework and highlights the importance of constructing biochemically realistic models in systems biology. PMID:23192354

  8. Preparation and Characterization of Silica-Coated Magnetic–Fluorescent Bifunctional Microspheres

    Directory of Open Access Journals (Sweden)

    Xiao Qi

    2009-01-01

    Full Text Available Abstract Bifunctional magnetic–fluorescent composite nanoparticles (MPQDs with Fe3O4MPs and Mn:ZnS/ZnS core–shell quantum dots (QDs encapsulated in silica spheres were synthesized through reverse microemulsion method and characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, vibration sample magnetometer, and photoluminescence (PL spectra. Our strategy could offer the following features: (1 the formation of Mn:ZnS/ZnS core/shell QDs resulted in enhancement of the PL intensity with respect to that of bare Mn:ZnS nanocrystals due to the effective elimination of the surface defects; (2 the magnetic nanoparticles were coated with silica, in order to reduce any detrimental effects on the QD PL by the magnetic cores; and (3 both Fe3O4MPs and Mn:ZnS/ZnS core–shell QDs were encapsulated in silica spheres, and the obtained MPQDs became water soluble. The experimental conditions for the silica coating on the surface of Fe3O4nanoparticles, such as the ratio of water to surfactant (R, the amount of ammonia, and the amount of tetraethoxysilane, on the photoluminescence properties of MPQDs were studied. It was found that the silica coating on the surface of Fe3O4could effectively suppress the interaction between the Fe3O4and the QDs under the most optimal parameters, and the emission intensity of MPQDs showed a maximum. The bifunctional MPQDs prepared under the most optimal parameters have a typical diameter of 35 nm and a saturation magnetization of 4.35 emu/g at room temperature and exhibit strong photoluminescence intensity.

  9. 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

  10. 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

  11. A bifunctional endoglucanase/endoxylanase from Cellulomonas flavigena with potential use in industrial processes at different pH.

    Science.gov (United States)

    Pérez-Avalos, Odilia; Sánchez-Herrera, Leticia M; Salgado, Luis M; Ponce-Noyola, Teresa

    2008-07-01

    Cellulomonas flavigena CDBB-531 was found to secrete a bifunctional cellulase/xylanase with a molecular mass of 49 kDa and pI 4.3. This enzyme was active on Remazol brilliant blue-carboxymethylcellulose (RBB-CMC) and Remazol brilliant blue-xylan (RBB-X). Based on thin-layer chromatographic analysis of the degradation products, the cellulase activity produced glucose, cellobiose, cellotriose, and cellotetraose from CMC as the substrate. When xylan from birchwood was used, end products were xylose, arabinose, and xylobiose. The bifunctional enzyme showed a pH optimum of 6 for cellulase activity and 9 for xylanase activity, which pointed out that this enzyme had separate sites for each activity. In both cases, the apparent optimum temperature was 50 degrees C. The predicted amino acid sequence of purified protein showed similarity with the catalytic domain of several glycosyl hydrolases of family 10.

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

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Yi-Hung [Life Science Group, Research Division, National Synchrotron Radiation Research Center, Hsinchu 30076,Taiwan (China); Peng, Wen-Yan [Institute of Bioinformatics and Structural Biology, National Tsing-Hua University, Hsinchu 30013,Taiwan (China); Huang, Yen-Chieh [Life Science Group, Research Division, National Synchrotron Radiation Research Center, Hsinchu 30076,Taiwan (China); Guan, Hong-Hsiang; Hsieh, Ying-Cheng [Life Science Group, Research Division, National Synchrotron Radiation Research Center, Hsinchu 30076,Taiwan (China); Institute of Bioinformatics and Structural Biology, National Tsing-Hua University, Hsinchu 30013,Taiwan (China); Liu, Ming-Yih [Life Science Group, Research Division, National Synchrotron Radiation Research Center, Hsinchu 30076,Taiwan (China); Chang, Tschining [Department of Hospitality Management, Nan Jeon Institute of Technology, Yen-Shui, Tainan 73746,Taiwan (China); Chen, Chun-Jung, E-mail: cjchen@nsrrc.org.tw [Life Science Group, Research Division, National Synchrotron Radiation Research Center, Hsinchu 30076,Taiwan (China); Department of Physics, National Tsing-Hua University, Hsinchu 30013,Taiwan (China)

    2006-08-01

    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{sub 1}2{sub 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. 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

  14. Nitrogen-Doped Graphene on Transition Metal Substrates as Efficient Bifunctional Catalysts for Oxygen Reduction and Oxygen Evolution Reactions.

    Science.gov (United States)

    Zhou, Si; Liu, Nanshu; Wang, Zhiyu; Zhao, Jijun

    2017-07-12

    Composites of transition metal and carbon-based materials are promising bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and are widely used in rechargeable metal-air batteries. However, the mechanism of their enhanced bicatalytic activities remains elusive. Herein, we construct N-doped graphene supported by Co(111) and Fe(110) substrates as bifunctional catalysts for ORR and OER in alkaline media. First-principles calculations show that these heterostructures possess a large number of active sites for ORR and OER with overpotentials comparable to those of noble metal benchmark catalysts. The catalytic activity is modulated by the coupling strength between graphene and the metal substrates, as well as the charge distribution in the graphitic sheet, which is delicately mediated by N dopants. These theoretical results uncover the key parameters that govern the bicatalytic properties of hybrid materials and help prescribe the principles for designing multifunctional electrocatalysts of high performance.

  15. 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.

  16. 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

  17. 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.

  18. Development of a Sono-Assembled, Bifunctional Soy Peptide Nanoparticle for Cellular Delivery of Hydrophobic Active Cargoes

    DEFF Research Database (Denmark)

    Zhang, Yuanhong; Zhao, Mouming; Ning, Zhengxiang

    2018-01-01

    Soy proteins are prone to aggregate upon proteolysis, hindering their sustainable development in food processing. Here, a continuous work on the large insoluble peptide aggregates was carried out, aiming to develop a new type of soy peptide-based nanoparticle (SPN) for active cargo delivery. Sono...... in protecting glutamate-induced toxicity in PC12 cells, where the matrix SPN can simultaneously reduce lipid peroxidation and elevate antioxidant enzymes levels, innovatively demonstrating its bifunctionality during cellular delivery....

  19. 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.

  20. 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,...

  1. Adenosine-5?-phosphosulfate ? a multifaceted modulator of bifunctional 3?-phospho-adenosine-5?-phosphosulfate synthases and related enzymes

    OpenAIRE

    Mueller, Jonathan W; Shafqat, Naeem

    2013-01-01

    All sulfation reactions rely on active sulfate in the form of 3?-phospho-adenosine-5?-phosphosulfate (PAPS). In fungi, bacteria, and plants, the enzymes responsible for PAPS synthesis, ATP sulfurylase and adenosine-5?-phosphosulfate (APS) kinase, reside on separate polypeptide chains. In metazoans, however, bifunctional PAPS synthases catalyze the consecutive steps of sulfate activation by converting sulfate to PAPS via the intermediate APS. This intricate molecule and the related nucleotides...

  2. Engineering a trifunctional proline utilization A chimaera by fusing a DNA-binding domain to a bifunctional PutA.

    Science.gov (United States)

    Arentson, Benjamin W; Hayes, Erin L; Zhu, Weidong; Singh, Harkewal; Tanner, John J; Becker, Donald F

    2016-12-01

    Proline utilization A (PutA) is a bifunctional flavoenzyme with proline dehydrogenase (PRODH) and Δ 1 -pyrroline-5-carboxylate (P5C) dehydrogenase (P5CDH) domains that catalyses the two-step oxidation of proline to glutamate. Trifunctional PutAs also have an N-terminal ribbon-helix-helix (RHH) DNA-binding domain and moonlight as autogenous transcriptional repressors of the put regulon. A unique property of trifunctional PutA is the ability to switch functions from DNA-bound repressor to membrane-associated enzyme in response to cellular nutritional needs and proline availability. In the present study, we attempt to construct a trifunctional PutA by fusing the RHH domain of Escherichia coli PutA (EcRHH) to the bifunctional Rhodobacter capsulatus PutA (RcPutA) in order to explore the modular design of functional switching in trifunctional PutAs. The EcRHH-RcPutA chimaera retains the catalytic properties of RcPutA while acquiring the oligomeric state, quaternary structure and DNA-binding properties of EcPutA. Furthermore, the EcRHH-RcPutA chimaera exhibits proline-induced lipid association, which is a fundamental characteristic of functional switching. Unexpectedly, RcPutA lipid binding is also activated by proline, which shows for the first time that bifunctional PutAs exhibit a limited form of functional switching. Altogether, these results suggest that the C-terminal domain (CTD), which is conserved by trifunctional PutAs and certain bifunctional PutAs, is essential for functional switching in trifunctional PutAs. © 2016 The Author(s).

  3. Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application.

    Science.gov (United States)

    Chen, Zhu; Yu, Aiping; Higgins, Drew; Li, Hui; Wang, Haijiang; Chen, Zhongwei

    2012-04-11

    A new class of core-corona structured bifunctional catalyst (CCBC) consisting of lanthanum nickelate centers supporting nitrogen-doped carbon nanotubes (NCNT) has been developed for rechargeable metal-air battery application. The nanostructured design of the catalyst allows the core and corona to catalyze the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), respectively. These materials displayed exemplary OER and ORR activity through half-cell testing, comparable to state of the art commercial lanthanum nickelate (LaNiO(3)) and carbon-supported platinum (Pt/C), with added bifunctional capabilities allowing metal-air battery rechargeability. LaNiO(3) and Pt/C are currently the most accepted benchmark electrocatalyst materials for the OER and ORR, respectively; thus with comparable activity toward both of these reactions, CCBC are presented as a novel, inexpensive catalyst component for the cathode of rechargeable metal-air batteries. Moreover, after full-range degradation testing (FDT) CCBC retained excellent activity, retaining 3 and 13 times greater ORR and OER current upon comparison to state of the art Pt/C. Zinc-air battery performances of CCBC is in good agreement with the half-cell experiments with this bifunctional electrocatalyst displaying high activity and stability during battery discharge, charge, and cycling processes. Owing to its outstanding performance toward both the OER and ORR, comparable with the highest performing commercial catalysts to date for each of the respective reaction, coupled with high stability and rechargeability, CCBC is presented as a novel class of bifunctional catalyst material that is very applicable to future generation rechargeable metal-air batteries. © 2012 American Chemical Society

  4. Synergistic bifunctional catalyst design based on perovskite oxide nanoparticles and intertwined carbon nanotubes for rechargeable zinc-air battery applications.

    Science.gov (United States)

    Lee, Dong Un; Park, Hey Woong; Park, Moon Gyu; Ismayilov, Vugar; Chen, Zhongwei

    2015-01-14

    Advanced morphology of intertwined core-corona structured bifunctional catalyst (IT-CCBC) is introduced where perovskite lanthanum nickel oxide nanoparticles (LaNiO3 NP) are encapsulated by high surface area network of nitrogen-doped carbon nanotubes (NCNT) to produce highly active and durable bifunctional catalyst for rechargeable metal-air battery applications. The unique composite morphology of IT-CCBC not only enhances the charge transport property by providing rapid electron-conduction pathway but also facilitates in diffusion of hydroxyl and oxygen reactants through the highly porous framework. Confirmed by electrochemical half-cell testing, IT-CCBC in fact exhibits very strong synergy between LaNiO3 NP and NCNT demonstrating bifunctionality with significantly improved catalytic activities of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, when compared to the state-of-art catalysts, IT-CCBC outperforms Pt/C and Ir/C in terms of ORR and OER, respectively, and shows improved electrochemical stability compared to them after cycle degradation testing. The practicality of the catalyst is corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where IT-CCBC demonstrates superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. These improved electrochemical properties of the catalyst are attributed to the nanosized dimensions of LaNiO3 NP controlled by simple hydrothermal technique, which enables prolific growth of and encapsulation by highly porous NCNT network. The excellent electrochemical results presented in this study highlight IT-CCBC as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery applications.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. Bifunctional recombinant fusion enzyme between maltooligosyltrehalose synthase and maltooligosyltrehalose trehalohydrolase of thermophilic microorganism Metallosphaera hakonensis.

    Science.gov (United States)

    Seo, Ju-Seok; An, Ju Hee; Cheong, Jong-Joo; Choi, Yang Do; Kim, Chung Ho

    2008-09-01

    MhMTS and MhMTH are trehalose (alpha-D-glucopyranosyl- [1,1]-alpha-D-glucopyranose) biosynthesis genes of the thermophilic microorganism Metallosphaera hakonensis, and encode a maltooligosyltrehalose synthase (MhMTS) and a maltooligosyltrehalose trehalohydrolase (MhMTH), respectively. In this study, the two genes were fused inframe in a recombinant DNA, and expressed in Escherichia coli to produce a bifunctional fusion enzyme, MhMTSH. Similar to the two-step reactions with MhMTS and MhMTH, the fusion enzyme catalyzed the sequential reactions on maltopentaose, maltotriosyltrehalose formation, and following hydrolysis, producing trehalose and maltotriose. Optimum conditions for the fusion enzyme-catalyzed trehalose synthesis were around 70 degrees and pH 5.0-6.0. The MhMTSH fusion enzyme exhibited a high degree of thermostability, retaining 80% of the activity when pre-incubated at 70 degrees for 48 h. The stability was gradually abolished by incubating the fusion enzyme at above 80 degrees . The MhMTSH fusion enzyme was active on various sizes of maltooligosaccharides, extending its substrate specificity to soluble starch, the most abundant natural source of trehalose production.

  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. Bifunctional polyacrylonitrile fiber-mediated conversion of sucrose to 5-hydroxymethylfurfural in mixed-aqueous systems.

    Science.gov (United States)

    Shi, Xian-Lei; Zhang, Min; Lin, Huikun; Tao, Minli; Li, Yongdan; Zhang, Wenqin

    2015-03-01

    A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF-PA[BnBr]) and a metal chloride was employed to produce 5-hydroxymethylfurfural (HMF) from sucrose in mixed-aqueous systems. The promoter of PANF-PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8%) of HMF, superior recyclability (6 cycles) of the process, and effective scale-up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix-bed reactor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. 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.

  15. 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.

  16. Bifunctional monomer magnetic imprinted nanomaterials for selective separation of tetracyclines directly from milk samples.

    Science.gov (United States)

    Xu, Yuan; Tang, Yuhai; Zhao, Yayun; Gao, Ruixia; Zhang, Junjie; Fu, Delai; Li, Zhaolun; Li, Hecheng; Tang, Xiaoshuang

    2018-04-01

    Novel magnetic molecularly imprinted nanomaterials (DA + BSA-MMIPs) were prepared adopting bovine serum albumin (BSA) and dopamine as bifunctional monomers for the first time. Besides the role of assistant functional monomer, BSA can exclude the proteins with like charges and promote low molecular weight tetracyclines to be adsorbed. Thus, the DA + BSA-MMIPs could fulfil the selective separation of tetracyclines directly from milk samples. The characteristics, polymerization conditions, and adsorption performances of the resultant nanomaterials were investigated in detail. In addition of uniform imprinting layers, stable crystalline phase, and good magnetism of the DA + BSA-MMIPs, they have rapid binding kinetic, high adsorption capacity, and favorable reusability. The imprinted nanomaterials were coupled with HPLC to selectively extract and determine trace tetracyclines from untreated milk samples. The recoveries of tetracyclines are in the range of 84.1-95.8% with relative standard deviations of less than 6.7%. The developed method is especially suitable for the selective enrichment and detection of target compounds directly from a complex sample with proteins. Copyright © 2018 Elsevier Inc. All rights reserved.

  17. 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.

  18. Crystal structure of the bifunctional proline utilization A flavoenzyme from Bradyrhizobium japonicum

    Energy Technology Data Exchange (ETDEWEB)

    Srivastava, Dhiraj; Schuermann, Jonathan P.; White, Tommi A.; Krishnan, Navasona; Sanyal, Nikhilesh; Hura, Greg L.; Tan, Anmin; Henzl, Michael T.; Becker, Donald F.; Tanner, John J. (UNL); (LBNL); (UMC)

    2010-04-26

    The bifunctional proline catabolic flavoenzyme, proline utilization A (PutA), catalyzes the oxidation of proline to glutamate via the sequential activities of FAD-dependent proline dehydrogenase (PRODH) and NAD{sup +}-dependent {Delta}{sup 1}-pyrroline-5-carboxylate dehydrogenase (P5CDH) domains. Although structures for some of the domains of PutA are known, a structure for the full-length protein has not previously been solved. Here we report the 2.1 {angstrom} resolution crystal structure of PutA from Bradyrhizobium japonicum, along with data from small-angle x-ray scattering, analytical ultracentrifugation, and steady-state and rapid-reaction kinetics. PutA forms a ring-shaped tetramer in solution having a diameter of 150 {angstrom}. Within each protomer, the PRODH and P5CDH active sites face each other at a distance of 41 {angstrom} and are connected by a large, irregularly shaped cavity. Kinetics measurements show that glutamate production occurs without a lag phase, suggesting that the intermediate, {Delta}{sup 1}-pyrroline-5-carboxylate, is preferably transferred to the P5CDH domain rather than released into the bulk medium. The structural and kinetic data imply that the cavity serves both as a microscopic vessel for the hydrolysis of {Delta}{sup 1}-pyrroline-5-carboxylate to glutamate semialdehyde and a protected conduit for the transport of glutamate semialdehyde to the P5CDH active site.

  19. 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.

  20. Cobalt Phosphide Hollow Polyhedron as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Hydrogen and Oxygen.

    Science.gov (United States)

    Liu, Mengjia; Li, Jinghong

    2016-01-27

    The development of efficient and low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts for renewable-energy conversion techniques is highly desired. A kind of hollow polyhedral cobalt phosphide (CoP hollow polyhedron) is developed as efficient bifunctional electrocatalysts for HER and OER templated by Co-centered metal-organic frameworks. The as-prepared CoP hollow polyhedron, which have large specific surface area and high porosity providing rich catalytic active sites, show excellent electrocatalytic performances for both HER and OER in acidic and alkaline media, respectively, with onset overpotentials of 35 and 300 mV, Tafel slopes of 59 and 57 mV dec(-1), and a current density of 10 mA cm(-2) at overpotentials of 159 and 400 mV for HER and OER, respectively, which are remarkably superior to those of particulate CoP (CoP particles) and comparable to those of commercial noble-metal catalysts. In addition, the CoP hollow polyhedron also show good durability after long-term operations.

  1. Activating the Bifunctionality of a Perovskite Oxide toward Oxygen Reduction and Oxygen Evolution Reactions.

    Science.gov (United States)

    Lyu, Yu-Qi; Ciucci, Francesco

    2017-10-18

    This article presents a facile and effective approach to activate the bifunctionality of calcium-manganese perovskites toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). We substituted Nb into the Mn site of CaMnO 3 (CMO) and treated the material with H 2 . The as-obtained CaMn 0.75 Nb 0.25 O 3-δ (H 2 -CMNO) displays the same structure as that of CMO, and compared to that of CMO, H 2 -CMNO exhibits significantly improved OER performance, including a lower overpotential, a reduced Tafel slope, a higher mass activity, and enhanced stability. In addition, the ORR performance of H 2 -CMNO is also greatly enhanced, relative to CMO, with a higher ORR activity and a more efficient electron-transfer pathway. H 2 -CMNO shows an even higher activity-per-catalyst cost and superior stability than that of state-of-the-art materials, such as IrO 2 and Pt/C. This great enhancement in ORR and OER activity of H 2 -CMNO is attributed to several factors, including phase stabilization, optimized e g filling, better OH - adsorption, and improved electrical conductivity.

  2. Three crystal forms of the bifunctional enzyme proline utilization A (PutA) from Bradyrhizobium japonicum

    International Nuclear Information System (INIS)

    Schuermann, Jonathan P.; White, Tommi A.; Srivastava, Dhiraj; Karr, Dale B.; Tanner, John J.

    2008-01-01

    The first diffraction-quality crystals of a PutA protein are reported. One of the three crystal forms described here exhibits pseudo-merohedral twinning. Removal of the N-terminal histidine tag aided the crystallization of another form. Proline utilization A proteins (PutAs) are large (1000–1300 residues) membrane-associated bifunctional flavoenzymes that catalyze the two-step oxidation of proline to glutamate by the sequential action of proline dehydrogenase and Δ 1 -pyrroline-5-carboxylate dehydrogenase domains. Here, the first successful crystallization efforts for a PutA protein are described. Three crystal forms of PutA from Bradyrhizobium japonicum are reported: apparent tetragonal, hexagonal and centered monoclinic. The apparent tetragonal and hexagonal crystals were grown in the presence of PEG 3350 and sodium formate near pH 7. The apparent tetragonal form diffracted to 2.7 Å resolution and exhibited pseudo-merohedral twinning such that the true space group is P2 1 2 1 2 1 with four molecules in the asymmetric unit. The hexagonal form diffracted to 2.3 Å resolution and belonged to space group P6 2 22 with one molecule in the asymmetric unit. Centered monoclinic crystals were grown in ammonium sulfate, diffracted to 2.3 Å resolution and had two molecules in the asymmetric unit. Removing the histidine tag was important in order to obtain the C2 crystal form

  3. Three crystal forms of the bifunctional enzyme proline utilization A (PutA) from Bradyrhizobium japonicum.

    Science.gov (United States)

    Schuermann, Jonathan P; White, Tommi A; Srivastava, Dhiraj; Karr, Dale B; Tanner, John J

    2008-10-01

    Proline utilization A proteins (PutAs) are large (1000-1300 residues) membrane-associated bifunctional flavoenzymes that catalyze the two-step oxidation of proline to glutamate by the sequential action of proline dehydrogenase and Delta(1)-pyrroline-5-carboxylate dehydrogenase domains. Here, the first successful crystallization efforts for a PutA protein are described. Three crystal forms of PutA from Bradyrhizobium japonicum are reported: apparent tetragonal, hexagonal and centered monoclinic. The apparent tetragonal and hexagonal crystals were grown in the presence of PEG 3350 and sodium formate near pH 7. The apparent tetragonal form diffracted to 2.7 A resolution and exhibited pseudo-merohedral twinning such that the true space group is P2(1)2(1)2(1) with four molecules in the asymmetric unit. The hexagonal form diffracted to 2.3 A resolution and belonged to space group P6(2)22 with one molecule in the asymmetric unit. Centered monoclinic crystals were grown in ammonium sulfate, diffracted to 2.3 A resolution and had two molecules in the asymmetric unit. Removing the histidine tag was important in order to obtain the C2 crystal form.

  4. Highly Active and Durable Nanocrystal-Decorated Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

    Science.gov (United States)

    Lee, Dong Un; Park, Moon Gyu; Park, Hey Woong; Seo, Min Ho; Wang, Xiaolei; Chen, Zhongwei

    2015-09-21

    A highly active and durable bifunctional electrocatalyst that consists of cobalt oxide nanocrystals (Co3 O4 NC) decorated on the surface of N-doped carbon nanotubes (N-CNT) is introduced as effective electrode material for electrically rechargeable zinc-air batteries. This active hybrid catalyst is synthesized by a facile surfactant-assisted method to produce Co3 O4 NC that are then decorated on the surface of N-CNT through hydrophobic attraction. Confirmed by half-cell testing, Co3 O4 NC/N-CNT demonstrates superior oxygen reduction and oxygen evolution catalytic activities and has a superior electrochemical stability compared to Pt/C and Ir/C. Furthermore, rechargeable zinc-air battery testing of Co3 O4 NC/N-CNT reveals superior galvanodynamic charge and discharge voltages with a significantly extended cycle life of over 100 h, which suggests its potential as a replacement for precious-metal-based catalysts for electric vehicles and grid energy storage applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Subunit topography of RNA polymerase from Escherichia coli. A cross-linking study with bifunctional reagents.

    Science.gov (United States)

    Hillel, Z; Wu, C W

    1977-07-26

    The quaternary structures of Escherichia coli DNA-dependent RNA polymerase holenzyme (alpha 2 beta beta' sigma) and core enzyme (alpha 2 beta beta') have been investigated by chemical cross-linking with a cleavable bifunctional reagent, methyl 4-mercaptobutyrimidate, and noncleavable reagents, dimethyl suberimidate and N,N'-(1,4-phenylene)bismaleimide. A model of the subunit organization deduced from cross-linked subunit neighbors identified by dodecyl sulfate-polyacrylamide gel electrophoresis indicates that the large beta and beta' subunits constitute the backbone of both core and holoenzyme, while sigma and two alpha subunits interact with this structure along the contact domain of beta and beta' subunits. In holoenzyme, sigma subunit is in the vicinity of at least one alpha subunit. The two alpha subunits are close to each other in holoenzyme, core enzyme, and the isolated alpha 2 beta complex. Cross-linking of the "premature" core and holoenzyme intermediates in the in vitro reconstitution of active enzyme from isolated subunits suggests that these species are composed of subunit complexes of molecular weight lower than that of native core and holoenzyme, respectively. The structural information obtained for RNA polymerase and its subcomplexes has important implications for the enzyme-promoter recognition as well as the mechanism of subunit assembly of the enzyme.

  6. Enhanced metal extractive behavior using dual mechanism bifunctional polymer: an effective metal chelatogen.

    Science.gov (United States)

    Prabhakaran, D; Subramanian, M S

    2003-11-12

    A new class of chelating polymers using Amberlite XAD-16 (AXAD-16) modified with (N-(3,4-dihydroxy)benzyl)-4-amino,3-hydroxynapthalene-1-sulphonic acid has been developed based on dual mechanism bifunctional polymers, for the extraction of transition and post-transition metal ions. The optimum pH conditions for the quantitative sorption of metal ions were studied. The developed method showed superior extraction qualities with high metal loading capacities of 71, 85, 182, 130 and 46 mg g(-1) for Ni(II), Cd(II), Pb(II), Cu(II) and Co(II), respectively. The rate of metal ion uptake i.e. kinetics studies performed under optimum levels showed a time duration of metal ion saturation. Desorption of metal ions were effective with 15 ml of 2 M HCl/HNO(3) prior to detection using flame atomic absorption spectrophotometer. The chelating polymer was highly ion-selective in nature even in the presence of large concentrations of alkali and alkaline earth metal ions, with a high preconcentrating ability for the metal ions of interest. The developed chelating matrix was tested on its utility with synthetic and real samples like river/sea/tap/well water samples and also with multivitamin/mineral tablets, showed R.S.D. values of <2.5% reflecting on the accuracy and reproducibility of data using the newly developed resin matrix.

  7. A new bifunctional hybrid nanostructure as an active platform for photothermal therapy and MR imaging.

    Science.gov (United States)

    Khafaji, Mona; Vossoughi, Manouchehr; Hormozi-Nezhad, M Reza; Dinarvand, Rassoul; Börrnert, Felix; Irajizad, Azam

    2016-06-14

    As a bi-functional cancer treatment agent, a new hybrid nanostructure is presented which can be used for photothermal therapy by exposure to one order of magnitude lower laser powers compared to similar nanostructures in addition to substantial enhancment in magnetic resonance imaging (MRI) contrast. This gold-iron oxide hybrid nanostructure (GIHN) is synthesized by a cost-effective and high yield water-based approach. The GIHN is sheilded by PEG. Therefore, it shows high hemo and biocompatibility and more than six month stability. Alongside earlier nanostructures, the heat generation rate of GIHN is compareable with surfactnat-capped gold nanorods (GNRs). Two reasons are behind this enhancement: Firstly the distance between GNRs and SPIONs is adjusted in a way that the surface plasmon resonance of the new nanostructure is similar to bare GNRs and secondly the fraction of GNRs is raised in the hybrid nanostructure. GIHN is then applied as a photothermal agent using laser irradiation with power as low as 0.5 W.cm(-2) and only 32% of human breast adenocarcinoma cells could survive. The GIHN also acts as a dose-dependent transvers relaxation time (T2) MRI contrast agent. The results show that the GINH can be considered as a good candidate for multimodal photothermal therapy and MRI.

  8. 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.

  9. 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.

  10. "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.

  11. 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.

  12. 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.

  13. 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.

  14. Phenyl-N,N-dibutylcarbamoylmethyl sulfoxide as a new bifunctional extractant for extraction of uranium(VI) in toluene

    International Nuclear Information System (INIS)

    Han Jing-Tian; Sun Guo-Xin; Shao Hua; Bao Bo-Rong; Chen Shu-Feng

    1999-01-01

    A new bifunctional extractant named phenyl-N,N-dibutylcarbamoylmethyl sulfoxide (PCMSO) is synthesized and characterized in order to investigate its selectivity and capability in the extraction from acidic nitrate media in nuclear reprocessing. The extraction of uranium(VI) with PCMSO in toluene has been studied at various concentrations of nitric acid, extractant and salting-out agent (LiNO 3 ). The mechanism of extraction is discussed in the light of the results obtained. The extracted species has also been investigated using FT-IR spectrometry. The related thermodynamic functions were calculated. The IR spectral study was also made of the extracted species. (author)

  15. Stable expression of a bifunctional diterpene synthase in the chloroplast of Chlamydomonas reinhardtii

    DEFF Research Database (Denmark)

    Zedler, Julie Annemarie Zita; Gangl, Doris; Hamberger, Björn Robert

    2015-01-01

    the generation of transgenic lines without the use of antibiotic-resistance genes. Here, we have expressed a bifunctional diterpene synthase in C. reinhardtii chloroplasts. Homoplasmic transformants were obtained with the expressed enzyme accounting for 3.7 % of total soluble protein. The enzyme was purified...... to homogeneity and expression was shown to have a small but reproducible effect on growth rate at the end of log phase growth. These results demonstrate that large recombinant enzymes can be synthesised in the algal chloroplast, and serve to underline its potential as a platform for the biosynthesis of novel...

  16. Engineering a trifunctional proline utilization A chimaera by fusing a DNA-binding domain to a bifunctional PutA

    OpenAIRE

    Arentson, Benjamin?W.; Hayes, Erin?L.; Zhu, Weidong; Singh, Harkewal; Tanner, John?J.; Becker, Donald?F.

    2016-01-01

    Proline utilization A (PutA) is a bifunctional flavoenzyme with proline dehydrogenase (PRODH) and ?1-pyrroline-5-carboxylate (P5C) dehydrogenase (P5CDH) domains that catalyses the two-step oxidation of proline to glutamate. Trifunctional PutAs also have an N-terminal ribbon?helix?helix (RHH) DNA-binding domain and moonlight as autogenous transcriptional repressors of the put regulon. A unique property of trifunctional PutA is the ability to switch functions from DNA-bound repressor to membran...

  17. Recyclable Bifunctional Polystyrene and Silica Gel-Supported Organocatalyst for the Coupling of CO2 with Epoxides.

    Science.gov (United States)

    Kohrt, Christina; Werner, Thomas

    2015-06-22

    A bifunctional ammonium salt covalently bound to a polystyrene or silica support proved to be an efficient and recyclable catalyst for the solvent-free synthesis of cyclic carbonates from epoxides and CO2 . The catalyst can be easily recovered by simple filtration after the reaction and reused in up to 13 consecutive runs with retention of high activity and selectivity even at 90 °C. The scope and limitations of the reaction has been evaluated in terms of reaction conditions and substrate scope. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. 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.

  19. Photocatalytic isotopic exchange between cyclopentane and deuterium over a bifunctional Pt/TiO2 catalyst

    International Nuclear Information System (INIS)

    Courbon, H.; Herrmann, J.M.; Pichat, P.

    1981-01-01

    Cyclopentane-deuterium isotopic exchange (CDIE) was performed at -10 0 C with a C 5 H 10 /D 2 ratio of approx. =6.4% over an illuminated (300 to 410 nm) 0.5 wt% Pt/anatase catalyst. A selectivity in C 5 H 9 D of approx. =90% was found with a total quantum yield of approx. =1.8%. The photocatalytic nature of CDIE under these conditions was established from these results: (i) no CDIE in the absence of photons of wavelengths shorter than the absorption edge of anatase or when TiO 2 was replaced by SiO 2 , whereas the CDIE observed at higher temperatures (from 0 0 C) without uv light mainly produced multiply exchanged cyclopentane, (ii) a linear CDIE rate-illumination time relationship was found, and (iii) an experiment carried out with the same catalyst sample showed that it was capable of exchanging, in successive runs, without decrease in activity, an amount of C 5 H 10 78 times greater than that corresponding to a photoinduced stoichiometric surface reaction. By contrast, CDIE over pure TiO 2 was limited and was only observed for hydroxylated specimens pretreated in D 2 at 300 0 C. It is concluded that (i) CDIE occurred on anatase between weakly adsorbed C 5 H 10 and OD - ions activated by the trapping of photoproduced positive holes, and (ii) Pt, besides attracting the support-free electrons which decreased the recombination of electron-hole pairs, regenerated the titania OD - ions after their isotopic exchange, which involved D 2 dissociative adsorption on the metal and subsequent migration of D atoms to the oxide. This constitutes an example of bifunctional heterogeneous photocatalysis

  20. 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.

  1. 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.

  2. 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

  3. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

    Science.gov (United States)

    Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai; Dai, Liming

    2015-05-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO2 and MnO2) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ˜1,663 m2 g-1 and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn-1 (corresponding to an energy density of 835 Wh kgZn-1), a peak power density of 55 mW cm-2, and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm-2. We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.

  4. Novel configuration of bifunctional air electrodes for rechargeable zinc-air batteries

    Science.gov (United States)

    Li, Po-Chieh; Chien, Yu-Ju; Hu, Chi-Chang

    2016-05-01

    A novel configuration of two electrodes containing electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) pressed into a bifunctional air electrode is designed for rechargeable Zn-air batteries. MOC/25BC carbon paper (MOC consisting of α-MnO2 and XC-72 carbon black) and Fe0.1Ni0.9Co2O4/Ti mesh on this air electrode mainly serve as the cathode for the ORR and the anode for the OER, respectively. The morphology and physicochemical properties of Fe0.1Ni0.9Co2O4 are investigated through scanning electron microscopy, inductively coupled plasma-mass spectrometry, and X-ray diffraction. Electrochemical studies comprise linear sweep voltammetry, rotating ring-disk electrode voltammetry, and the full-cell charge-discharge-cycling test. The discharge peak power density of the Zn-air battery with the unique air electrode reaches 88.8 mW cm-2 at 133.6 mA cm-2 and 0.66 V in an alkaline electrolyte under an ambient atmosphere. After 100 charge-discharge cycles at 10 mA cm-2, an increase of 0.3 V between charge and discharge cell voltages is observed. The deep charge-discharge curve (10 h in each step) indicates that the cell voltages of discharge (1.3 V) and charge (1.97 V) remain constant throughout the process. The performance of the proposed rechargeable Zn-air battery is superior to that of most other similar batteries reported in recent studies.

  5. 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

  6. Characterization of a bifunctional glyoxylate cycle enzyme, malate synthase/isocitrate lyase, of Euglena gracilis.

    Science.gov (United States)

    Nakazawa, Masami; Nishimura, Masaaki; Inoue, Kengo; Ueda, Mitsuhiro; Inui, Hiroshi; Nakano, Yoshihisa; Miyatake, Kazutaka

    2011-01-01

    The glyoxylate cycle is a modified form of the tricarboxylic acid cycle, which enables organisms to synthesize carbohydrates from C2 compounds. In the protozoan Euglena gracilis, the key enzyme activities of the glyoxylate cycle, isocitrate lyase (ICL) and malate synthase (MS), are conferred by a single bifunctional protein named glyoxylate cycle enzyme (Euglena gracilis glyoxylate cycle enzyme [EgGCE]). We analyzed the enzymatic properties of recombinant EgGCE to determine the functions of its different domains. The 62-kDa N-terminal domain of EgGCE was sufficient to provide the MS activity as expected from an analysis of the deduced amino acid sequence. In contrast, expression of the 67-kDa C-terminal domain of EgGCE failed to yield ICL activity even though this domain was structurally similar to ICL family enzymes. Analyses of truncation mutants suggested that the N-terminal residues of EgGCE are critical for both the ICL and MS activities. The ICL activity of EgGCE increased in the presence of micro-molar concentrations of acetyl-coenzyme A (CoA). Acetyl-CoA also increased the activity in a mutant type EgGCE with a mutation at the acetyl-CoA binding site in the MS domain of EgGCE. This suggests that acetyl-CoA regulates the ICL reaction by binding to a site other than the catalytic center of the MS reaction. © 2011 The Author(s). Journal of Eukaryotic Microbiology© 2011 International Society of Protistologists.

  7. Crystal structure of two new bifunctional nonsubstrate type thrombin inhibitors complexed with human alpha-thrombin.

    Science.gov (United States)

    Féthière, J; Tsuda, Y; Coulombe, R; Konishi, Y; Cygler, M

    1996-06-01

    The crystal structures of two new thrombin inhibitors, P498 and P500, complexed with human alpha-thrombin have been determined at 2.0 A resolution and refined to crystallographic R-factors of 0.170 and 0.169, respectively. These compounds, with picomolar binding constants, belong to a family of potent bifunctional inhibitors that bind thrombin at two remote sites: the active site and the fibrinogen recognition exosite (FRE). The inhibitors incorporate a nonsubstrate type active site binding fragment: Dansyl-Arg-(D)Pipecolic acid (Dns-Arg-(D)Pip), reminiscent of the active-site directed inhibitors MD-805 and MQPA, rendering them resistant to thrombin-induced hydrolysis. The FRE binding fragment of these inhibitors corresponds to the hirudin55-65 sequence. They differ in the chemical nature of the nonpeptidyl linker bridging these two functional activities. In both cases, the active site binding fragment is well defined in the electron density. The DnsH1, ArgH2, and (D)PipH3 groups occupy the S3, S1, and S2 subsites of thrombin, respectively, in a way similar to that observed in the thrombin-MQPA complexes. Binding in the active site of thrombin is characterized by numerous van der Waals contacts and ring-ring system interactions. Unlike in the substrate-like inhibitors, ArgH2 enters the S1 specificity pocket from the P2 position and adopts a bent conformation to make an hydrogen bond to the carboxylate of Asp189. In this noncanonical position, its carbonyl points away from the oxyanion hole, which is now occupied by well-ordered solvent molecules. The linkers fit in the groove extending from the active site to the FRE. The C-terminal fragments of both inhibitors bind in the same way as analogous FRE binding elements in previously described complexes.

  8. Molecular Evolution and Functional Characterization of a Bifunctional Decarboxylase Involved in Lycopodium Alkaloid Biosynthesis1[OPEN

    Science.gov (United States)

    Bunsupa, Somnuk; Hanada, Kousuke; Maruyama, Akira; Aoyagi, Kaori; Komatsu, Kana; Ueno, Hideki; Yamashita, Madoka; Sasaki, Ryosuke; Oikawa, Akira; Yamazaki, Mami

    2016-01-01

    Lycopodium alkaloids (LAs) are derived from lysine (Lys) and are found mainly in Huperziaceae and Lycopodiaceae. LAs are potentially useful against Alzheimer’s disease, schizophrenia, and myasthenia gravis. Here, we cloned the bifunctional lysine/ornithine decarboxylase (L/ODC), the first gene involved in LA biosynthesis, from the LA-producing plants Lycopodium clavatum and Huperzia serrata. We describe the in vitro and in vivo functional characterization of the L. clavatum L/ODC (LcL/ODC). The recombinant LcL/ODC preferentially catalyzed the decarboxylation of l-Lys over l-ornithine (l-Orn) by about 5 times. Transient expression of LcL/ODC fused with the amino or carboxyl terminus of green fluorescent protein, in onion (Allium cepa) epidermal cells and Nicotiana benthamiana leaves, showed LcL/ODC localization in the cytosol. Transgenic tobacco (Nicotiana tabacum) hairy roots and Arabidopsis (Arabidopsis thaliana) plants expressing LcL/ODC enhanced the production of a Lys-derived alkaloid, anabasine, and cadaverine, respectively, thus, confirming the function of LcL/ODC in plants. In addition, we present an example of the convergent evolution of plant Lys decarboxylase that resulted in the production of Lys-derived alkaloids in Leguminosae (legumes) and Lycopodiaceae (clubmosses). This convergent evolution event probably occurred via the promiscuous functions of the ancestral Orn decarboxylase, which is an enzyme involved in the primary metabolism of polyamine. The positive selection sites were detected by statistical analyses using phylogenetic trees and were confirmed by site-directed mutagenesis, suggesting the importance of those sites in granting the promiscuous function to Lys decarboxylase while retaining the ancestral Orn decarboxylase function. This study contributes to a better understanding of LA biosynthesis and the molecular evolution of plant Lys decarboxylase. PMID:27303024

  9. 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

  10. 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.

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

    International Nuclear Information System (INIS)

    Przybylak, Marcin; Maciejewski, Hieronim; Dutkiewicz, Agnieszka

    2016-01-01

    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.

  12. 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.

  13. 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

  14. A novel bifunctional hybrid with marine bacterium alkaline phosphatase and Far Eastern holothurian mannan-binding lectin activities.

    Directory of Open Access Journals (Sweden)

    Larissa Balabanova

    Full Text Available A fusion between the genes encoding the marine bacterium Cobetia marina alkaline phosphatase (CmAP and Far Eastern holothurian Apostichopus japonicus mannan-binding C-type lectin (MBL-AJ was performed. Expression of the fusion gene in E. coli cells resulted in yield of soluble recombinant chimeric protein CmAP/MBL-AJ with the high alkaline phosphatase activity and specificity of the lectin MBL-AJ. The bifunctional hybrid CmAP/MBL-AJ was produced as a dimer with the molecular mass of 200 kDa. The CmAP/MBL-AJ dimer model showed the two-subunit lectin part that is associated with two molecules of alkaline phosphatase functioning independently from each other. The highly active CmAP label genetically linked to MBL-AJ has advantaged the lectin-binding assay in its sensitivity and time. The double substitution A156N/F159K in the lectin domain of CmAP/MBL-AJ has enhanced its lectin activity by 25 ± 5%. The bifunctional hybrid holothurian's lectin could be promising tool for developing non-invasive methods for biological markers assessment, particularly for improving the MBL-AJ-based method for early detection of a malignant condition in cervical specimens.

  15. MOF-Derived Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Hydrogen Evolution Reaction and Oxygen Evolution Reaction Electrocatalysts

    Directory of Open Access Journals (Sweden)

    Hong Li

    2018-02-01

    Full Text Available The development of a highly efficient and stable bifunctional electrocatalyst for water splitting is still a challenging issue in obtaining clean and sustainable chemical fuels. Herein, a novel bifunctional catalyst consisting of 2D transition-metal phosphide nanosheets with abundant reactive sites templated by Co-centered metal−organic framework nanosheets, denoted as CoP-NS/C, has been developed through a facile one-step low-temperature phosphidation process. The as-prepared CoP-NS/C has large specific surface area and ultrathin nanosheets morphology providing rich catalytic active sites. It shows excellent electrocatalytic performances for hydrogen evolution reaction (HER and oxygen evolution reaction (OER in acidic and alkaline media, with the Tafel slopes of 59 and 64 mV/dec and a current density of 10 mA/cm2 at the overpotentials of 140 and 292 mV, respectively, which are remarkably superior to those of CoP/C, CoP particles, and comparable to those of commercial noble-metal catalysts. In addition, the CoP-NS/C also shows good durability after a long-term test.

  16. MOF-Derived Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Hydrogen Evolution Reaction and Oxygen Evolution Reaction Electrocatalysts.

    Science.gov (United States)

    Li, Hong; Ke, Fei; Zhu, Junfa

    2018-02-07

    The development of a highly efficient and stable bifunctional electrocatalyst for water splitting is still a challenging issue in obtaining clean and sustainable chemical fuels. Herein, a novel bifunctional catalyst consisting of 2D transition-metal phosphide nanosheets with abundant reactive sites templated by Co-centered metal-organic framework nanosheets, denoted as CoP-NS/C, has been developed through a facile one-step low-temperature phosphidation process. The as-prepared CoP-NS/C has large specific surface area and ultrathin nanosheets morphology providing rich catalytic active sites. It shows excellent electrocatalytic performances for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic and alkaline media, with the Tafel slopes of 59 and 64 mV/dec and a current density of 10 mA/cm² at the overpotentials of 140 and 292 mV, respectively, which are remarkably superior to those of CoP/C, CoP particles, and comparable to those of commercial noble-metal catalysts. In addition, the CoP-NS/C also shows good durability after a long-term test.

  17. Isothiocyanate-functionalized bifunctional chelates and fac-[MI(CO)3]+ (M = Re, 99mTc) complexes for targeting uPAR in prostate cancer

    Science.gov (United States)

    Developing strategies to rapidly incorporate the fac-[MI(CO)3]+ (M = Re, 99mTc) core into biological targeting vectors is a growing realm in radiopharmaceutical development. This work presents the preparation of a novel isothiocyanate-functionalized bifunctional chelate based on 2,2´-dipicolylamine ...

  18. Steam reforming of acetic acid as a biomass derived oxygenate: Bifunctional pathway for hydrogen formation over Pt/ZrO2 catalysts.

    NARCIS (Netherlands)

    Takanabe, K.; Aika, Ken-ichi; Inazu, Koji; Baba, Toshihide; Seshan, Kulathuiyer; Lefferts, Leonardus

    2006-01-01

    Mechanistic studies on steam reforming of acetic acid over Pt/ZrO2 catalysts were performed as extension of our previous work [K. Takanabe, K. Aika, K. Seshan, L. Lefferts, J. Catal. 227 (2004) 101]. An overall picture of the bifunctional mechanism is established for steam reforming of acetic acid,

  19. 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

  20. Enantioselective Michael Addition of 3-Aryl-Substituted Oxindoles to Methyl Vinyl Ketone Catalyzed by a Binaphthyl-Modified Bifunctional Organocatalyst

    Directory of Open Access Journals (Sweden)

    Saet Byeol Woo

    2012-06-01

    Full Text Available The enantioselective conjugate addition reaction of 3-aryl-substituted oxindoles with methyl vinyl ketone promoted by binaphthyl-modified bifunctional organocatalysts was investigated. The corresponding Michael adducts, containing a quaternary center at the C3-position of the oxindoles, were generally obtained in high yields with excellent enantioselectivities (up to 91% ee.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. Alginic acid: A mild and renewable bifunctional heterogeneous biopolymeric organocatalyst for efficient and facile synthesis of polyhydroquinolines.

    Science.gov (United States)

    Dekamin, Mohammad G; Karimi, Zahra; Latifidoost, Zahra; Ilkhanizadeh, Siamand; Daemi, Hamed; Naimi-Jamal, M Reza; Barikani, Mehdi

    2018-03-01

    Alginic acid, a widely used naturally occurring carbohydrate which is generally derived from brown seaweeds, can be considered as a bifunctional heterogeneous and green biopolymeric organocatalyst. Alginic acid, without any post-modification with active Bronsted or Lewis acid centers, was found to be a highly active, cost-effective, commercially-available, renewable and recoverable heterogeneous biopolymeric organocatalyst for the expeditious synthesis of polyhydroquinolines (PHQs). Polyhydroquinolines were synthesized from the four-component Hantzsch reaction of ethyl acetoacetate, different aldehydes, ammonium acetate and cyclic 1,3-diones under mild conditions in high to quantitative yields, 75-97%, using alginic acid. Furthermore, alginic acid was found to be reusable for at least 6 consecutive cycles without considerable loss of its catalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    2010-01-01

    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. PMID:20044937

  7. 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.

  8. RNA Secondary Structure Modulates FMRP’s Bi-Functional Role in the MicroRNA Pathway

    Directory of Open Access Journals (Sweden)

    Phillip Kenny

    2016-06-01

    Full Text Available MicroRNAs act by post-transcriptionally regulating the gene expression of 30%–60% of mammalian genomes. MicroRNAs are key regulators in all cellular processes, though the mechanism by which the cell activates or represses microRNA-mediated translational regulation is poorly understood. In this review, we discuss the RNA binding protein Fragile X Mental Retardation Protein (FMRP and its role in microRNA-mediated translational regulation. Historically, FMRP is known to function as a translational suppressor. However, emerging data suggests that FMRP has both an agonistic and antagonistic role in regulating microRNA-mediated translational suppression. This bi-functional role is dependent on FMRP’s interaction with the RNA helicase Moloney leukemia virus 10 (MOV10, which modifies the structural landscape of bound mRNA, therefore facilitating or inhibiting its association with the RNA-Induced Silencing Complex.

  9. A selectable bifunctional beta-galactosidase::phleomycin-resistance fusion protein as a potential marker for eukaryotic cells.

    Science.gov (United States)

    Baron, M; Reynes, J P; Stassi, D; Tiraby, G

    1992-05-15

    The Sh ble gene, conferring phleomycin resistance (PhR), was fused in frame to both the 3' and 5' ends of the Escherichia coli lacZ gene. The bifunctionality of the resulting 130-kDa hybrid proteins was demonstrated in E. coli and in the fungus, Tolypocladium geodes. PhR transformants of both organisms could be selected for. All transformants from E. coli and most from T. geodes displayed beta Gal activity. In the fungal host, higher transformation frequencies and greater levels of beta Gal activity were observed in clones harboring the lacZ::Sh ble fusion, as compared to the Sh ble::lacZ configuration. This system appears to be a potentially useful tool for the direct selection of transformants, and the evaluation of gene expression and regulation in a wide variety of prokaryotic and eukaryotic hosts.

  10. A novel bifunctional pectinase from Penicillium oxalicum SX6 with separate pectin methylesterase and polygalacturonase catalytic domains.

    Science.gov (United States)

    Tu, Tao; Bai, Yingguo; Luo, Huiying; Ma, Rui; Wang, Yaru; Shi, Pengjun; Yang, Peilong; Meng, Kun; Yao, Bin

    2014-06-01

    A multimodular pectinase of glycoside hydrolase family 28, S6A, was identified in Penicillium oxalicum SX6 that consists of an N-terminal catalytic domain of pectin methylesterase, a Thr/Ser-rich linker region, and a C-terminal catalytic domain of polygalacturonase. Recombinant S6A and its two derivatives, S6PE (the catalytic domain of pectin methylesterase) and S6PG (the catalytic domain of polygalacturonase), were produced in Pichia pastoris. S6A was a bifunctional protein and had both pectin methylesterase and polygalacturonase activities. Three enzymes showed similar biochemical properties, such as optimal pH and temperature (pH 5.0 and 50 °C) and excellent stability at pH 3.5-6.0 and 40 °C. Most metal ions tested (Na(+), K(+), Ca(2+), Li(+), Co(2+), Cr(3+), Ni(2+), Cu(2+), Mn(2+),Mg(2+), Fe(3+), Zn(2+), and Pb(2+)) enhanced the pectin methylesterase activities of S6PE and S6A, but had little or inhibitory effects on the polygalacturonase activities of S6A and S6PG. In comparison with most fungal pectin methylesterases, S6A had higher specific activity (271.1 U/mg) towards 70 % DM citrus pectin. When S6PE and S6PG were combined at the activity ratio of 1:4, the most significant synergistic effect was observed in citrus pectin degradation and degumming of sisal fiber, which is comparable with the performance of S6A (95 v.s. 100 % and 16.9 v.s. 17.2 %, respectively). To the best of our knowledge, this work represents the first report of gene cloning, heterologous expression, and biochemical characterization of a bifunctional pectinase with separate catalytic domains.

  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

    2014-06-01

    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.

  12. Electrosynthesis of Bifunctional WS3-x /Reduced Graphene Oxide Hybrid for Hydrogen Evolution Reaction and Oxygen Reduction Reaction Electrocatalysis.

    Science.gov (United States)

    Tan, Shu Min; Pumera, Martin

    2017-06-22

    A multitude of research into the application of transition-metal dichalcogenides as earth-abundant hydrogen evolution reaction (HER) electrocatalysts has been conducted. However, current synthetic methods generally deploy environmentally harmful chemicals and energy-consuming reaction conditions, despite the primary intent to attain renewable energy production. Here, the desirable properties of tungsten sulfide and reduced graphene oxide (rGO) have been combined and hybrid materials have been fabricated through simultaneous electrochemical reduction and synthesis, as a versatile and environmentally benign alternative to conventional fabrication techniques. Through concurrent studies of three rGO materials, the precursor of which was graphene oxide (GO), produced by Hummers, Staudenmaier, or Hofmann oxidation methods, the importance of the choice of oxidation method employed prior to the fabrication of the hybrid was shown. In this cardinal study, a mixed WS 2 /WS 3 film-like material (WS 3-x ) was synthesized directly onto GO-modified glassy carbon electrodes by cyclic voltammetry and the resultant hybrid materials (WS 3-x /rGO) were thoroughly characterized by SEM, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The excellent bifunctional electrocatalytic performances of WS 3-x /rGO towards both HER and oxygen reduction reaction stemmed from the coupled impacts of amplified electrical conductivity and surface area of rGO; the presence of metallic species within rGO, resulting from the oxidation process; and the amount of WS 3-x successfully electrodeposited in the hybrid. The efficacious fabrication of the WS 3-x /rGO composite through electrosynthesis reveals an innovative and eco-friendly methodology for the development of cost-effective and highly active bifunctional electrocatalysts for renewable energy generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. Optico-cochleo-dentate degeneration associated with severe peripheral neuropathy and caused by peroxisomal D-bifunctional protein deficiency.

    Science.gov (United States)

    Schröder, J M; Hackel, V; Wanders, R J A; Göhlich-Ratmann, G; Voit, T

    2004-08-01

    The clinical, neuroradiological, neuropathological and biochemical findings in a patient with optico-cochleo-dentate degeneration (OCDD; OMIM 258700) are presented in a severe case succumbing at the age of 4 years. The electron microscopic and biochemical data showed for the first time that OCDD may occur as the phenotypic expression of D-bifunctional protein deficiency, i.e., a peroxisomal disorder. The boy was born as the first child of healthy, consanguineous parents of Turkish origin. No other family members were affected. The main clinical symptoms consisted of muscle hypotonia ("floppy infant"), generalized epileptic fits, hypacusis, rotatory nystagmus, insufficient pupillary reactions, and mental retardation. Fibroblast cultures revealed D-bifunctional protein deficiency. Neuropathological examination displayed moderate frontoparietal and insular microgyria, and atrophy of the cerebellum. Loss of neurons was severe in the granular layer, the Purkinje cell band of the cerebellum, and rather complete in the dentate nucleus. A corresponding loss of myelinated fibers associated with characteristic periodic acid-Schiff-positive macrophages was most prominent in the white matter of the cerebellum. There was additional severe loss of myelinated fibers in the central portions of the optic nerve, reduction of the nerve fiber density in the cochlear nerve, and reduction of myelinated nerve fibers by about 80-90% in the sural nerve, which has not been studied in previous cases. At the electron microscopic level, characteristic inclusions mainly in perivascular macrophages and astrocytes were the most prominent finding. The inclusions usually showed a bilaminar structure, whereas trilaminar structures, typically seen in adrenoleukodystrophy, and multilaminar structures were less frequently seen.

  15. Engineering a Zirconium MOF through Tandem "Click" Reactions: A General Strategy for Quantitative Loading of Bifunctional Groups on the Pore Surface.

    Science.gov (United States)

    Zhang, Yingfan; Gui, Bo; Chen, Rufan; Hu, Guiping; Meng, Yi; Yuan, Daqiang; Zeller, Matthias; Wang, Cheng

    2018-02-19

    Metal-organic frameworks (MOFs) assembled from linkers of identical length but with different functional groups have gained increasing interests recently. However, it is very challenging for precise control of the ratios of different functionalities. Herein, we reported a stable azide- and alkyne-appended Zr-MOF that can undergo quantitative tandem click reactions on the different functional sites, thus providing a unique platform for quantitative loading of bifunctional moieties. As an added advantage, the same MOF product can be obtained via two independent routes. The method is versatile and can tolerate a wide variety of functional groups, and furthermore, a heterogeneous acid-base MOF organocatalyst was synthesized by tandemly introducing both acidic and basic groups onto the predesigned pore surface. The presented strategy provides a general way toward the construction of bifunctional MOFs with a precise control of ratio of different functionalities for desirable applications in future.

  16. Striking hierarchical urchin-like peapoded NiCo2O4@C as advanced bifunctional electrocatalyst for overall water splitting

    Science.gov (United States)

    Deng, Ju; Zhang, Huijuan; Zhang, Yan; Luo, Pan; Liu, Li; Wang, Yu

    2017-12-01

    Developing bifunctional electrocatalysts with features of wide source, low price and high efficiency for overall water splitting has the extremely vital significance on the energy front. Herein, we have designed and fabricated urchin-like peapoded NiCo2O4@C architecture for the first time, playing a prominent role in bifunctional alkaline catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 M NaOH ascribed to outstanding catalytic performance and good stability. When the urchin-like peapoded NiCo2O4@C electrodes are integrated into the two-electrode system for alkaline overall water splitting, the potential as small as ∼1.608 V is a requisite for the current density of 10 mA cm-2. Given high activity and long-term stability, the harvested urchin-like peapoded NiCo2O4@C is of great potential for practical application.

  17. 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)

  18. 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

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

    International Nuclear Information System (INIS)

    Chang, Yoke-Chen; Wang, James D.; Hahn, Rita A.; Gordon, Marion K.; Joseph, Laurie B.; Heck, Diane E.; Heindel, Ned D.; Young, Sherri C.; Sinko, Patrick J.; Casillas, Robert P.; Laskin, Jeffrey D.; Laskin, Debra L.; Gerecke, Donald R.

    2014-01-01

    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

  20. A universal and facile way for the development of superior bifunctional electrocatalysts for oxygen reduction and evolution reactions utilizing the synergistic effect.

    Science.gov (United States)

    Zhu, Yinlong; Su, Chao; Xu, Xiaomin; Zhou, Wei; Ran, Ran; Shao, Zongping

    2014-11-17

    Increasing energy demands have stimulated intense research activities on reversible electrochemical conversion and storage systems with high efficiency, low cost, and environmental benignity. It is highly challenging but desirable to develop efficient bifunctional catalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A universal and facile method for the development of bifunctional electrocatalysts with outstanding electrocatalytic activity for both the ORR and OER in alkaline medium is reported. A mixture of Pt/C catalyst with superior ORR activity and a perovskite oxide based catalyst with outstanding OER activity was employed in appropriate ratios, and prepared by simple ultrasonic mixing. Nanosized platinum particles with a wide range of platinum to oxide mass ratios was realized easily in this way. The as-formed Pt/C-oxide composites showed better ORR activity than a single Pt/C catalyst and better OER activity than a single oxide to bring about much improved bifunctionality (ΔE is only ≈0.8 V for Pt/C-BSCF; BSCF=Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ ), due to the synergistic effect. The electronic transfer mechanism and the rate-determining step and spillover mechanism were two possible origins of such a synergistic effect. Additionally, the phenomenon was found to be universal, although the best performance could be reached at different platinum to oxide mass ratios for different oxide catalysts. This work thus provides an innovative strategy for the development of new bifunctional electrocatalysts with wide application potentials in high-energy and efficient electrochemical energy storage and conversion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Catalytic Asymmetric Synthesis of Both Enantiomers of 4‑Substituted 1,4-Dihydropyridines with the Use of Bifunctional Thiourea-Ammonium Salts Bearing Different Counterions

    Directory of Open Access Journals (Sweden)

    Kohzo Yoshida

    2010-11-01

    Full Text Available Organoammonium salts composed of a Brønsted acid and an anilinothiourea promoted the Michael addition of β-keto esters and α,β-unsaturated aldehydes in the presence of primary amines to give functionalized 1,4-dihydropyridines enantioselectively. With the use of the different Brønsted acids such as DFA and HBF4 with the same bifunctional thiourea, both enantiomers of 4-substituted 1,4-dihydropyridine were synthesized from the same starting materials.

  2. 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

  3. Engineering of restriction endonucleases: using methylation activity of the bifunctional endonuclease Eco57I to select the mutant with a novel sequence specificity.

    Science.gov (United States)

    Rimseliene, Renata; Maneliene, Zita; Lubys, Arvydas; Janulaitis, Arvydas

    2003-03-21

    Type II restriction endonucleases (REs) are widely used tools in molecular biology, biotechnology and diagnostics. Efforts to generate new specificities by structure-guided design and random mutagenesis have been unsuccessful so far. We have developed a new procedure called the methylation activity-based selection (MABS) for generating REs with a new specificity. MABS uses a unique property of bifunctional type II REs to methylate DNA targets they recognize. The procedure includes three steps: (1) conversion of a bifunctional RE into a monofunctional DNA-modifying enzyme by cleavage center disruption; (2) mutagenesis and selection of mutants with altered DNA modification specificity based on their ability to protect predetermined DNA targets; (3) reconstitution of the cleavage center's wild-type structure. The efficiency of the MABS technique was demonstrated by altering the sequence specificity of the bifunctional RE Eco57I from 5'-CTGAAG to 5'-CTGRAG, and thus generating the mutant restriction endonuclease (and DNA methyltransferase) of a specificity not known before. This study provides evidence that MABS is a promising technique for generation of REs with new specificities.

  4. Bifunctional phosphoglucose/phosphomannose isomerases from the Archaea Aeropyrum pernix and Thermoplasma acidophilum constitute a novel enzyme family within the phosphoglucose isomerase superfamily.

    Science.gov (United States)

    Hansen, Thomas; Wendorff, Daniel; Schönheit, Peter

    2004-01-16

    The hyperthermophilic crenarchaeon Aeropyrum pernix contains phosphoglucose isomerase (PGI) activity. However, obvious homologs with significant identity to known PGIs could not be identified in the sequenced genome of this organism. The PGI activity from A. pernix was purified and characterized. Kinetic analysis revealed that, unlike all known PGIs, the enzyme catalyzed reversible isomerization not only of glucose 6-phosphate but also of epimeric mannose 6-phosphate at similar catalytic efficiency, thus defining the protein as bifunctional phosphoglucose/phosphomannose isomerase (PGI/PMI). The gene pgi/pmi encoding PGI/PMI (open reading frame APE0768) was identified by matrix-assisted laser desorption ionization time-of-flight analyses; the gene was overexpressed in Escherichia coli as functional PGI/PMI. Putative PGI/PMI homologs were identified in several (hyper)thermophilic archaea and two bacteria. The homolog from Thermoplasma acidophilum (Ta1419) was overexpressed in E. coli, and the recombinant enzyme was characterized as bifunctional PGI/PMI. PGI/PMIs showed low sequence identity to the PGI superfamily and formed a distinct phylogenetic cluster. However, secondary structure predictions and the presence of several conserved amino acids potentially involved in catalysis indicate some structural and functional similarity to the PGI superfamily. Thus, we propose that bifunctional PGI/PMI constitutes a novel protein family within the PGI superfamily.

  5. An Efficient Bifunctional Electrocatalyst for a Zinc-Air Battery Derived from Fe/N/C and Bimetallic Metal-Organic Framework Composites.

    Science.gov (United States)

    Wang, Mengfan; Qian, Tao; Zhou, Jinqiu; Yan, Chenglin

    2017-02-15

    Efficient bifunctional electrocatalysts with desirable oxygen activities are closely related to practical applications of renewable energy systems including metal-air batteries, fuel cells, and water splitting. Here a composite material derived from a combination of bimetallic zeolitic imidazolate frameworks (denoted as BMZIFs) and Fe/N/C framework was reported as an efficient bifunctional catalyst. Although BMZIF or Fe/N/C alone exhibits undesirable oxygen reaction activity, a combination of these materials shows unprecedented ORR (half-wave potential of 0.85 V as well as comparatively superior OER activities (potential@10 mA cm -2 of 1.64 V), outperforming not only a commercial Pt/C electrocatalyst but also most reported bifunctional electrocatalysts. We then tested its practical application in Zn-air batteries. The primary batteries exhibit a high peak power density of 235 mW cm -2 , and the batteries are able to be operated smoothly for 100 cycles at a curent density of 10 mA cm -2 . The unprecedented catalytic activity can be attritued to chemical coupling effects between Fe/N/C and BMZIF and will aid the development of highly active electrocatalysts and applications for electrochemical energy devices.

  6. Self-assembly of cobalt-centered metal organic framework and multiwalled carbon nanotubes hybrids as a highly active and corrosion-resistant bifunctional oxygen catalyst

    Science.gov (United States)

    Fang, Yiyun; Li, Xinzhe; Li, Feng; Lin, Xiaoqing; Tian, Min; Long, Xuefeng; An, Xingcai; Fu, Yan; Jin, Jun; Ma, Jiantai

    2016-09-01

    Metal organic frameworks (MOF) derived carbonaceous materials have emerged as promising bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts for electrochemical energy conversion and storage. But previous attempts to overcome the poor electrical conductivity of MOFs hybrids involve a harsh high-template pyrolytic process to in situ form carbon, which suffer from extremely complex operation and inevitable carbon corrosion at high positive potentials when OER is operated. Herein, a self-assembly approach is presented to synthesize a non-precious metal-based, high active and strong durable Co-MOF@CNTs bifunctional catalyst for OER and ORR. CNTs not only improve the transportation of the electrons but also can sustain the harsh oxidative environment of OER without carbon corrosion. Meanwhile, the unique 3D hierarchical structure offers a large surface area and stable anchoring sites for active centers and CNTs, which enables the superior durability of hybrid. Moreover, a synergistic catalysis of Co(II), organic ligands and CNTs will enhance the bifunctional electrocatalytic performance. Impressively, the hybrid exhibits comparable OER and ORR catalytic activity to RuO2 and 20 wt% Pt/C catalysts and superior stability. This facile and versatile strategy to fabricating MOF-based hybrids may be extended to other electrode materials for fuel cell and water splitting applications.

  7. From Chlorella to Nestlike Framework Constructed with Doped Carbon Nanotubes: A Biomass-Derived, High-Performance, Bifunctional Oxygen Reduction/Evolution Catalyst.

    Science.gov (United States)

    Wang, Guanghua; Deng, Yijie; Yu, Jinnan; Zheng, Long; Du, Li; Song, Huiyu; Liao, Shijun

    2017-09-20

    The development of effective bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is significant for energy conversion systems, such as Li-air batteries, fuel cells, and water splitting technologies. Herein, a Chlorella-derived catalyst with a nestlike framework, composed of bamboolike nanotubes that encapsulate cobalt nanoparticles, has been prepared through a facile pyrolysis process. It achieves perfect bifunctional catalysis both in ORR and OER on a single catalyst. For our optimal catalyst Co/M-Chlorella-900, its ORR half-wave potential is positively shifted by 40 mV compared to that of a commercial Pt/C catalyst, and the overpotential at 10 mA cm -2 for the OER is 23 mV lower than that of a commercial IrO 2 /C catalyst in an alkaline medium. This superior bifunctional catalytic performance is benefited from the simultaneous increase of pyridinic N sites for ORR and graphitic N sites for OER. In addition, N-doped carbon-encapsulated Co nanoparticles improve both ORR and OER performance by forming new active centers. The unique nestlike carbon nanotube framework not only afforded highly dense ORR and OER active sites but also promoted the electron and mass transfer. Our catalyst also displays notable durability during the ORR and OER, making it promising for use in ORR/OER-related energy conversion systems.

  8. Ni3FeN-Supported Fe3Pt Intermetallic Nanoalloy as a High-Performance Bifunctional Catalyst for Metal-Air Batteries.

    Science.gov (United States)

    Cui, Zhiming; Fu, Gengtao; Li, Yutao; Goodenough, John B

    2017-08-07

    Electrocatalysts for both the oxygen reduction and evolution reactions (ORR and OER) are vital for the performances of rechargeable metal-air batteries. Herein, we report an advanced bifunctional oxygen electrocatalyst consisting of porous metallic nickel-iron nitride (Ni 3 FeN) supporting ordered Fe 3 Pt intermetallic nanoalloy. In this hybrid catalyst, the bimetallic nitride Ni 3 FeN mainly contributes to the high activity for the OER while the ordered Fe 3 Pt nanoalloy contributes to the excellent activity for the ORR. Robust Ni 3 FeN-supported Fe 3 Pt catalysts show superior catalytic performance to the state-of-the-art ORR catalyst (Pt/C) and OER catalyst (Ir/C). The Fe 3 Pt/Ni 3 FeN bifunctional catalyst enables Zn-air batteries to achieve a long-term cycling performance of over 480 h at 10 mA cm -2 with high efficiency. The extraordinarily high performance of the Fe 3 Pt/Ni 3 FeN bifunctional catalyst makes it a very promising air cathode in alkaline electrolyte. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Bifunctional TaqII restriction endonuclease: redefining the prototype DNA recognition site and establishing the Fidelity Index for partial cleaving.

    Science.gov (United States)

    Zylicz-Stachula, Agnieszka; Zołnierkiewicz, Olga; Sliwińska, Katarzyna; Jeżewska-Frąckowiak, Joanna; Skowron, Piotr M

    2011-12-05

    The TaqII enzyme is a member of the Thermus sp. enzyme family that we propounded previously within Type IIS restriction endonucleases, containing related thermophilic bifunctional endonucleases-methyltransferases from various Thermus sp.: TaqII, Tth111II, TthHB27I, TspGWI, TspDTI and TsoI. These enzymes show significant nucleotide and amino acid sequence similarities, a rare phenomenon among restriction endonucleases, along with similarities in biochemical properties, molecular size, DNA recognition sequences and cleavage sites. They also feature some characteristics of Types I and III. Barker et al. reported the Type IIS/IIC restriction endonuclease TaqII as recognizing two distinct cognate site variants (5'-GACCGA-3' and 5'-CACCCA-3') while cleaving 11/9 nucleotides downstream. We used four independent methods, namely, shotgun cloning and sequencing, restriction pattern analysis, digestion of particular custom substrates and GeneScan analysis, to demonstrate that the recombinant enzyme recognizes only 5'-GACCGA-3' sites and cleaves 11/9 nucleotides downstream. We did not observe any 5'-CACCCA-3' cleavage under a variety of conditions and site arrangements tested. We also characterized the enzyme biochemically and established new digestion conditions optimal for practical enzyme applications. Finally, we developed and propose a new version of the Fidelity Index - the Fidelity Index for Partial Cleavage (FI-PC). The DNA recognition sequence of the bifunctional prototype TaqII endonuclease-methyltransferase from Thermus aquaticus has been redefined as recognizing only 5'-GACCGA-3' cognate sites. The reaction conditions (pH and salt concentrations) were designed either to minimize (pH = 8.0 and 10 mM ammonium sulphate) or to enhance star activity (pH = 6.0 and no salt). Redefinition of the recognition site and reaction conditions makes this prototype endonuclease a useful tool for DNA manipulation; as yet, this enzyme has no practical applications. The extension of

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. Spherical nitrogen-doped hollow mesoporous carbon as an efficient bifunctional electrocatalyst for Zn-air batteries.

    Science.gov (United States)

    Hadidi, Lida; Davari, Elaheh; Iqbal, Muhammad; Purkait, Tapas K; Ivey, Douglas G; Veinot, Jonathan G C

    2015-12-28

    Materials based upon porous carbon have gained considerable attention due to their high surface area, electric conductivity, thermal and chemical stability, low density, and availability. These superior properties make them ideal for diverse applications. Doping these carbon nanostructures holds promise of designing the properties of these structures and opening the door to practical applications. Herein, we report the preparation of hollow N-doped mesoporous carbon (HMC) spheres fabricated via polymerization and carbonization of dopamine on a sacrificial spherical SiO(2) template that is removed upon hydrofluoric acid etching. The morphology and structural features of these HMCs were evaluated using scanning electron microscopy and transmission electron microscopy and the N-doping (7.1 at%) was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen reduction/evolution reaction (ORR/OER) performance of N-doped HMC was evaluated using rotating disk electrode (RDE) voltammetry in an alkaline electrolyte. N-doped HMC demonstrated a high ORR onset potential of -0.055 V (vs. Hg/HgO) and excellent stability. The outstanding bifunctional activity was implemented in a practical Zn-air battery (ZAB), which exhibited a small charge-discharge voltage polarization of 0.89 V and high stability over repeated cycling.

  15. Bifunctional fluoroionphore-ionic liquid hybrid for toxic heavy metal ions: improving its performance via the synergistic extraction strategy.

    Science.gov (United States)

    Jin, Zhen; Xie, De-Xun; Zhang, Xiao-Bing; Gong, Yi-Jun; Tan, Weihong

    2012-05-15

    Several heavy metal ions (HMIs), such as Cd(2+), Pb(2+), and Hg(2+), are highly toxic even at very low concentrations. Although a large number of fluoroionphores have been synthesized for HMIs, only a few of them show detection limits that are below the maximum contamination levels in drinking water (usually in the nM range), and few of them can simultaneously detect and remove HMIs. In this work, we report a new fluoroionphore-ionic liquid hybrid-based strategy to improve the performance of classic fluoroionphores via a synergistic extraction effect and realize simultaneous instrument-free detection and removal of HMIs. As a proof-of-concept, Hg(2+) was chosen as a model HMI, and a rhodamine thiospirolactam was chosen as a model fluoroionphore to construct bifunctional fluoroionphore-ionic liquid hybrid 1. The new sensing system could provide obviously improved sensitivity by simply increasing the aqueous-to-ionic liquid phase volume ratio to 10:1, resulting in a detection limit of 800 pM for Hg(2+), and afford extraction efficiencies larger than 99% for Hg(2+). The novel strategy provides a general platform for highly sensitive detection and removal of various HMIs in aqueous samples and holds promise for environmental and biomedical applications.

  16. Coordination Chemistry of Bifunctional Chemical Agents Designed for Applications in64Cu PET Imaging for Alzheimer's Disease.

    Science.gov (United States)

    Sharma, Anuj K; Schultz, Jason W; Prior, John T; Rath, Nigam P; Mirica, Liviu M

    2017-11-20

    Positron emission tomography (PET) is emerging as one of the most important diagnostic tools for brain imaging, yet the most commonly used radioisotopes in PET imaging, 11 C and 18 F, have short half-lives, and their usage is thus somewhat limited. By comparison, the 64 Cu radionuclide has a half-life of 12.7 h, which is ideal for administering and imaging purposes. In spite of appreciable research efforts, high-affinity copper chelators suitable for brain imaging applications are still lacking. Herein, we present the synthesis and characterization of a series of bifunctional compounds (BFCs) based on macrocyclic 1,4,7-triazacyclononane and 2,11-diaza[3.3](2,6)pyridinophane ligand frameworks that exhibit a high affinity for Cu 2+ ions. In addition, these BFCs contain a 2-phenylbenzothiazole fragment that is known to interact tightly with amyloid β fibrillar aggregates. Determination of the protonation constants (pK a values) and stability constants (log β values) of these BFCs, as well as characterization of the isolated copper complexes using X-ray crystallography, electron paramagnetic resonance spectroscopy, and electrochemical studies, suggests that these BFCs exhibit desirable properties for the development of novel 64 Cu PET imaging agents for Alzheimer's disease.

  17. 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.

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

    Science.gov (United States)

    Dang, Suying; Hong, Tao; Wisniewski, Thomas; Zhang, Wei

    2011-01-01

    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, pAPAC + 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.

  19. A Copper Porphyrin-Based Conjugated Mesoporous Polymer-Derived Bifunctional Electrocatalyst for Hydrogen and Oxygen Evolution.

    Science.gov (United States)

    Cui, Shengsheng; Qian, Manman; Liu, Xiang; Sun, Zijun; Du, Pingwu

    2016-09-08

    Scalable and robust catalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are required for the implementation of water splitting technologies as a globally applicable method of producing renewable hydrogen. Herein, we report nitrogen-enriched porous carbon materials containing copper/copper oxide, derived from copper porphyrin-based conjugated mesoporous polymers (CMPs), as a bifunctional catalyst for both HER and OER. These catalysts have a high surface area, unique tubular structure, and strong synergistic effect of copper/copper oxide and porous carbons, resulting in excellent performance for water splitting. Under optimal conditions, the catalyst exhibits a quite low overpotential for OER (350 mV to reach 1.0 mA cm(-2) and 450 mV to reach 10 mA cm(-2) ) in alkaline media, which places it among the best copper-based water oxidation catalysts reported in the literature. Furthermore, the catalyst shows good catalytic activity for HER at a low overpotential (190 mV to reach 1.0 mA cm(-2) ) as well as a high current density (470 mV to reach 50 mA cm(-2) ). The results suggest that hybridized copper/carbon materials are attractive noble-metal-free catalysts for water splitting. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Three-dimensional radial α-MnO2 synthesized from different redox potential for bifunctional oxygen electrocatalytic activities

    Science.gov (United States)

    Zheng, Xiaoying; Yu, Lin; Lan, Bang; Cheng, Gao; Lin, Ting; He, Binbin; Ye, Wenjin; Sun, Ming; Ye, Fei

    2017-09-01

    The morphology of manganese dioxides has great effects on their electrocatalytic activities. Herein, two different types of three-dimensional (3D) radial α-MnO2 (dandelion- and urchin-like) catalysts are readily fabricated via two different redox reactions through the hydrothermal method, and their electrocatalytic activities are studied for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). As a result, the dandelion-like α-MnO2 exhibits a higher electrocatalytic performance than urchin-like α-MnO2, with a lower overpotential (20 mV lower for ORR and 90 mV lower for OER), higher mass activity and lower Tafel slope. The excellent electrocatalytic activity of dandelion-like α-MnO2 can be attributed to its relatively larger BET and electrochemical active surface area, richer defects, higher amount of Mn3+, and less charge transfer resistance. Our results shed insights into developing new way in constructing the deficient α-MnO2 bifunctional oxygen electrocatalysts.

  1. Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting

    Science.gov (United States)

    Wang, Haotian; Lee, Hyun-Wook; Deng, Yong; Lu, Zhiyi; Hsu, Po-Chun; Liu, Yayuan; Lin, Dingchang; Cui, Yi

    2015-01-01

    Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (∼20 nm) are electrochemically transformed into ultra-small diameter (2–5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeOx nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm−2 water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts. PMID:26099250

  2. 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.

  3. Triphenyl borate as a bi-functional additive to improve surface stability of Ni-rich cathode material

    Science.gov (United States)

    Yim, Taeeun; Jang, Seol Heui; Han, Young-Kyu

    2017-12-01

    Nickel-rich cathode material has received marked attention as an advanced cathode material, however, its inferior surface property limits the achievement of high performance in lithium-ion batteries. We propose the use of a bi-functional additive of triphenyl borate (TPB) for improvement of the safety and electrochemical performance of Ni-rich cathode materials. First, TPB removes residual lithium species from the Ni-rich cathode surface via chemical binding with anion part of residual lithium species, and effectively reduces swelling behavior of the cell. Second, TPB creates effective cathode-electrolyte interphase (CEI) layers on the electrode surface by an electrochemical reaction, and greatly enhances the surface stability of the nickel-rich cathode. This work demonstrate that a cell cycled with the TPB additive exhibits a remarkable retention of 88.6% at 60 °C after 100 cycles for an NCM721 cathode material. We suggest a working mechanism for TPB based on systematic analyses, including in-situ and ex-situ experiments.

  4. 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.)

  5. 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.

  6. A nanotherapy strategy significantly enhances anticryptosporidial activity of an inhibitor of bifunctional thymidylate synthase-dihydrofolate reductase from Cryptosporidium.

    Science.gov (United States)

    Mukerjee, Anindita; Iyidogan, Pinar; Castellanos-Gonzalez, Alejandro; Cisneros, José A; Czyzyk, Daniel; Ranjan, Amalendu Prakash; Jorgensen, William L; White, A Clinton; Vishwanatha, Jamboor K; Anderson, Karen S

    2015-01-01

    Cryptosporidiosis, a gastrointestinal disease caused by protozoans of the genus Cryptosporidium, is a common cause of diarrheal diseases and often fatal in immunocompromised individuals. Bifunctional thymidylate synthase-dihydrofolate reductase (TS-DHFR) from Cryptosporidium hominis (C. hominis) has been a molecular target for inhibitor design. C. hominis TS-DHFR inhibitors with nM potency at a biochemical level have been developed however drug delivery to achieve comparable antiparasitic activity in Cryptosporidium infected cell culture has been a major hurdle for designing effective therapies. Previous mechanistic and structural studies have identified compound 906 as a nM C. hominis TS-DHFR inhibitor in vitro, having μM antiparasitic activity in cell culture. In this work, proof of concept studies are presented using a nanotherapy approach to improve drug delivery and the antiparasitic activity of 906 in cell culture. We utilized PLGA nanoparticles that were loaded with 906 (NP-906) and conjugated with antibodies to the Cryptosporidium specific protein, CP2, on the nanoparticle surface in order to specifically target the parasite. Our results indicate that CP2 labeled NP-906 (CP2-NP-906) reduces the level of parasites by 200-fold in cell culture, while NP-906 resulted in 4.4-fold decrease. Moreover, the anticryptosporidial potency of 906 improved 15 to 78-fold confirming the utility of the antibody conjugated nanoparticles as an effective drug delivery strategy. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. 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

  8. 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.

  9. Revisiting the Nucleotide and Aminoglycoside Substrate Specificity of the Bifunctional Aminoglycoside Acetyltransferase(6′)-Ie/Aminoglycoside Phosphotransferase(2″)-Ia Enzyme*

    Science.gov (United States)

    Frase, Hilary; Toth, Marta; Vakulenko, Sergei B.

    2012-01-01

    The bifunctional aminoglycoside-modifying enzyme aminoglycoside acetyltransferase(6′)-Ie/aminoglycoside phosphotransferase(2″)-Ia, or AAC(6′)-Ie/APH(2″)-Ia, is the major source of aminoglycoside resistance in Gram-positive bacterial pathogens. In previous studies, using ATP as the cosubstrate, it was reported that the APH(2″)-Ia domain of this enzyme is unique among aminoglycoside phosphotransferases, having the ability to inactivate an unusually broad spectrum of aminoglycosides, including 4,6- and 4,5-disubstituted and atypical. We recently demonstrated that GTP, and not ATP, is the preferred cosubstrate of this enzyme. We now show, using competition assays between ATP and GTP, that GTP is the exclusive phosphate donor at intracellular nucleotide levels. In light of these findings, we reevaluated the substrate profile of the phosphotransferase domain of this clinically important enzyme. Steady-state kinetic characterization using the phosphate donor GTP demonstrates that AAC(6′)-Ie/APH(2″)-Ia phosphorylates 4,6-disubstituted aminoglycosides with high efficiency (kcat/Km = 105-107 m−1 s−1). Despite this proficiency, no resistance is conferred to some of these antibiotics by the enzyme in vivo. We now show that phosphorylation of 4,5-disubstituted and atypical aminoglycosides are negligible and thus these antibiotics are not substrates. Instead, these aminoglycosides tend to stimulate an intrinsic GTPase activity of the enzyme. Taken together, our data show that the bifunctional enzyme efficiently phosphorylates only 4,6-disubstituted antibiotics; however, phosphorylation does not necessarily result in bacterial resistance. Hence, the APH(2″)-Ia domain of the bifunctional AAC(6′)-Ie/APH(2″)-Ia enzyme is a bona fide GTP-dependent kinase with a narrow substrate profile, including only 4,6-disubstituted aminoglycosides. PMID:23115238

  10. CO2capture performance of bi-functional activated bleaching earth modified with basic-alcoholic solution and functionalization with monoethanolamine: isotherms, kinetics and thermodynamics.

    Science.gov (United States)

    Pongstabodee, Sangobtip; Pornaroontham, Phuwadej; Pintuyothin, Nuthapol; Pootrakulchote, Nuttapol; Thouchprasitchai, Nutthavich

    2016-10-01

    CO 2 capture performance of bifunctional activated bleaching earth (ABE) was investigated at atmospheric pressure. The sorbents were characterized by means of X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Caron-Hydrogen-Nitrogen analysis (CHN), Fourier transform infrared (FT-IR) and thermal gravimetric analysis (TGA). The CO 2 capacity was enhanced via basic-modification and monoethanolamine (MEA) loading of the ABE sorbent to obtain a bifunctional surface property. Here, basic-modified calcined ABE with a 30wt.% MEA loading (SAB-30) showed the highest CO 2 capture capacity, but this was decreased with excess MEA loading (>30wt.%). At a 10% (V/V) initial CO 2 concentration feed, the maximum capacity of SAB-30 increased from 2.71mmol/g at 30°C (without adding moisture to the feed) to 3.3mmol/g at 50°C when adding 10% (V/V) moisture to the feed. Increasing the moisture concentration further reduced the maximum CO 2 capacity due to the blocking effect of the excess moisture on the sorbent surface. However, SAB-30 could completely capture CO 2 even in a 100% (V/V) initial CO 2 concentration feed. A maximum CO 2 capacity of 5.7mmol/g for SAB-30 was achieved at 30°C. Varying the ratio of sorbent weight to total flow rate of the gas stream had no discernible effect on the equilibrium CO 2 capture capacity. Avrami's equation and Toth's isotherm model provided a good fitting for the data and suggested the presence of more than one reaction pathway in the CO 2 capture process and the heterogeneous adsorption surface of SAB-30. Thermodynamics studies revealed that CO 2 capture on the bifunctional SAB-30 is feasible, spontaneous and exothermic in nature. Copyright © 2016. Published by Elsevier B.V.

  11. Radioiodinating of protein using 2, 3, 5, 6-tetrafluorophenyl 3-(nodo-carboranyl) propionate (TCP) as a new bi-functional linker: synthesis and biodistribution in mice

    International Nuclear Information System (INIS)

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

    2008-01-01

    An active ester, 2, 3, 5, 6-tetrafluorophenyl 3-(nodo-carboranyl) propionate (TCP), was proposed as a pendant group for labeling proteins with suitable radionuclide for radionuclide therapy. In this paper, TCP, a new potential bi-functional linker for radioiodination of proteins or peptides, was synthesized. Then, the first attempt to conjugate bovine serum albumin (BSA) with 125 I via this bi-functional linker was made. The results showed that BSA could be conjugated with 125 I using TCP as the linker in a labeling yield of 58.3-65.8%%, and with radiochemical purity nearly of 100% after purification by Sephadex TM G-50. Even kept at room temperature for 72 hours, the radiochemical purity of 125 I-TCP-BSA was still more than 98%, much higher than that with the direct labeled BSA ( 125 I-BSA, 81.1%), implying that the conjugated BSA was fairly stable in vitro. Biodistribution of 125 I-TCP-BSA in mice suggested that 125 I accumulated mainly in liver post injection, with the maximum uptake of 11.42%I.D./g at 8 h, and mainly excreted by kidney. However, the uptake of 125 I in mice for 125 I-TCP-BSA in some key organs, especially in thyroid, stomach, lung and spleen were much less than that with the direct labeled BSA ( 125 I-BSA) and that of free iodine-125( 125 I - ). Additionally, it was noted that 125 I-TCP-BSA has much better in vivo stability than 125 I-BSA. This result indicated that 125 I-TCP-BSA has considerable stability in vivo as well as in vitro, and thus TCP could be used as a bi-functional linker for labeling proteins. (authors)

  12. 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

  13. 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.

  14. 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.

  15. Bifunctional star-burst amorphous molecular materials for OLEDs: achieving highly efficient solid-state luminescence and carrier transport induced by spontaneous molecular orientation.

    Science.gov (United States)

    Kim, Jun Yun; Yasuda, Takuma; Yang, Yu Seok; Adachi, Chihaya

    2013-05-21

    Bifunctional star-burst amorphous molecular materials displaying both efficient solid-state luminescence and high hole-transport properties are developed in this study. A high external electroluminescence quantum efficiency up to 5.9% is attained in OLEDs employing the developed amorphous materials. It is revealed that the spontaneous horizontal orientation of these light-emitting molecules in their molecular-condensed states leads to a remarkable enhancement of the electroluminescence efficiencies and carrier-transport properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. 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.

  17. 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.

  18. 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.

  19. The role of the methyltransferase domain of bifunctional restriction enzyme RM.BpuSI in cleavage activity.

    Directory of Open Access Journals (Sweden)

    Arthur Sarrade-Loucheur

    Full Text Available Restriction enzyme (REase RM.BpuSI can be described as a Type IIS/C/G REase for its cleavage site outside of the recognition sequence (Type IIS, bifunctional polypeptide possessing both methyltransferase (MTase and endonuclease activities (Type IIC and endonuclease activity stimulated by S-adenosyl-L-methionine (SAM (Type IIG. The stimulatory effect of SAM on cleavage activity presents a major paradox: a co-factor of the MTase activity that renders the substrate unsusceptible to cleavage enhances the cleavage activity. Here we show that the RM.BpuSI MTase activity modifies both cleavage substrate and product only when they are unmethylated. The MTase activity is, however, much lower than that of M1.BpuSI and is thought not to be the major MTase for host DNA protection. SAM and sinefungin (SIN increase the Vmax of the RM.BpuSI cleavage activity with a proportional change in Km, suggesting the presence of an energetically more favorable pathway is taken. We further showed that RM.BpuSI undergoes substantial conformational changes in the presence of Ca(2+, SIN, cleavage substrate and/or product. Distinct conformers are inferred as the pre-cleavage/cleavage state (in the presence of Ca(2+, substrate or both and MTase state (in the presence of SIN and substrate, SIN and product or product alone. Interestingly, RM.BpuSI adopts a unique conformation when only SIN is present. This SIN-bound state is inferred as a branch point for cleavage and MTase activity and an intermediate to an energetically favorable pathway for cleavage, probably through increasing the binding affinity of the substrate to the enzyme under cleavage conditions. Mutation of a SAM-binding residue resulted in altered conformational changes in the presence of substrate or Ca(2+ and eliminated cleavage activity. The present study underscores the role of the MTase domain as facilitator of efficient cleavage activity for RM.BpuSI.

  20. Structural origins for the loss of catalytic activities of bifunctional human LTA4H revealed through molecular dynamics simulations.

    Directory of Open Access Journals (Sweden)

    Sundarapandian Thangapandian

    Full Text Available Human leukotriene A4 hydrolase (hLTA4H, which is the final and rate-limiting enzyme of arachidonic acid pathway, converts the unstable epoxide LTA4 to a proinflammatory lipid mediator LTB4 through its hydrolase function. The LTA4H is a bi-functional enzyme that also exhibits aminopeptidase activity with a preference over arginyl tripeptides. Various mutations including E271Q, R563A, and K565A have completely or partially abolished both the functions of this enzyme. The crystal structures with these mutations have not shown any structural changes to address the loss of functions. Molecular dynamics simulations of LTA4 and tripeptide complex structures with functional mutations were performed to investigate the structural and conformation changes that scripts the observed differences in catalytic functions. The observed protein-ligand hydrogen bonds and distances between the important catalytic components have correlated well with the experimental results. This study also confirms based on the structural observation that E271 is very important for both the functions as it holds the catalytic metal ion at its location for the catalysis and it also acts as N-terminal recognition residue during peptide binding. The comparison of binding modes of substrates revealed the structural changes explaining the importance of R563 and K565 residues and the required alignment of substrate at the active site. The results of this study provide valuable information to be utilized in designing potent hLTA4H inhibitors as anti-inflammatory agents.

  1. 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

  2. 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.

  3. Polyfunctional radiosensitizers-v. sensitization of hypoxic chinese hamster cells, V. 79-753B, in vitro by a series of bifunctional nitroxyl compounds

    International Nuclear Information System (INIS)

    Millar, B.C.; Jenkins, T.C.; Fielden, E.M.

    1982-01-01

    A homologous series of uncharged nitroxyl biradicals have been examined as hyposic cell sensitizers. In the series piperidinic nitroxyl moieties were separated by alkane-dicarboxamide bridging groups containing an increasing number (0 - 7) of methylene groups. In each instance sensitization was characterized by changes in both extrapolation number (n) and the slope of the hypoxic cell survival curve. Increasing the cell-drug contact time from 1 to 3 hr produced an increase in the slope of the survival curve. This was not always associated with a further decrease in n. The present data support the hypothesis that lack of interaction between the radical centers in these and other bifunctional nitroxyls is important for events leading to shoulder modification. The degree of interaction between the radical moieties was assessed from their ESR spectra in solution. In addition, comparison has been made between charged and uncharged forms of a bifunctional nitroxyl compound. In this instance a 3-hr cell-drug contact time in the presence of the uncharge compound resulted in an increase in both slope and n, whereas there was no change in n when cells were irradiated in the presence of the charged compound. When cells which had been preexposed for 3 hr to a biradical, RSU-4072, were irradiated in the presence of a mixture of the biradical and the monoradical TMPN, the survival parameters were characteristic of those seen for TMPN alone. The implications of these results are discussed

  4. 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.

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

    Science.gov (United States)

    Dub, Pavel A; Scott, Brian L; Gordon, John C

    2017-01-25

    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). 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. 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.

  6. 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.

  7. Cobalt Nanoparticle-Embedded Porous Carbon Nanofibers with Inherent N- and F-Doping as Binder-Free Bifunctional Catalysts for Oxygen Reduction and Evolution Reactions.

    Science.gov (United States)

    Singhal, Richa; Kalra, Vibha

    2017-01-18

    Efficient, low-cost, non-precious metal-based, and stable bifunctional electrocatalysts are key to various energy storage and conversion devices such as regenerative fuel cells and metal-air batteries. In this work, we report cobalt nanoparticle-embedded porous carbon nanofibers with inherent N- and F-doping as binder-free bifunctional electrocatalysts with excellent activity for both the oxygen reduction and oxygen evolution reaction (ORR/OER) in an alkaline medium. Single-step electrospinning of a solution of the polymer mixture (carbon precursor) and the cobalt precursor followed by controlled pyrolysis with an intermediate reduction step in H 2 (to reduce cobalt oxides to cobalt) was utilized to synthesize an integrated freestanding catalyst. The fabricated catalyst with effective structural and electronic interaction between the cobalt metal nanoparticles and the N- and F-doped carbon defect sites showed enhanced catalytic properties compared to the benchmark catalysts for ORR and OER (Pt, Ir, and Ru). The ORR potential at the current density of -3 mA cm -2 was 0.81 V RHE and the OER potential at a current density of 10 mA cm -2 was 1.595 V RHE , resulting in a ΔE of only 0.785 V. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Co3O4 nanoparticle-modified MnO2 nanotube bifunctional oxygen cathode catalysts for rechargeable zinc-air batteries

    Science.gov (United States)

    Du, Guojun; Liu, Xiaogang; Zong, Yun; Hor, T. S. Andy; Yu, Aishui; Liu, Zhaolin

    2013-05-01

    We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone.We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone. Electronic supplementary information (ESI) available: Zinc-air cell device, XPS survey scan and power density of the cell. See DOI: 10.1039/c3nr00300k

  9. Facile Synthesis ZnS/ZnO/Ni(OH)2Composites Grown on Ni Foam: A Bifunctional Materials for Photocatalysts and Supercapacitors.

    Science.gov (United States)

    Hao, Jin; Wang, Xiaobing; Liu, Fanggang; Han, Shuang; Lian, Jianshe; Jiang, Qing

    2017-06-08

    A facile one-step hydrothermal reaction was employed to synthesis an integrated bifunctional composite composed by a network structure of ZnS/ZnO/Ni(OH) 2 nanosheets with ZnS/ZnO nanospheres in situ growing on Ni foam. The synergistic effect of these three substances make the composite having both improved electrochemical performances and photocatalytic activity. The ZnS/ZnO/Ni(OH) 2 -4mmol shows a high specific capacitance of 1173.8 F g -1 at 1 A g -1 , as well as good rate capability and relatively stable cyclability. Using as photocatalyst, the methyl orange dye in solution can be completely decomposed under ultraviolet-visible radiation in about 80 min. And the composite is easy to be repeatedly used because bulk Ni foam was used as a carrier. Such a bifunctional composite material provides a new insight for energy storage and utilization as well as the water pollution treatment.

  10. 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.

  11. In Situ Derived CoB Nanoarray: A High-Efficiency and Durable 3D Bifunctional Electrocatalyst for Overall Alkaline Water Splitting.

    Science.gov (United States)

    Lu, Wenbo; Liu, Tingting; Xie, Lisi; Tang, Chun; Liu, Danni; Hao, Shuai; Qu, Fengli; Du, Gu; Ma, Yongjun; Asiri, Abdullah M; Sun, Xuping

    2017-08-01

    The development of efficient bifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of extreme importance for future renewable energy systems. This Communication reports the recent finding that room-temperature treatment of CoO nanowire array on Ti mesh by NaBH 4 in alkaline media leads to in situ development of CoB nanoparticles on nanowire surface. The resulting self-supported CoB@CoO nanoarray behaves as a 3D bifunctional electrocatalyst with high activity and durability for both HER (<17% current density degradation after 20 h electrolysis) and OER (<14% current density degradation after 20 h electrolysis) with the need of the overpotentials of 102 and 290 mV to drive 50 mA cm -2 in 1.0 m KOH, respectively. Moreover, its two-electrode alkaline water electrolyzer also shows remarkably high durability and only demands a cell voltage of 1.67 V to deliver 50 mA cm -2 water-splitting current with a current density retention of 81% after 20 h electrolysis. This work provides a promising methodology for the designing and fabricating of metal-boride based nanoarray as a high-active water-splitting catalyst electrode for applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Simplified synthesis of the bifunctional chelating agent 2-(4-aminobenzyl)-1,4,7,10-tetraazacyclododecane-N,N``,N```-tetraacetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, A.K.; Gestin, J.F.; Benoist, E.; Faivre-Chauvet, A.; Chatal, J.F. [INSERM, 44 Nantes (France)

    1996-05-01

    The attachment of metal ions to antibodies by means of bifunctional chelating agents (BCA) for medical applications requires extremely high stability under physiological conditions, with no significant release of metals. Chelators that bind strongly with radio-metals like {sup 111}In, {sup 67}Ga, {sup 90} Y, and {sup 153} Sm, giving complexes that are highly stable under these conditions are essential for effective radioimmunotherapy, for tumor imaging or immunoscintigraphy. 2-(4-Nitrobenzyl)-1,4,7,10-tetraazacyclodecane-N, N`, N``, N``` -tetraacetic acid (nitrobenzyl-DOTA) is one of the most promising BCA. A convenient synthesis of 4-nitrobenzyl-substituted DOTA and its conversion to bifunctional chelating agents is described here. The process involves the reaction of a bisbromoamide with a p-nitrobenzyl ethylenediamine followed by reduction of the cyclic diamide. The bis-bromoamide resembles a crab with two reactive organo-bromide groups poised and ready to react, hence the term ``crab-like`` cyclization. The overall yield for the six-step synthesis sequence starting form p-nitrobenzyl ethylenediamine is 21.27 %. (authors). 14 refs., 1 fig.

  13. 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)

  14. Detection of amyloid plaques targeted by bifunctional USPIO in Alzheimer's disease transgenic mice using magnetic resonance microimaging.

    Directory of Open Access Journals (Sweden)

    Youssef Zaim Wadghiri

    Full Text Available Amyloid plaques are a key pathological hallmark of Alzheimer's disease (AD. The detection of amyloid plaques in the brain is important for the diagnosis of AD, as well as for following potential amyloid targeting therapeutic interventions. Our group has developed several contrast agents to detect amyloid plaques in vivo using magnetic resonance microimaging (µMRI in AD transgenic mice, where we used mannitol to enhance blood brain barrier (BBB permeability. In the present study, we used bifunctional ultrasmall superparamagnetic iron oxide (USPIO nanoparticles, chemically coupled with Aβ1-42 peptide to image amyloid plaque deposition in the mouse brain. We coupled the nanoparticles to polyethylene glycol (PEG in order to improve BBB permeability. These USPIO-PEG-Aβ1-42 nanoparticles were injected intravenously in AD model transgenic mice followed by initial in vivo and subsequent ex vivo μMRI. A 3D gradient multi-echo sequence was used for imaging with a 100 µm isotropic resolution. The amyloid plaques detected by T2*-weighted μMRI were confirmed with matched histological sections. The region of interest-based quantitative measurement of T2* values obtained from the in vivo μMRI showed contrast injected AD Tg mice had significantly reduced T2* values compared to wild-type mice. In addition, the ex vivo scans were examined with voxel-based analysis (VBA using statistical parametric mapping (SPM for comparison of USPIO-PEG-Aβ1-42 injected AD transgenic and USPIO alone injected AD transgenic mice. The regional differences seen by VBA in the USPIO-PEG-Aβ1-42 injected AD transgenic correlated with the amyloid plaque distribution histologically. Our results indicate that USPIO-PEG-Aβ1-42 can be used for amyloid plaque detection in vivo by intravenous injection without the need to co-inject an agent which increases permeability of the BBB. This technique could aid the development of novel amyloid targeting drugs by allowing therapeutic effects

  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. Persistence and Repair of Bifunctional DNA Adducts in Tissues of Laboratory Animals Exposed to 1,3-Butadiene by Inhalation

    Science.gov (United States)

    Goggin, Melissa; Sangaraju, Dewakar; Walker, Vernon E.; Wickliffe, Jeffrey; Swenberg, James A.; Tretyakova, Natalia

    2011-01-01

    1,3-butadiene (BD) is an important industrial and environmental chemical classified as a human carcinogen. The mechanism of BD-mediated cancer is of significant interest because of the widespread exposure of humans to BD from cigarette smoke and urban air. BD is metabolically activated to 1,2,3,4-diepoxybutane (DEB), which is a highly genotoxic and mutagenic bis-alkylating agent believed to be the ultimate carcinogenic species of BD. We have previously identified several types of DEB-specific DNA adducts, including bis-N7-guanine cross-links (bis-N7-BD), N6-adenine-N7-guanine cross-links (N6A-N7G-BD), and 1,N6-dA exocyclic adducts. These lesions were detected in tissues of laboratory rodents exposed to BD by inhalation (Goggin et al. Cancer Res. 2009;69:2479–2486). In the present work, persistence and repair of bifunctional DEB-DNA adducts in tissues of mice and rats exposed to BD by inhalation were investigated. The half-lives of the most abundant cross-links, bis-N7G-BD, in mouse liver, kidney, and lungs were 2.3–2.4 days, 4.6–5.7 days, and 4.9 days, respectively. The in vitro half-lives of bis-N7G-BD were 3.5 days (S,S isomer) and 4.0 days (meso isomer) due to their spontaneous depurination. In contrast, tissue concentrations of the minor DEB adducts, N7G-N1A-BD and 1,N6-HMHP-dA, remained essentially unchanged during the course of the experiment, with an estimated t 1/2 of 36–42 days. No differences were observed between DEB-DNA adduct levels in BD-treated wild type mice and the corresponding animals deficient in methyl purine glycosylase or the Xpa gene. Our results indicate that DEB-induced N7G-N1A-BD and 1,N6-HMHP-dA adducts persist in vivo, potentially contributing to mutations and cancer observed as a result of BD exposure. PMID:21452897

  17. 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.

  18. 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.).

  19. 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

  20. 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.

  1. Enhancement of Bacillus thuringiensis insecticidal activity by combining Cry1Ac and bi-functional toxin HWTX-XI from spider.

    Science.gov (United States)

    Sun, Yunjun; Fu, Zujiao; He, Xiaohong; Yuan, Chunhua; Ding, Xuezhi; Xia, Liqiu

    2016-03-01

    In order to assess the potency of bi-functional HWTX-XI toxin from spider Ornithoctonus huwena in improving the insecticidal activity of Bacillus thuringiensis, a fusion gene of cry1Ac and hwtx-XI was constructed and expressed in an acrystalliferous B. thuringiensis strain Cry(-)B. Western blot analysis and microscopic observation revealed that the recombinant strain could express 140-kDa Cry1Ac-HWTX-XI fusion protein and produce parasporal inclusions during sporulation. Bioassay using the larvae of Helicoverpa armigera and Spodoptera exigua showed that the Cry1Ac-HWTX-XI fusion was more toxic than the control Cry1Ac protoxin, as revealed by 95% lethal concentration. Our study indicated that the HWTX-XI from spider might be a candidate for enhancing the toxicity of B. thuringiensis products. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. [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.

  3. 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.

  4. 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.

  5. Hierarchical nanostructured NiCo2O4 as an efficient bifunctional non-precious metal catalyst for rechargeable zinc-air batteries

    Science.gov (United States)

    Prabu, Moni; Ketpang, Kriangsak; Shanmugam, Sangaraju

    2014-02-01

    A nickel-doped cobalt oxide spinel structure is a promising non-precious metal electrocatalyst for oxygen evolution and oxygen reduction in rechargeable metal-air batteries and water electrolyzers operating with alkaline electrolytes. One dimensional NiCo2O4 (NCO) nanostructures were prepared by using a simple electrospinning technique with two different metal precursors (metal nitrate/PAN and metal acetylacetonate/PAN). The effect of precursor concentration on the morphologies was investigated. Single-phase, NCO with an average diameter of 100 nm, porous interconnected fibrous morphology was revealed by FESEM and FETEM analysis. The hierarchical nanostructured 1D-spinel NiCo2O4 materials showed a remarkable electrocatalytic activity towards oxygen reduction and evolution in an aqueous alkaline medium. The extraordinary bi-functional catalytic activity towards both ORR and OER was observed by the low over potential (0.84 V), which is better than that of noble metal catalysts [Pt/C (1.16 V), Ru/C (1.01 V) and Ir/C (0.92 V)], making them promising cathode materials for metal-air batteries. Furthermore, the rechargeable zinc-air battery with NCO-A1 as a bifunctional electrocatalyst displays high activity and stability during battery discharge, charge, and cycling processes.A nickel-doped cobalt oxide spinel structure is a promising non-precious metal electrocatalyst for oxygen evolution and oxygen reduction in rechargeable metal-air batteries and water electrolyzers operating with alkaline electrolytes. One dimensional NiCo2O4 (NCO) nanostructures were prepared by using a simple electrospinning technique with two different metal precursors (metal nitrate/PAN and metal acetylacetonate/PAN). The effect of precursor concentration on the morphologies was investigated. Single-phase, NCO with an average diameter of 100 nm, porous interconnected fibrous morphology was revealed by FESEM and FETEM analysis. The hierarchical nanostructured 1D-spinel NiCo2O4 materials showed a

  6. Active Salt/Silica-Templated 2D Mesoporous FeCo-Nx-Carbon as Bifunctional Oxygen Electrodes for Zinc-Air Batteries.

    Science.gov (United States)

    Li, Shuang; Cheng, Chong; Zhao, Xiaojia; Schmidt, Johannes; Thomas, Arne

    2018-02-12

    Two types of templates, an active metal salt and silica nanoparticles, are used concurrently to achieve the facile synthesis of hierarchical meso/microporous FeCo-N x -carbon nanosheets (meso/micro-FeCo-N x -CN) with highly dispersed metal sites. The resulting meso/micro-FeCo-N x -CN shows high and reversible oxygen electrocatalytic performances for both ORR and OER, thus having potential for applications in rechargeable Zn-air battery. Our approach creates a new pathway to fabricate 2D meso/microporous structured carbon architectures for bifunctional oxygen electrodes in rechargeable Zn-air battery as well as opens avenues to the scale-up production of rationally designed heteroatom-doped catalytic materials for a broad range of applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 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)

  8. 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.

  9. Facile synthesis of chiral spirooxindole-based isotetronic acids and 5-1H-pyrrol-2-ones through cascade reactions with bifunctional organocatalysts.

    Science.gov (United States)

    Guo, Wengang; Wang, Xu; Zhang, Boyu; Shen, Shuai; Zhou, Xin; Wang, Peng; Liu, Yan; Li, Can

    2014-07-07

    Unprecedented organocatalyzed asymmetric cascade reactions have been developed for the facile synthesis of chiral spirooxindole-based isotetronic acids and 5-1H-pyrrol-2-ones.The asymmetric 1,2-addition reactions of α-ketoesters to isatins and imines by using an acid-base bifunctional 6'-OH cinchona alkaloid catalyst, followed by cyclization and enolization of the resulting adducts, gave chiral spiroisotetronic acids and 5-1H-pyrrol-2-ones, respectively, in excellent optical purities (up to 98 % ee). FT-IR analysis supported the existence of hydrogen-bonding interaction between the 6'-OH group of the cinchona catalyst and an isatin carbonyl group, an interaction that might be crucial for catalyst activity and stereocontrol. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Structure of the bifunctional aminoglycoside-resistance enzyme AAC(6')-Ie-APH(2'')-Ia revealed by crystallographic and small-angle X-ray scattering analysis.

    Science.gov (United States)

    Smith, Clyde A; Toth, Marta; Weiss, Thomas M; Frase, Hilary; Vakulenko, Sergei B

    2014-10-01

    Broad-spectrum resistance to aminoglycoside antibiotics in clinically important Gram-positive staphylococcal and enterococcal pathogens is primarily conferred by the bifunctional enzyme AAC(6')-Ie-APH(2'')-Ia. This enzyme possesses an N-terminal coenzyme A-dependent acetyltransferase domain [AAC(6')-Ie] and a C-terminal GTP-dependent phosphotransferase domain [APH(2'')-Ia], and together they produce resistance to almost all known aminoglycosides in clinical use. Despite considerable effort over the last two or more decades, structural details of AAC(6')-Ie-APH(2'')-Ia have remained elusive. In a recent breakthrough, the structure of the isolated C-terminal APH(2'')-Ia enzyme was determined as the binary Mg2GDP complex. Here, the high-resolution structure of the N-terminal AAC(6')-Ie enzyme is reported as a ternary kanamycin/coenzyme A abortive complex. The structure of the full-length bifunctional enzyme has subsequently been elucidated based upon small-angle X-ray scattering data using the two crystallographic models. The AAC(6')-Ie enzyme is joined to APH(2'')-Ia by a short, predominantly rigid linker at the N-terminal end of a long α-helix. This α-helix is in turn intrinsically associated with the N-terminus of APH(2'')-Ia. This structural arrangement supports earlier observations that the presence of the intact α-helix is essential to the activity of both functionalities of the full-length AAC(6')-Ie-APH(2'')-Ia enzyme.

  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. Ultrafast synthesis of bifunctional Er3+/Yb3+-codoped NaBiF4 upconverting nanoparticles for nanothermometer and optical heater.

    Science.gov (United States)

    Du, Peng; Luo, Laihui; Huang, Xiaoyong; Yu, Jae Su

    2018-03-15

    We reported a simple and ultrafast route to synthesize the bifunctional Er 3+ /Yb 3+ -codoped NaBiF 4 upconverting nanoparticles. It was found that the phase composition and microstructure of the prepared samples were strongly dependent on the NH 4 F content. When the NH 4 F content was 14 mmol, after 1 min reaction at room temperature, the resultant compounds exhibited pure single phase and were composed of uniform spherical nanoparticles. Under 980 nm light irradiation, the synthesized nanoparticles emitted visible emissions originating from the intra-4f transitions of Er 3+ ions and the involved upconversion luminescence mechanism was associated with the typical two-photon process. With the aid of the fluorescence intensity ratio technique, the optical thermometric behaviors of the studied nanoparticle based on the ( 2 H 11/2 , 4 S 3/2 ) thermally-coupled levels in the temperature range of 303-483 K were systematically analyzed and the maximum sensor sensitivity was determined to be about 0.0057 K -1 at 483 K. Furthermore, the internal heating properties of the resultant nanoparticles induced by the laser power source were also studied. With elevating the pump power from 159 to 658 mW, the temperature of the upconverting nanoparticles was improved from 304 to 464 K. These results suggest that the Er 3+ /Yb 3+ -codoped NaBiF 4 upconverting nanoparticles are promising bifunctional luminescent materials for nanothermometer and optical heater applications. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. 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.

  14. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst.

    Science.gov (United States)

    Yang, Hong Bin; Miao, Jianwei; Hung, Sung-Fu; Chen, Jiazang; Tao, Hua Bing; Wang, Xizu; Zhang, Liping; Chen, Rong; Gao, Jiajian; Chen, Hao Ming; Dai, Liming; Liu, Bin

    2016-04-01

    Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical to renewable energy conversion and storage technologies. Heteroatom-doped carbon nanomaterials have been reported to be efficient metal-free electrocatalysts for ORR in fuel cells for energy conversion, as well as ORR and OER in metal-air batteries for energy storage. We reported that metal-free three-dimensional (3D) graphene nanoribbon networks (N-GRW) doped with nitrogen exhibited superb bifunctional electrocatalytic activities for both ORR and OER, with an excellent stability in alkaline electrolytes (for example, KOH). For the first time, it was experimentally demonstrated that the electron-donating quaternary N sites were responsible for ORR, whereas the electron-withdrawing pyridinic N moieties in N-GRW served as active sites for OER. The unique 3D nanoarchitecture provided a high density of the ORR and OER active sites and facilitated the electrolyte and electron transports. As a result, the as-prepared N-GRW holds great potential as a low-cost, highly efficient air cathode in rechargeable metal-air batteries. Rechargeable zinc-air batteries with the N-GRW air electrode in a two-electrode configuration exhibited an open-circuit voltage of 1.46 V, a specific capacity of 873 mAh g(-1), and a peak power density of 65 mW cm(-2), which could be continuously charged and discharged with an excellent cycling stability. Our work should open up new avenues for the development of various carbon-based metal-free bifunctional electrocatalysts of practical significance.

  15. 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.

  16. Bifunctional ADP-dependent phosphofructokinase/glucokinase activity in the order Methanococcales--biochemical characterization of the mesophilic enzyme from Methanococcus maripaludis.

    Science.gov (United States)

    Castro-Fernandez, Victor; Bravo-Moraga, Felipe; Herrera-Morande, Alejandra; Guixe, Victoria

    2014-04-01

    In some archaea, the phosphorylation of glucose and fructose 6-phosphate (fructose 6P) is carried out by enzymes that are specific for either substrate and that use ADP as phosphoryl donor. In the hyperthermophilic archaeon Methanocaldococcus jannaschii, a bifunctional enzyme able to phosphorylate glucose and fructose 6P has been described. To determine whether the ability to phosphorylate both glucose and fructose 6P is a common feature for all enzymes of the order Methanococcales, we expressed, purified and characterized the unique homologous protein of the mesophilic archaea Methanococcus maripaludis. Assay of the enzyme activity with different sugars, metals and nucleotides allows us to conclude that the enzyme is able to phosphorylate both fructose 6P and glucose in the presence of ADP and a divalent metal cation. Kinetic characterization of the enzyme revealed complex regulation by the free Mg(2+) concentration and AMP, with the latter appearing to be a key metabolite. To determine whether this enzyme could have a role in gluconeogenesis, we evaluated the reversibility of both reactions and found that glucokinase activity is reversible, whereas phosphofructokinase activity is not. To determine the important residues for glucose and fructose 6P binding, we modeled the bifunctional phosphofructokinase/glucokinase enzyme from M. maripaludis and its interactions with both sugar substrates using protein–ligand docking. Comparison of the active site of the phosphofructokinase/glucokinase enzyme from M. maripaludis with the structural models constructed for all the homology sequences present in the order Methanococcales shows that all of the ADP-dependent kinases from this order would be able to phosphorylate glucose and fructose 6P, which rules out the current annotation of these enzymes as specific phosphofructokinases.

  17. Adenosine-5′-phosphosulfate – a multifaceted modulator of bifunctional 3′-phospho-adenosine-5′-phosphosulfate synthases and related enzymes

    Science.gov (United States)

    Mueller, Jonathan W; Shafqat, Naeem

    2013-01-01

    All sulfation reactions rely on active sulfate in the form of 3′-phospho-adenosine-5′-phosphosulfate (PAPS). In fungi, bacteria, and plants, the enzymes responsible for PAPS synthesis, ATP sulfurylase and adenosine-5′-phosphosulfate (APS) kinase, reside on separate polypeptide chains. In metazoans, however, bifunctional PAPS synthases catalyze the consecutive steps of sulfate activation by converting sulfate to PAPS via the intermediate APS. This intricate molecule and the related nucleotides PAPS and 3′-phospho-adenosine-5′-phosphate modulate the function of various enzymes from sulfation pathways, and these effects are summarized in this review. On the ATP sulfurylase domain that initially produces APS from sulfate and ATP, APS acts as a potent product inhibitor, being competitive with both ATP and sulfate. For the APS kinase domain that phosphorylates APS to PAPS, APS is an uncompetitive substrate inhibitor that can bind both at the ATP/ADP-binding site and the PAPS/APS-binding site. For human PAPS synthase 1, the steady-state concentration of APS has been modelled to be 1.6 μm, but this may increase up to 60 μm under conditions of sulfate excess. It is noteworthy that the APS concentration for maximal APS kinase activity is 15 μm. Finally, we recognized APS as a highly specific stabilizer of bifunctional PAPS synthases. APS most likely stabilizes the APS kinase part of these proteins by forming a dead-end enzyme–ADP–APS complex at APS concentrations between 0.5 and 5 μm; at higher concentrations, APS may bind to the catalytic centers of ATP sulfurylase. Based on the assumption that cellular concentrations of APS fluctuate within this range, APS can therefore be regarded as a key modulator of PAPS synthase functions. PMID:23517310

  18. 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.

  19. Expression of the bifunctional Bacillus subtilis TatAd protein in Escherichia coli reveals distinct TatA/B-family and TatB-specific domains.

    Science.gov (United States)

    Barnett, James P; Lawrence, Janna; Mendel, Sharon; Robinson, Colin

    2011-08-01

    In the Tat protein export pathway of Gram-negative bacteria, TatA and TatB are homologous proteins that carry out distinct and essential functions in separate sub-complexes. In contrast, Gram-positive Tat systems usually lack TatB and the TatA protein is bifunctional. We have used a mutagenesis approach to delineate TatA/B-type domains in the bifunctional TatAd protein from Bacillus subtilis. This involved expression of mutated TatAd variants in Escherichia coli and tests to determine whether the variants could function as TatA or TatB by complementing E. coli tatA and/or tatB mutants. We show that mutations in the C-terminal half of the transmembrane span and the subsequent FGP 'hinge' motif are critical for TatAd function with its partner TatCd subunit, and the same determinants are required for complementation of either tatA or tatB mutants in Escherichia coli. This is thus a critical domain in both TatA and TatB proteins. In contrast, substitution of a series of residues at the N-terminus specifically blocks the ability of TatAd to substitute for E. coli TatB. The results point to the presence of a universally conserved domain in the TatA/B-family, together with a separate N-terminal domain that is linked to the TatB-type function in Gram-negative bacteria.

  20. 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.

  1. Utilization of specific and non-specific peptide interactions with inorganic nanomaterials on the surface of bacteriophage M13: Methodologies towards phage supported bi-functional materials

    Science.gov (United States)

    Avery, Kendra Nicole

    Many types of organisms create a variety of nano and micro scale materials from precursors available in their surrounding environments by a process called biomineralization. As scientists begin to understand how these organisms utilize specific and non-specific interactions with a variety of biopolymers such as chitin, peptides, proteins and nucleic acids with these precursors to create inorganic/organic composite materials, they have begun to wonder about the synthesis of other types of non-biologically templated synthetic techniques that might be possible. Bioengineered organisms and biopolymers have begun to be used for these types of studies. A variety of selection techniques exist for discovering biopolymers with an affinity for a target material, however, one of the most notable is a technique called peptide phage display. This is a technique that utilizes a commercially available randomized peptide library attached at the tip of the filamentous bacteriophage M13. In this dissertation capabilities of bacteriophage M13 are explored in regard to the creation of bi-functional nano materials by exploiting both specific peptide interactions as well as non-specific peptide interactions on the surface of the organism. Chapter 2 focuses on utilizing the specific peptide interactions of the randomized library at pIII in order to discover peptides with high binding affinity for a variety of nanomaterials. Selection studies called biopanning are performed on a variety of nanomaterials such as CaMoO4, allotropes of Ni, Fe2O3 and Fe3O4, and Rh and Pt with the fcc type crystal structure. Similarities and differences between peptides discovered for these materials are discussed. Chapter 3 focuses on utilizing the non-specific peptide interactions on the long axis of M13 called pVIII. The pVIII region consists of 2700 copies of the same 50 amino acid protein which as a negatively charged domain which is exposed to solution. The pVIII region therefore provides the surface of

  2. 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.

  3. 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

  4. Morphology Control of Carbon-Free Spinel NiCo2O4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media.

    Science.gov (United States)

    Devaguptapu, Surya V; Hwang, Sooyeon; Karakalos, Stavros; Zhao, Shuai; Gupta, Shiva; Su, Dong; Xu, Hui; Wu, Gang

    2017-12-27

    Spinel NiCo 2 O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2 O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods followed by calcination. Whereas the hard-template yields spherelike dense structures, soft-template assists the formation of a unique nanoneedle cluster assembly containing abundant meso- and macropores. Furthermore, the effect of morphology of NiCo 2 O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flowerlike nanoneedle assembly NiCo 2 O 4 catalyst via the soft-template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V versus reversible hydrogen electrode, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2 O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20 000 potential cycles (0-1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust three-dimensional architecture with increased surface areas and enhanced mass transfer. Importantly, the soft template can yield a high degree of spinel crystallinity with ideal

  5. 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

  6. In vitro and in vivo evaluation of the bifunctional chelator NODIA-Me in combination with a prostate-specific membrane antigen targeting vector.

    Science.gov (United States)

    Läppchen, Tilman; Kiefer, Yvonne; Holland, Jason P; Bartholomä, Mark D

    2018-03-10

    We recently developed a chelating platform based on the macrocycle 1,4,7-triazacyclononane with up to three five-membered azaheterocyclic arms for complexation of the PET nuclides gallium-68 and copper-64. The main objective of this study was to evaluate the stability and pharmacokinetics of 68 Ga- and 64 Cu-complexes of the bifunctional chelator NODIA-Me 1 covalently bound to a PSMA targeting vector in vivo. NODIA-Me 1 was conjugated to the PSMA targeting Glu-NH-CO-NH-Lys moiety to give the bioconjugate NODIA-Me-NaI-Ahx-PSMA 4. The stability of [ 68 Ga]4 and [ 64 Cu]4 was assessed in vitro by serum stability studies. The PSMA binding affinity was determined in competitive cell experiments in LNCaP cells using 68 Ga-PSMA-HBED-CC as radioligand. The stability and pharmacokinetics of [ 68 Ga]4 and [ 64 Cu]4 was evaluated by PET imaging and ex vivo biodistribution studies in mice bearing subcutaneous LNCaP tumors. In human serum, [ 68 Ga]4 and [ 64 Cu]4 remained intact to 85% (3 h) and 92% (24 h), respectively. Nature of the metal chelate influenced PSMA binding affinity with IC 50 of 233 ± 10 nM for uncomplexed 4, 681 ± 7 nM for Cu-4 and 176 ± 10 nM for Ga-4. In animal studies, [ 68 Ga]4 and [ 64 Cu]4 revealed low uptake (≤1% IA g -1 ) in the majority of organs. Kidney uptake at 1 h p.i. was 6.28 ± 0.92% IA g -1 and 4.96 ± 0.79% IA g -1 and specific tumor uptake was 1.33 ± 0.46% IA g -1 and 2.15 ± 0.38% IA g -1 for [ 68 Ga]4 and [ 64 Cu]4, respectively. The bifunctional chelator NODIA-Me 1 was successfully conjugated to a PSMA targeting moiety. In small-animal PET imaging and ex vivo biodistribution studies, 68 Ga- and 64 Cu-labelled conjugates specifically delineated PSMA-positive LNCaP tumors and exhibited rapid renal clearance from non-target tissues with no significant demetallation/transchelation in vivo. The results support further development of this novel chelating platform for production of 68 Ga- and 64 Cu

  7. Cloning and analysis of a bifunctional methyltransferase/restriction endonuclease TspGWI, the prototype of a Thermus sp. enzyme family.

    Science.gov (United States)

    Zylicz-Stachula, Agnieszka; Bujnicki, Janusz M; Skowron, Piotr M

    2009-05-29

    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. 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. 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/E)XK nuclease domain related to the corresponding domains in HsdR subunits, but lacks the ATP-dependent translocase module of the HsdR subunit and the additional domains that

  8. 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

  9. Cellulose nanocrystals/ZnO as a bifunctional reinforcing nanocomposite for poly(vinyl alcohol)/chitosan blend films: fabrication, characterization and properties.

    Science.gov (United States)

    Azizi, Susan; Ahmad, Mansor B; Ibrahim, Nor Azowa; Hussein, Mohd Zobir; Namvar, Farideh

    2014-06-18

    In this study, cellulose nanocrystals/zinc oxide (CNCs/ZnO) nanocomposites were dispersed as bifunctional nano-sized fillers into poly(vinyl alcohol) (PVA) and chitosan (Cs) blend by a solvent casting method to prepare PVA/Cs/CNCs/ZnO bio-nanocomposites films. The morphology, thermal, mechanical and UV-vis absorption properties, as well antimicrobial effects of the bio-nanocomposite films were investigated. It demonstrated that CNCs/ZnO were compatible with PVA/Cs and dispersed homogeneously in the polymer blend matrix. CNCs/ZnO improved tensile strength and modulus of PVA/Cs significantly. Tensile strength and modulus of bio-nanocomposite films increased from 55.0 to 153.2 MPa and from 395 to 932 MPa, respectively with increasing nano-sized filler amount from 0 to 5.0 wt %. The thermal stability of PVA/Cs was also enhanced at 1.0 wt % CNCs/ZnO loading. UV light can be efficiently absorbed by incorporating ZnO nanoparticles into a PVA/Cs matrix, signifying that these bio-nanocomposite films show good UV-shielding effects. Moreover, the biocomposites films showed antibacterial activity toward the bacterial species Salmonella choleraesuis and Staphylococcus aureus. The improved physical properties obtained by incorporating CNCs/ZnO can be useful in variety uses.

  10. A facile method for the preparation of bifunctional Mn:ZnS/ZnS/Fe3O4 magnetic and fluorescent nanocrystals

    Science.gov (United States)

    Labiadh, Houcine; Ben Chaabane, Tahar; Sibille, Romain; Balan, Lavinia

    2015-01-01

    Summary Bifunctional magnetic and fluorescent core/shell/shell Mn:ZnS/ZnS/Fe3O4 nanocrystals were synthesized in a basic aqueous solution using 3-mercaptopropionic acid (MPA) as a capping ligand. The structural and optical properties of the heterostructures were characterized by X-ray diffraction (XRD), dynamic light scattering (DLS), transmission electron microscopy (TEM), UV–vis spectroscopy and photoluminescence (PL) spectroscopy. The PL spectra of Mn:ZnS/ZnS/Fe3O4 quantum dots (QDs) showed marked visible emission around 584 nm related to the 4T1 → 6A1 Mn2+ transition. The PL quantum yield (QY) and the remnant magnetization can be regulated by varying the thickness of the magnetic shell. The results showed that an increase in the thickness of the Fe3O4 magnetite layer around the Mn:ZnS/ZnS core reduced the PL QY but improved the magnetic properties of the composites. Nevertheless, a good compromise was achieved in order to maintain the dual modality of the nanocrystals, which may be promising candidates for various biological applications. PMID:26425426

  11. Study of pulsed-current loading of direct methanol fuel cells using a new time-domain model based on bi-functional methanol oxidation kinetics

    Science.gov (United States)

    Vilar, Eric; Dougal, R. A.

    This work describes a non-linear time-domain model of a direct methanol fuel cell (DMFC) and uses that model to show that pulsed-current loading of a direct methanol fuel cell does not improve average efficiency. Unlike previous system level models, the one presented here is capable of predicting the step response of the fuel cell over its entire voltage range. This improved model is based on bi-functional methanol oxidation reaction kinetics and is derived from a lumped, four-step reaction mechanism. In total, six states are incorporated into the model: three states for intermediate surface adsorbates on the anode electrode, two states for the anode and cathode potentials, and one state for the liquid methanol concentration in the anode compartment. Model parameters were identified using experimental data from a real DMFC. The model was applied to study the steady-state and transient performance of a DMFC with the objective to understand the possibility of improving the efficiency of the DMFC by using periodic current pulses to drive adsorbed CO from the anode catalyst. Our results indicate that the pulsed-current method does indeed boost the average potential of the DMFC by 40 mV; but on the other hand, executing that strategy reduces the overall operating efficiency and does not yield any net benefit.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Development of a plasmid-based expression system in Clostridium thermocellum and its use to screen heterologous expression of bifunctional alcohol dehydrogenases (adhEs)

    Energy Technology Data Exchange (ETDEWEB)

    Hon, Shuen [Dartmouth College, Hanover, NH (United States); Lanahan, Anthony [Dartmouth College, Hanover, NH (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Tian, Liang [Dartmouth College, Hanover, NH (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Giannone, Richard J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Hettich, Robert L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Olson, Daniel G. [Dartmouth College, Hanover, NH (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lynd, Lee R. [Dartmouth College, Hanover, NH (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2016-04-22

    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.

  17. A facile method for the preparation of bifunctional Mn:ZnS/ZnS/Fe3O4 magnetic and fluorescent nanocrystals.

    Science.gov (United States)

    Labiadh, Houcine; Ben Chaabane, Tahar; Sibille, Romain; Balan, Lavinia; Schneider, Raphaël

    2015-01-01

    Bifunctional magnetic and fluorescent core/shell/shell Mn:ZnS/ZnS/Fe3O4 nanocrystals were synthesized in a basic aqueous solution using 3-mercaptopropionic acid (MPA) as a capping ligand. The structural and optical properties of the heterostructures were characterized by X-ray diffraction (XRD), dynamic light scattering (DLS), transmission electron microscopy (TEM), UV-vis spectroscopy and photoluminescence (PL) spectroscopy. The PL spectra of Mn:ZnS/ZnS/Fe3O4 quantum dots (QDs) showed marked visible emission around 584 nm related to the (4)T1 → (6)A1 Mn(2+) transition. The PL quantum yield (QY) and the remnant magnetization can be regulated by varying the thickness of the magnetic shell. The results showed that an increase in the thickness of the Fe3O4 magnetite layer around the Mn:ZnS/ZnS core reduced the PL QY but improved the magnetic properties of the composites. Nevertheless, a good compromise was achieved in order to maintain the dual modality of the nanocrystals, which may be promising candidates for various biological applications.

  18. A facile method for the preparation of bifunctional Mn:ZnS/ZnS/Fe3O4 magnetic and fluorescent nanocrystals

    Directory of Open Access Journals (Sweden)

    Houcine Labiadh

    2015-08-01

    Full Text Available Bifunctional magnetic and fluorescent core/shell/shell Mn:ZnS/ZnS/Fe3O4 nanocrystals were synthesized in a basic aqueous solution using 3-mercaptopropionic acid (MPA as a capping ligand. The structural and optical properties of the heterostructures were characterized by X-ray diffraction (XRD, dynamic light scattering (DLS, transmission electron microscopy (TEM, UV–vis spectroscopy and photoluminescence (PL spectroscopy. The PL spectra of Mn:ZnS/ZnS/Fe3O4 quantum dots (QDs showed marked visible emission around 584 nm related to the 4T1 → 6A1 Mn2+ transition. The PL quantum yield (QY and the remnant magnetization can be regulated by varying the thickness of the magnetic shell. The results showed that an increase in the thickness of the Fe3O4 magnetite layer around the Mn:ZnS/ZnS core reduced the PL QY but improved the magnetic properties of the composites. Nevertheless, a good compromise was achieved in order to maintain the dual modality of the nanocrystals, which may be promising candidates for various biological applications.

  19. Fabrication of three-dimensional ordered macroporous spinel CoFe2O4as efficient bifunctional catalysts for the positive electrode of lithium-oxygen batteries.

    Science.gov (United States)

    Kim, Jong Guk; Noh, Yuseong; Kim, Youngmin; Lee, Seonhwa; Kim, Won Bae

    2017-04-20

    Three-dimensionally ordered macroporous (3DOM) CoFe 2 O 4 (CFO) catalysts were prepared by using the colloidal crystal templating method to be used as bifunctional catalysts of Li-O 2 battery positive electrodes. In order to study the relationship between the macropore diameter and charge/discharge behavior, 3DOM CFO catalysts with two different pore diameters of 140 and 60 nm were prepared. The physicochemical properties of the 3DOM CFO catalysts were investigated by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. When the 3DOM CFO catalyst with a pore diameter of 140 nm (CFO@140) was used in the O 2 -electrode of Li-O 2 batteries, it exhibited a substantially enhanced discharge capacity (ca. 11 658.5 mA h g -1 ) in the first cycle. Moreover, the Li-O 2 cells with the CFO@140 catalyst showed cycling stability over 47 cycles at a limited capacity of 500 mA h g -1 with a reduced potential polarization of 1.13 V, as compared with that with Ketjen Black carbon and the 3DOM CFO of 60 nm pore diameter (CFO@60). Their high cycling stability, low overpotential, high round-trip efficiency, and high rate performance suggest that these 3DOM CFO catalysts could be promising O 2 -electrode catalysts for next-generation lithium-oxygen batteries.

  20. 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.

  1. Preparation and characterization of bifunctional dendrimer modified Fe3O4/CdTe nanoparticles with both luminescent and superparamagnetic properties

    International Nuclear Information System (INIS)

    Wang, Xiuling; Gu, Yinjun; Dong, Shuling; Zhao, Qin; Liu, Yongjian

    2015-01-01

    Highlights: • The fluorescent superparamagnetic dendrimeric Fe 3 O 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 3 O 4 were prepared by hydrothermal coprecipitation of ferric and ferrous ions using NaOH. The surface modification of Fe 3 O 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 3 O 4 /CdTe nanoparticles were successfully prepared using this technique and characterized by microscopy. The optical and magnetic properties of the dendrimeric Fe 3 O 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

  2. The urchin-like sphere arrays Co3O4 as a bifunctional catalyst for hydrogen evolution reaction and oxygen evolution reaction

    Science.gov (United States)

    Li, Ruchun; Zhou, Dan; Luo, Jiaxian; Xu, Weiming; Li, Jingwei; Li, Shuoshuo; Cheng, Pengpeng; Yuan, Dingsheng

    2017-02-01

    Electrochemical water splitting has attracted great interest because of the growing demand for sustainable energy and increasing concerns for the environment. We present a facile strategy to design the three-dimensional (3D) urchin-like sphere arrays Co3O4 as an effective bifunctional catalyst for electrochemical water splitting. The 3D urchin-like Co3O4 was directly grown on Ni foam by a hydrothermal reaction and annealing treatment at a low temperature. This process offers several advantages including facile synthesis, binder-free, and low cost. The 3D urchin-like Co3O4 as a catalyst for hydrogen evolution reaction exhibits a low onset potential (-130 mV vs. RHE) and good cycling stability in an alkaline electrolyte. When urchin-like Co3O4 is used as a catalyst for oxygen evolution reaction, the onset potential is at 1.46 V (vs. RHE) with a low overpotential of only 230 mV. The good catalytic activity can be attributed to the unique urchin-like nanostructure, abundant mesopores, and low charge-transfer resistance (compared with Co3O4 NPs). In addition, H2 and O2 generation was performed using Co3O4 as both cathode and anode catalysts with a potential of 1.64 V to reach a current density of 10 mA cm-2.

  3. 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.)

  4. Three-Dimensional Framework of Graphene Nanomeshes Shell/Co3O4Synthesized as Superior Bifunctional Electrocatalyst for Zinc-Air Batteries.

    Science.gov (United States)

    Wang, Congwei; Zhao, Zheng; Li, Xiaofeng; Yan, Rui; Wang, Jie; Li, Anni; Duan, Xiaoyong; Wang, Junying; Liu, Yong; Wang, Junzhong

    2017-11-29

    The synthesis of durable and low-cost electrocatalyst is crucial but challenging. Here, we developed a one-pot pyrolysis approach toward the preparation of heteroatom-doped hierarchical porous three-dimensional (3D) graphene frameworks decorated with multilayer graphene shell-coated cobalt oxide nanocrystal. Large literal sheet size of graphene nanomeshes may stimulate rapid thermolysis with cobalt-oleate complex to form Co 3 O 4 nanocrystals and in situ growth of multilayer graphene coating co-doped by boron and nitrogen with controlling heating rate up to 600 °C. This new material worked as superior bifunctional electrocatalyst on oxygen reduction reaction and oxygen evolution reaction to commercial Pt/C with better onset potential/half-wave potentials, larger current density, better stability, and stronger methanol tolerance. The heteroatom co-doping into porous/curved graphene confined nanocrystals in 3D porous walls provided adequate accessibility of created catalytic active sites and ideal mass transport route for the excellent catalytic activity on redox reaction of oxygen. The synthesized material-based Zn-air battery further confirmed its superior electrolytic activity with high specific capacity and smaller overpotential. This one-pot pyrolysis method shows a great potential of scalable synthesis of high-performance practical electrocatalyst for metal-air batteries and fuel cells at a low cost.

  5. Catalytic asymmetric aza-Morita-Baylis-Hillman reaction of methyl acrylate: role of a bifunctional La(O-iPr)3/linked-BINOL complex.

    Science.gov (United States)

    Yukawa, Takafumi; Seelig, Bianca; Xu, Yingjie; Morimoto, Hiroyuki; Matsunaga, Shigeki; Berkessel, Albrecht; Shibasaki, Masakatsu

    2010-09-01

    The catalytic asymmetric aza-Morita-Baylis-Hillman reaction using unactivated methyl acrylate is described. A simple Lewis acidic metal catalyst, such as La(OTf)(3), was not suitable for the reaction, but rare earth metal alkoxide/linked-BINOL complexes possessing bifunctional Lewis acid and Brønsted base properties efficiently promoted the reaction in combination with an achiral nucleophilic organocatalyst. The combined use of a La(O-iPr)(3)/(S,S)-TMS-linked-BINOL complex with a catalytic amount of DABCO promoted the aza-Morita-Baylis-Hillman reaction of a broad range of N-diphenylphosphinoyl imines. Products from aryl, heteroaryl, and alkenyl imines were obtained in 67-99% yield and 81-95% ee. It is noteworthy that isomerizable alkyl imines could be employed as well, giving products in 78-89% yield and 94-98% ee. Initial rate kinetic studies as well as kinetic isotope effect experiments using alpha-deuterio-methyl acrylate support the importance of both the nucleophilicity of La-enolate and the Brønsted basicity of a La-catalyst for promoting the reaction.

  6. A systematic study on the utility of CHX-A''-DTPA-NCS and NOTA-NCS as bifunctional chelators for177Lu radiopharmaceuticals.

    Science.gov (United States)

    Pandey, Usha; Gamre, Naresh; Lohar, Sharad Pandurang; Dash, Ashutosh

    2017-09-01

    This paper describes the evaluation of [(R)-2-Amino-3-(4-isothiocyanatophenyl)propyl]-trans-(S,S)-cyclohexane-1,2-diamine-pentaacetic acid (CHX-A''-DTPA-NCS) and 2-S-(4-isothiocyanatobenzyl)-1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA-NCS) as bifunctional chelators for 177 Lu. While 177 Lu-CHX-A''-DTPA-NCS could be obtained in high yields at equimolar ratios of lutetium to CHX-A''-DTPA-NCS, >95% yield of 177 Lu-NOTA-NCS could be achieved at 1:2M ratio of lutetium to NOTA-NCS. Trace metals reduced the yields of 177 Lu-NOTA-NCS significantly as compared to 177 Lu-CHX-A''-DTPA-NCS. In vitro stability of 177 Lu-CHX-A''-DTPA-NCS was also superior to 177 Lu-NOTA-NCS. It could be concluded from this study that among the two chelators evaluated, CHX-A''-DTPA-NCS is more appropriate for preparation of 177 Lu radiopharmaceuticals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. 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.

  8. 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.

  9. 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

  10. 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)

  11. Robust Fe3Mo3C Supported IrMn Clusters as Highly Efficient Bifunctional Air Electrode for Metal-Air Battery.

    Science.gov (United States)

    Cui, Zhiming; Li, Yutao; Fu, Gengtao; Li, Xiang; Goodenough, John B

    2017-10-01

    Catalysts at the air cathode for oxygen reduction and evolution reactions are central to the stability of rechargeable metal-air batteries, an issue that is gaining increasing interest in recent years. Herein, a highly durable and efficient carbide-based bifunctional catalyst consisting of iron-molybdenum carbide (Fe 3 Mo 3 C) and IrMn nanoalloys is demonstratred. This carbide is chemically stable in alkaline media and over the potential range of an air cathode. More importantly, Fe 3 Mo 3 C is very active for oxygen reduction reaction (ORR) in alkaline media. Fe 3 Mo 3 C supported IrMn as a bifunictional catalysts exhibits superior catalytic performance than the state of the art ORR catalyst (Pt/C) and the oxygen evolution reaction catalyst (Ir/C). IrMn/Fe 3 Mo 3 C enables Zn-air batteries to achieve long-term cycling performance over 200 h with high efficiency. The extraordinarily high performance of IrMn/Fe 3 Mo 3 C bifunictional catalyst provides a very promising alternative to the conventional Pt/C and Ir/C catalyst for an air cathode in alkaline electrolyte. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Characterization of a bifunctional PutA homologue from Bradyrhizobium japonicum and identification of an active site residue that modulates proline reduction of the flavin adenine dinucleotide cofactor.

    Science.gov (United States)

    Krishnan, Navasona; Becker, Donald F

    2005-06-28

    PutA is a bifunctional flavoenzyme in bacteria that catalyzes the four-electron oxidation of proline to glutamate. In certain prokaryotes such as Escherichia coli, PutA is also a transcriptional repressor of the proline utilization (put) genes and thus is trifunctional. In this work, we have begun to assess differences between bifunctional and trifunctional PutA enzymes by examining the PutA protein from Bradyrhizobium japonicum (BjPutA). Primary structure analysis of BjPutA shows it lacks the DNA-binding domain of E. coli PutA (EcPutA). Consistent with this prediction, purified BjPutA does not exhibit DNA-binding activity in native gel mobility shift assays with promoter regions of the putA gene from B. japonicum. The catalytic and redox properties of BjPutA were characterized and a reduction potential (E(m)) value of -0.132 V (pH 7.5) was determined for the bound FAD/FADH(2) couple in BjPutA that is significantly more negative ( approximately 55 mV) than the E(m) for EcPutA-bound FAD. The more negative E(m) value thermodynamically limits proline reduction of the FAD cofactor in BjPutA. In the presence of phospholipids, reduction of BjPutA is stimulated, suggesting lipids influence the FAD redox environment. Accordingly, an E(m) value of -0.114 V (pH 7.5) was determined for BjPutA-bound FAD in the presence of polar lipids. The molecular basis for the lower reduction potential of FAD in BjPutA relative to EcPutA was explored by site-directed mutagenesis. Amino acid sequence alignment between BjPutA and EcPutA indicates only one difference in active site residues near the isoalloxazine ring of FAD: Val402 in EcPutA is substituted at the analogous position in BjPutA with Ala310. Replacement of A310 by Val in the BjPutA mutant A310V raised the reduction potential of bound FAD relative to wild-type BjPutA to an E(m) value of -0.09 V (pH 7.5). The >40-mV positive shift in the potential of the BjPutA mutant A310V suggests that the corresponding Val residue in Ec

  13. sCD4-17b bifunctional protein: Extremely broad and potent neutralization of HIV-1 Env pseudotyped viruses from genetically diverse primary isolates

    Directory of Open Access Journals (Sweden)

    Dey Barna

    2010-02-01

    Full Text Available Abstract Background We previously described a potent recombinant HIV-1 neutralizing protein, sCD4-17b, composed of soluble CD4 attached via a flexible polypeptide linker to an SCFv of the 17b human monoclonal antibody directed against the highly conserved CD4-induced bridging sheet of gp120 involved in coreceptor binding. The sCD4 moiety of the bifunctional protein binds to gp120 on free virions, thereby enabling the 17b SCFv moiety to bind and block the gp120/coreceptor interaction required for entry. The previous studies using the MAGI-CCR5 assay system indicated that sCD4-17b (in concentrated cell culture medium, or partially purified potently neutralized several genetically diverse HIIV-1 primary isolates; however, at the concentrations tested it was ineffective against several other strains despite the conservation of binding sites for both CD4 and 17b. To address this puzzle, we designed variants of sCD4-17b with different linker lengths, and tested the neutralizing activities of the immunoaffinity purified proteins over a broader concentration range against a large number of genetically diverse HIV-1 primary isolates, using the TZM-bl Env pseudotype assay system. We also examined the sCD4-17b sensitivities of isogenic viruses generated from different producer cell types. Results We observed that immunoaffinity purified sCD4-17b effectively neutralized HIV-1 pseudotypes, including those from HIV-1 isolates previously found to be relatively insensitive in the MAGI-CCR5 assay. The potencies were equivalent for the original construct and a variant with a longer linker, as observed with both pseudotype particles and infectious virions; by contrast, a construct with a linker too short to enable simultaneous binding of the sCD4 and 17b SCFv moieties was much less effective. sCD4-17b displayed potent neutralizing activity against 100% of nearly 4 dozen HIV-1 primary isolates from diverse genetic subtypes (clades A, B, C, D, F, and circulating

  14. The Cytophaga hutchinsonii ChTPSP: First characterized bifunctional TPS-TPP protein as putative ancestor of all eukaryotic trehalose biosynthesis proteins.

    Science.gov (United States)

    Avonce, Nelson; Wuyts, Jan; Verschooten, Katrien; Vandesteene, Lies; Van Dijck, Patrick

    2010-02-01

    The most widely distributed pathway to synthesize trehalose in nature consists of two consecutive enzymatic reactions with a trehalose-6-P (T6P)-synthase (TPS) enzyme, producing the intermediate T6P, and a T6P-phosphatase (TPP) enzyme, which dephosphorylates T6P to produce trehalose and inorganic phosphate. In plants, these enzymes are called Class I and Class II proteins, respectively, with some Class I proteins being active enzymes. The Class II proteins possess both TPS and TPP consensus regions but appear to have lost enzymatic activity during evolution. Plants also contain an extra group of enzymes of small protein size, of which some members have been characterized as functional TPPs. These Class III proteins have less sequence similarity with the Class I and Class II proteins. Here, we characterize for the first time, by using biochemical analysis and yeast growth complementation assays, the existence of a natural TPS-TPP bifunctional enzyme found in the bacterial species Cytophaga hutchinsonii. Through phylogenetic analysis, we show that prokaryotic genes such as ChTPSP might be the ancestor of the eukaryotic trehalose biosynthesis genes. Second, we show that plants have recruited during evolution, possibly by horizontal transfer from bacteria such as Rhodoferax ferrireducens, a new type of small protein, encoding TPP activity, which have been named Class III proteins. RfTPP has very high TPP activity upon expression in yeast. Finally, we demonstrate that TPS gene duplication, the recruitment of the Class III enzymes, and recruitment of an N-terminal regulatory element, which regulates the Class I enzyme activity in higher plants, were initiated very early in eukaryan evolution as the three classes of trehalose biosynthesis genes are already present in the alga Ostreococcus tauri.

  15. Isothiocyanate-Functionalized Bifunctional Chelates and fac-[M(I)(CO)3](+) (M = Re, (99m)Tc) Complexes for Targeting uPAR in Prostate Cancer.

    Science.gov (United States)

    Kasten, Benjamin B; Ma, Xiaowei; Cheng, Kai; Bu, Lihong; Slocumb, Winston S; Hayes, Thomas R; Trabue, Steven; Cheng, Zhen; Benny, Paul D

    2016-01-20

    Developing new strategies to rapidly incorporate the fac-[M(I)(CO)3](+) (M = Re, (99m)Tc) core into biological targeting vectors in radiopharmaceuticals continues to expand as molecules become more complex and as efforts to minimize nonspecific binding increase. This work examines a novel isothiocyanate-functionalized bifunctional chelate based on 2,2'-dipicolylamine (DPA) specifically designed for complexing the fac-[M(I)(CO)3](+) core. Two strategies (postlabeling and prelabeling) were explored using the isothiocyanate-functionalized DPA to determine the effectiveness of assembly on the overall yield and purity of the complex with amine containing biomolecules. A model amino acid (lysine) examined (1) amine conjugation of isothiocyanate-functionalized DPA followed by complexation with fac-[M(I)(CO)3](+) (postlabeling) and (2) complexation of fac-[M(I)(CO)3](+) with isothiocyanate-functionalized DPA followed by amine conjugation (prelabeling). Conducted with stable Re and radioactive (99m)Tc analogs, both strategies formed the product in good to excellent yields under macroscopic and radiotracer concentrations. A synthetic peptide (AE105) which targets an emerging biomarker in CaP prognosis, urokinase-type plasminogen activator receptor (uPAR), was also explored using the isothiocyanate-functionalized DPA strategy. In vitro PC-3 (uPAR+) cell uptake assays with the (99m)Tc-labeled peptide (8a) showed 4.2 ± 0.5% uptake at 4 h. In a murine model bearing PC-3 tumor xenografts, in vivo biodistribution of 8a led to favorable tumor uptake (3.7 ± 0.7% ID/g) at 4 h p.i. with relatively low accumulation (fac-[M(I)(CO)3](+).

  16. 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

    2017-11-07

    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.

  17. Ni- and Mn-Promoted Mesoporous Co3O4: A Stable Bifunctional Catalyst with Surface-Structure-Dependent Activity for Oxygen Reduction Reaction and Oxygen Evolution Reaction.

    Science.gov (United States)

    Song, Wenqiao; Ren, Zheng; Chen, Sheng-Yu; Meng, Yongtao; Biswas, Sourav; Nandi, Partha; Elsen, Heather A; Gao, Pu-Xian; Suib, Steven L

    2016-08-17

    Efficient bifunctional catalysts for electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable due to their wide applications in fuel cells and rechargeable metal air batteries. However, the development of nonprecious metal catalysts with comparable activities to noble metals is still challenging. Here we report a one-step wet-chemical synthesis of Ni-/Mn-promoted mesoporous cobalt oxides through an inverse micelle process. Various characterization techniques including powder X-ray diffraction (PXRD), N2 sorption, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) confirm the successful incorporation of Ni and Mn leading to the formation of Co-Ni(Mn)-O solid solutions with retained mesoporosity. Among these catalysts, cobalt oxide with 5% Ni doping demonstrates promising activities for both ORR and OER, with an overpotential of 399 mV for ORR (at -3 mA/cm(2)) and 381 mV (at 10 mA/cm(2)) for OER. Furthermore, it shows better durability than precious metals featuring little activity decay throughout 24 h continuous operation. Analyses of cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), Raman, and O2-temperature-programmed desorption (O2-TPD) reveal that redox activity of Co(3+) to Co(4+) is crucial for OER performance, while the population of surface oxygen vacancies and surface area determine ORR activities. The comprehensive investigation of the intrinsic active sites for ORR and OER by correlating different physicochemical properties to the electrochemical activities is believed to provide important insight toward the rational design of high-performance electrocatalysts for ORR and OER reactions.

  18. Paragenesis of Palladium-Cobalt Nanoparticle in Nitrogen-Rich Carbon Nanotubes as a Bifunctional Electrocatalyst for Hydrogen-Evolution Reaction and Oxygen-Reduction Reaction.

    Science.gov (United States)

    Huang, Binbin; Chen, Liyu; Wang, Yan; Ouyang, Liuzhang; Ye, Jianshan

    2017-06-07

    The hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) play important roles in many energy conversion and storage systems. To accelerate the reaction processes, there is a constant need for efficient new catalysts. In the present work, we have developed a facile pyrolysis-based process for the co-synthesis of palladium-cobalt nanoparticles supported on carbon nanotubes (Pd-CoCNTs), which exhibit superior catalytic activity for the HER and enhanced ORR performance. Non-agglomerated Pd nanoparticles of diameters 2-4 nm are uniformly distributed on the surface of CoCNTs, while the inner Co particles are an essential element in forming the framework of the CoCNTs. Compared to the Pd-free N-rich CoCNTs, Pd-CoCNTs have a more defective surface with a larger electrochemically active surface area (ECSA), and show enhanced ORR activity, outstanding methanol tolerance, and long-term stability in alkaline solution. At a low Pd loading of 0.0292 mg cm -2 , the Pd-CoCNTs require overpotentials of 0.024 V and 0.215 V to catalyze the HER and to drive a current density of 50 mA cm -2 in acidic solution, respectively. The palladium nanoparticles on the surface of the CoCNTs are considered to be highly active sites for HER, based on the results of control experiments, and it is easy to adjust the catalytic activity of the Pd-CoCNTs by changing the concentration of Pd therein. The proposed method provides a means of fabricating efficient bifunctional catalysts with controllable low contents of precious metals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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

    2018-04-04

    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 mesoporous carbon (Co3O4/MnO2/PQ-7). The optimized Co3O4/MnO2/PQ-7 exhibited a comparable ORR performance with commercial Pt/C, and a more superior OER performance than all the other prepared catalysts including commercial Pt/C. When applied to the practical aqueous (6.0 M KOH) zinc-air batteries, the Co3O4/MnO2/mesoporous 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 hours with negligible deactivation so far. More importantly, a series of flexible all-solid-state zinc-air batteries can be fabricated by the Co3O4/MnO2/mesoporous carbon with a layer-by-layer method. The optimal catalyst (Co3O4/MnO2/PQ-7) exhibited an excellent peak power density of 45 mW cm-2. The discharge potentials almost remained unchanged for 6 hours at 5 mA cm-2 and possessed a long cycle life (2.5 h @ 5 mA cm-2). These results make the optimized Co3O4/MnO2/PQ-7 as a promising cathode candidate for both liquid-type and flexible all-solid-state zinc-air batteries.

  20. Bifunctional CD4-DC-SIGN fusion proteins demonstrate enhanced avidity to gp120 and inhibit HIV-1 infection and dissemination.

    Science.gov (United States)

    Du, Tao; Hu, Kai; Yang, Jun; Jin, Jing; Li, Chang; Stieh, Daniel; Griffin, George E; Shattock, Robin J; Hu, Qinxue

    2012-09-01

    Early stages of mucosal infection are potential targets for HIV-1 prevention. CD4 is the primary receptor in HIV-1 infection whereas DC-SIGN likely plays an important role in HIV-1 dissemination, particularly during sexual transmission. To test the hypothesis that an inhibitor simultaneously targeting both CD4 and DC-SIGN binding sites on gp120 may provide a potent anti-HIV strategy, we designed constructs by fusing the extracellular CD4 and DC-SIGN domains together with varied arrangements of the lengths of CD4, DC-SIGN and the linker. We expressed, purified and characterized a series of soluble CD4-linker-DC-SIGN (CLD) fusion proteins. Several CLDs, composed of a longer linker and an extra neck domain of DC-SIGN, had enhanced affinity for gp120 as evidenced by molecular-interaction analysis. Furthermore, such CLDs exhibited significantly enhanced neutralization activity against both laboratory-adapted and primary HIV-1 isolates. Moreover, CLDs efficiently inhibited HIV-1 infection in trans via a DC-SIGN-expressing cell line and primary human dendritic cells. This was further strengthened by the results from the human cervical explant model, showing that CLDs potently prevented both localized and disseminated infections. This is the first time that soluble DC-SIGN-based bifunctional proteins have demonstrated anti-HIV potency. Our study provides proof of the concept that targeting both CD4 and DC-SIGN binding sites on gp120 represents a novel antiviral strategy. Given that DC-SIGN binding to gp120 increases exposure of the CD4 binding site and that the soluble forms of CD4 and DC-SIGN occur in vivo, further improvement of CLDs may render them potentially useful in prophylaxis or therapeutics.

  1. 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

  2. Paclitaxel conjugated Fe3O4@LaF3:Ce3+,Tb3+ nanoparticles as bifunctional targeting carriers for Cancer theranostics application

    Science.gov (United States)

    Mangaiyarkarasi, Rajendiran; Chinnathambi, Shanmugavel; Karthikeyan, Subramani; Aruna, Prakasarao; Ganesan, Singaravelu

    2016-02-01

    The bi-functional Chitosan functionalized magnetite doped luminescent rare earth nanoparticles (Fe3O4@LaF3: Ce3+,Tb3+/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 Fe3O4@LaF3: Ce3+,Tb3+/chi nanoparticles were studied using X-ray diffraction, vibrating sample magnetometer and scanning electron micrograph. The nature of interactions between PTX and Fe3O4@LaF3: Ce3+,Tb3+/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 Fe3O4@LaF3:Tb3+/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 Fe3O4@LaF3: Ce3+,Tb3+/chi NPs respectively. In addition with that, antitumoral activity study of PTX conjugated Fe3O4@LaF3:Tb3+/chi nanoparticles exhibits increased cytotoxic effects on A549 lung cancer cell lines than that of unconjugated PTX.

  3. Synergy of adsorption and visible-light photocatalytic degradation of methylene blue by a bifunctional Z-scheme heterojunction of WO3/g-C3N4

    Science.gov (United States)

    Liu, Xin; Jin, Ailing; Jia, Yushuai; Xia, Tonglin; Deng, Chenxin; Zhu, Meihua; Chen, Changfeng; Chen, Xiangshu

    2017-05-01

    A novel bifunctional Z-scheme heterojunction possessing high adsorption and photocatalytic activity, WO3/g-C3N4 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% WO3/g-C3N4. Under illumination, the photodegradation performance of 30 wt% WO3/g-C3N4 is improved to 2.5 and 2.7 times that of pure g-C3N4 and pure WO3, 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% WO3/g-C3N4 is enhanced to 4 times that of pure WO3, with a maximum of 97.00 mg g-1 determined by Langmuir isotherm. As evidenced by N2 physisorption, zeta potential and time-resolved photoluminescence measurements, the significant enhancement of the integrated adsorption and photocatalytic degradation efficiency is mainly due to the synergistic advantages of large surface area, negative zeta potential and facilitated charge separation of the composite.

  4. Related bifunctional restriction endonuclease-methyltransferase triplets: TspDTI, Tth111II/TthHB27I and TsoI with distinct specificities.

    Science.gov (United States)

    Zylicz-Stachula, Agnieszka; Zolnierkiewicz, Olga; Lubys, Arvydas; Ramanauskaite, Danute; Mitkaite, Goda; Bujnicki, Janusz M; Skowron, Piotr M

    2012-04-10

    We previously defined a family of restriction endonucleases (REases) from Thermus sp., which share common biochemical and biophysical features, such as the fusion of both the nuclease and methyltransferase (MTase) activities in a single polypeptide, cleavage at a distance from the recognition site, large molecular size, modulation of activity by S-adenosylmethionine (SAM), and incomplete cleavage of the substrate DNA. Members include related thermophilic REases with five distinct specificities: TspGWI, TaqII, Tth111II/TthHB27I, TspDTI and TsoI. TspDTI, TsoI and isoschizomers Tth111II/TthHB27I recognize different, but related sequences: 5'-ATGAA-3', 5'-TARCCA-3' and 5'-CAARCA-3' respectively. Their amino acid sequences are similar, which is unusual among REases of different specificity. To gain insight into this group of REases, TspDTI, the prototype member of the Thermus sp. enzyme family, was cloned and characterized using a recently developed method for partially cleaving REases. TspDTI, TsoI and isoschizomers Tth111II/TthHB27I are closely related bifunctional enzymes. They comprise a tandem arrangement of Type I-like domains, like other Type IIC enzymes (those with a fusion of a REase and MTase domains), e.g. TspGWI, TaqII and MmeI, but their sequences are only remotely similar to these previously characterized enzymes. The characterization of TspDTI, a prototype member of this group, extends our understanding of sequence-function relationships among multifunctional restriction-modification enzymes.

  5. Expression of a bacterial bi-functional chorismate mutase/prephenate dehydratase modulates primary and secondary metabolism associated with aromatic amino acids in Arabidopsis.

    Science.gov (United States)

    Tzin, Vered; Malitsky, Sergey; Aharoni, Asaph; Galili, Gad

    2009-10-01

    Plants can synthesize the aromatic amino acid Phe via arogenate, but it is still not known whether they also use an alternative route for Phe biosynthesis via phenylpyruvate, like many micro-organisms. To examine this possibility, we expressed a bacterial bi-functional PheA (chorismate mutase/prephenate dehydratase) gene in Arabidopsis thaliana that converts chorismate via prephenate into phenylpyruvate. The PheA-expressing plants showed a large increase in the level of Phe, implying that they can convert phenylpyruvate into Phe. In addition, PheA expression rendered the plants more sensitive than wild-type plants to the Trp biosynthesis inhibitor 5-methyl-Trp, implying that Phe biosynthesis competes with Trp biosynthesis from their common precursor chorismate. Surprisingly, GC-MS, LC-MS and microarray analyses showed that this increase in Phe accumulation only had a very minor effect on the levels of other primary metabolites as well as on the transcriptome profile, implying little regulatory cross-interaction between the aromatic amino acid biosynthesis network and the bulk of the Arabidopsis transcriptome and primary metabolism. However, the levels of a number of secondary metabolites derived from all three aromatic amino acids (Phe, Trp and Tyr) were altered in the PheA plants, implying regulatory cross-interactions between the flux of aromatic amino acid biosynthesis from chorismate and their further metabolism into various secondary metabolites. Taken together, our results provide insights into the regulatory mechanisms of aromatic amino acid biosynthesis and their interaction with central primary metabolism, as well as the regulatory interface between primary and secondary metabolism.

  6. The N-terminus and the Chain-length Determination (CLD) Domain Play a Role in the Length of the Isoprenoid Product of the Bifunctional Toxoplasma gondii Farnesyl-diphosphate Synthase

    Science.gov (United States)

    Li, Zhu-Hong; Cintrón, Roxana; Koon, Noah A.; Moreno, Silvia N.J.

    2015-01-01

    Toxoplasma gondii possesses a bifunctional farnesyl diphosphate (FPP)/geranylgeranyl diphosphate (GGPP) synthase (TgFPPS) that synthesizes C15 and C20 isoprenoid diphosphates from isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP). This enzyme has a unique arrangement of the 4th and 5th amino acid upstream to the First Aspartic Rich Domain (FARM) where the 4th amino acid is aromatic and the 5th is a cysteine. We mutated these amino acids converting the enzyme to an absolute FPPS by changing the cysteine to a tyrosine. The enzyme could be converted to an absolute GGPPS by changing both the 4th and 5th amino acids to alanines. We also constructed four mutated TgFPPSs whose regions around the first aspartate-rich motif were replaced with the corresponding regions of FPP synthases from Arabidopsis thaliana or Saccharomyces cerevisiae or with the corresponding regions of GGPP synthases from Homo sapiens or S. cerevisiae. We determined that the presence of a cysteine at the 4th position is essential for the TgFPPS bifunctionality. We also found that the length of the N-terminal domain has a role in determining the specificity and the length of the isoprenoid product. Phylogenetic analysis supports the grouping of this enzyme with other Type I FPPSs but the biochemical data indicates that TgFPPS has unique characteristics that differentiate it from mammalian FPPSs and GGPPSs and is therefore an important drug target. PMID:22931372

  7. 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

    . The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X......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 synthesis......-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential...

  8. 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.

    Science.gov (United States)

    Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

    2017-06-01

    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 synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

  9. 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.

  10. Atomically Thin Mesoporous Co3O4Layers Strongly Coupled with N-rGO Nanosheets as High-Performance Bifunctional Catalysts for 1D Knittable Zinc-Air Batteries.

    Science.gov (United States)

    Li, Yingbo; Zhong, Cheng; Liu, Jie; Zeng, Xiaoqiao; Qu, Shengxiang; Han, Xiaopeng; Deng, Yida; Hu, Wenbin; Lu, Jun

    2018-01-01

    Under development for next-generation wearable electronics are flexible, knittable, and wearable energy-storage devices with high energy density that can be integrated into textiles. Herein, knittable fiber-shaped zinc-air batteries with high volumetric energy density (36.1 mWh cm -3 ) are fabricated via a facile and continuous method with low-cost materials. Furthermore, a high-yield method is developed to prepare the key component of the fiber-shaped zinc-air battery, i.e., a bifunctional catalyst composed of atomically thin layer-by-layer mesoporous Co 3 O 4 /nitrogen-doped reduced graphene oxide (N-rGO) nanosheets. Benefiting from the high surface area, mesoporous structure, and strong synergetic effect between the Co 3 O 4 and N-rGO nanosheets, the bifunctional catalyst exhibits high activity and superior durability for oxygen reduction and evolution reactions. Compared to a fiber-shaped zinc-air battery using state-of-the-art Pt/C + RuO 2 catalysts, the battery based on these Co 3 O 4 /N-rGO nanosheets demonstrates enhanced and stable electrochemical performance, even under severe deformation. Such batteries, for the first time, can be successfully knitted into clothes without short circuits under external forces and can power various electronic devices and even charge a cellphone. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A new bifunctional chelating agent conjugated with monoclonal antibody and labelled with technetium-99m for targeted scintigraphy: 6-(4-isothiocyanatobenzyl)-5,7-dioxo-1,11-(carboxymethyl)-1,4,8,11-tetraazacyclotridecane.

    Science.gov (United States)

    Mishra, Anil Kumar; Panwar, Puja; Hosono, Makoto; Chuttani, Krishna; Mishra, Pushpa; Sharma, Rakesh Kumar; Chatal, Jean-Francois

    2004-01-01

    The purpose of this study was to obtain the convenient, synthetically useful bifunctional chelating agent, 6-(4-isothiocyanatobenzyl)-5,7-dioxo-1,11-(carboxymethyl)-1,4,8,11-tetraazacyclotridecane, and to apply it to stable (99m)Tc-labelling of monoclonal antibodies (mAbs). The chelate was synthesised by reaction of nitrobenzyl malonate and triethylenetetramine followed by alkylation by reacting with bromoacetic acid at pH 10. The amino group was converted to isothiocyanato derivative by reacting with thiophosgene at pH 2.0. Conjugation with mAbs [(anti-carcinoembryonic antigen (CEA) and anti-epidermal growth factor receptor (EGFr)] was performed at pH 8.4 using trisodium phosphate solution by incubating at 37 degrees C for 1 h and subjected to purification on size exclusion chromatography. When radioimmunoconjugates were labelled with (99m)Tc, the specific activity of immunoconjugates was 20-30 mCi/mg of protein and their immunoreactivity exceeded 80%. The stability in serum indicated that the metal remained bound to antibodies. Biodistribution studies in athymic mice grafted with U-87 human glioblastoma multiforme and MDA-MB-468 human breast carcinoma tumours revealed significant localisation of (99m)Tc-labelled antibodies in tumours and reduced accumulation in normal organs. This bifunctional chelating agent is promising for immunoscintigraphy because of good tumour-to-normal organ contrast.

  12. 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

  13. 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.

  14. 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

  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. Bifunctional Fe{sub 3}O{sub 4}@Gd{sub 2}O{sub 3}:Eu{sup 3+}nanocomposites obtained by the homogeneous precipitation method

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Hongxia [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shanxi Key Laboratory of Physico-Inorganic Chemistry, School of Chemistry and Materials Science, Northwest University, Xi’an, Shanxi 710069 (China); Cui, Bin, E-mail: cuibin@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shanxi Key Laboratory of Physico-Inorganic Chemistry, School of Chemistry and Materials Science, Northwest University, Xi’an, Shanxi 710069 (China); Wang, Yingsai [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shanxi Key Laboratory of Physico-Inorganic Chemistry, School of Chemistry and Materials Science, Northwest University, Xi’an, Shanxi 710069 (China)

    2013-05-15

    Graphical abstract: The TEM images reveal clearly the core–shell structures because of the obvious difference in contrast between the central part and the fringe, which indicates the Gd{sub 2}O{sub 3}:Eu{sup 3+} layer had successfully deposited on the magnetite Fe{sub 3}O{sub 4} cores. And Fe{sub 3}O{sub 4}@Gd{sub 2}O{sub 3}:Eu{sup 3+} nanoparticles keep the spherical morphology, non-aggregation and rough surface. The images reveal that the average diameters of the Fe{sub 3}O{sub 4} and Fe{sub 3}O{sub 4}@Gd{sub 2}O{sub 3}:Eu{sup 3+} nanoparticles are ∼200 nm and ∼250 nm, respectively. The thickness of Gd{sub 2}O{sub 3}:Eu{sup 3+} layer is ∼25 nm. Highlights: ► Fe{sub 3}O{sub 4}@Gd{sub 2}O{sub 3}:Eu{sup 3+} nanocomposites were synthesized by homogeneous precipitation method. ► Formation of core–shell nanostructure revealed by transmission electron microscopy. ► Fe{sub 3}O{sub 4}@Gd{sub 2}O{sub 3}:Eu{sup 3+} nanocomposites showed magnetic behavior and fluorescence properties. ► Possible applications including bioseparation, drug delivery system, bio-labels, etc. - Abstract: An easy homogeneous precipitation method was developed for the synthesis of bifunctional magnetic-fluorescent nanocomposites with Fe{sub 3}O{sub 4} nanoparticles as the core and europium-doped gadolinium oxide (Gd{sub 2}O{sub 3}:Eu{sup 3+}) as the shell. The nanocomposites showed both strong magnetic behavior and unique Eu-related fluorescence properties with a high emission intensity, which may lead to development of nanocomposites with great potential for applications in drug targeting, biosensors, and diagnostic analysis.

  17. Two-stage gene assembly/cloning of a member of the TspDTI subfamily of bifunctional restriction endonucleases, TthHB27I.

    Science.gov (United States)

    Krefft, Daria; Zylicz-Stachula, Agnieszka; Mulkiewicz, Ewa; Papkov, Aliaksei; Jezewska-Frackowiak, Joanna; Skowron, Piotr M

    2015-01-20

    The Thermus sp. family of bifunctional type IIS/IIG/IIC restriction endonucleases (REase)-methyltransferases (MTase) comprises thermo-stable TaqII, TspGWI, TspDTI, TsoI, Tth111II/TthHB27I enzymes as well as a number of putative enzymes/open reading frames (ORFs). All of the family members share properties including a large protein size (ca. 120kDa), amino acid (aa) sequence homologies, enzymatic activity modulation by S-adenosylmethionine (SAM), recognition of similar asymmetric cognate DNA sites and cleavage at a distance of 11/9 nt. Analysis of the enzyme aa sequences and domain/motif organisation led to further Thermus sp. family division into the TspDTI and TspGWI subfamilies. The latter exhibits an unprecedented phenomenon of DNA recognition change upon substitution of SAM by its analogue, sinefungin (SIN), towards a very frequent DNA cleavage. We report cloning in Escherichia coli (E. coli), using a two-stage procedure and a putative tthHB27IRM gene, detected by bioinformatics analysis of the Thermus thermophilus HB27 (T. thermophilus) genome. The functionality of a 3366 base pair (bp)-/1121 aa-long, high GC content ORF was validated experimentally through the expression in E. coli. Protein features corroborated with the reclassification of TthHB27I into the TspDTI subfamily, which manifested in terms of aa-sequence/motif homologies and insensitivity to SIN-induced specificity shift. However, both SAM and SIN stimulated the REase DNA cleavage activity by at least 16-32 times; the highest was observed for the Thermus sp. family. The availability of TthHB27I and the need to include SAM or SIN in the reaction in order to convert the enzyme from "hibernation" status to efficient DNA cleavage is of practical significance in molecular biotechnology, extending the palette of available REase specificities. Copyright © 2014 Elsevier B.V. All rights reserved.

  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. Molecular organization of the reagents in the kinetics and catalysis of liquid-phase reactions. II. Catalysis of the reactions of isocyanates with hydroxy-containing compounds of bifunctional nature in the presence of Sn(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Berlin, P.A.; Tiger, R.P.; Chirkov, Yu.N.; Entelis, S.G.

    1988-05-01

    The kinetic principles of the reaction of m-chlorophenyl isocyanate with glycols with different chain lengths, diethylene glycol monoethyl ether, and n-butanol in the presence of Bu/sub 3/SnAc as the catalyst in dichloroethane were studied. The transition from a noncatalytic reaction to a reaction catalyzed by Sn(IV) involves the replacement of two of the four OH groups in the yield channel by a molecule of the catalyst. The catalytic reaction of monofunctional compounds proceeds with the participation of dimerized (through H bonds) OH groups. Owing to the bifunctional character of the glycols and their ability to form an intromolecular H bond of the OH...OH type, one molecule of the glycol participates in the elementary act of the catalytic reaction.

  1. Simple, mild, one-step labelling of proteins with gallium-68 using a tris(hydroxypyridinone) bifunctional chelator: a 68Ga-THP-scFv targeting the prostate-specific membrane antigen.

    Science.gov (United States)

    Nawaz, Saima; Mullen, Gregory E D; Sunassee, Kavitha; Bordoloi, Jayanta; Blower, Philip J; Ballinger, James R

    2017-10-25

    Labelling proteins with gallium-68 using bifunctional chelators is often problematic because of unsuitably harsh labelling conditions such as low pH or high temperature and may entail post-labelling purification. To determine whether tris(hydroxypyridinone) (THP) bifunctional chelators offer a potential solution to this problem, we have evaluated the labelling and biodistribution of a THP conjugate with a new single-chain antibody against the prostate-specific membrane antigen (PSMA), an attractive target for staging prostate cancer (PCa). A single-chain variable fragment (scFv) of J591, a monoclonal antibody that recognises an external epitope of PSMA, was prepared in order to achieve biokinetics matched to the half-life of gallium-68. The scFv, J591c-scFv, was engineered with a C-terminal cysteine. J591c-scFv was produced in HEK293T cells and purified by size-exclusion chromatography. A maleimide THP derivative (THP-mal) was coupled site-specifically to the C-terminal cysteine residue. The THP-mal-J591c-scFv conjugate was labelled with ammonium acetate-buffered gallium-68 from a 68 Ge/ 68 Ga generator at room temperature and neutral pH. The labelled conjugate was evaluated in the PCa cell line DU145 and its PSMA-overexpressing variant in vitro and xenografted in SCID mice. J591c-scFv was produced in yields of 4-6 mg/l culture supernatant and efficiently coupled with the THP-mal bifunctional chelator. Labelling yields > 95% were achieved at room temperature following incubation of 5 μg conjugate with gallium-68 for 5 min without post-labelling purification. 68 Ga-THP-mal-J591c-scFv was stable in serum and showed selective binding to the DU145-PSMA cell line, allowing an IC50 value of 31.5 nM to be determined for unmodified J591c-scFv. Serial PET/CT imaging showed rapid, specific tumour uptake and clearance via renal elimination. Accumulation in DU145-PSMA xenografts at 90 min post-injection was 5.4 ± 0.5%ID/g compared with 0.5 ± 0.2%ID/g in DU145

  2. The first bis-cyanoxime: synthesis and properties of a new versatile and accessible polydentate bifunctional building block for coordination and supramolecular chemistry.

    Science.gov (United States)

    Cheadle, Carl; Gerasimchuk, Nikolay; Barnes, Charles L; Tyukhtenko, Sergiy I; Silchenko, Svitlana

    2013-04-14

    A new multidentate bifunctional organic ligand – di-N,N′-(2-cyano-2-oximinoacetyl)piperazine – was synthesized in high yield using a two-step procedure carried out under ambient conditions. At first, the reaction of piperazine and neat methylcyanoacetate led to the di-N,N′-(cyanoacetyl)piperazine (1), which then was converted into bis-cyanoxime, di-N,N′-(2-cyano-2-oximinoacetyl)piperazine (HL, 2) using a room temperature nitrosation reaction with gaseous methylnitrite. Synthesized bis-cyanoxime was characterized by 1H, 13C NMR, UV-visible, IR spectroscopy and the X-ray analysis. The ligand 2 exists as a mixture of three diastereomers arising from the syn- and anti-geometry of the cyanoxime group. The prolonged crystallization of 2 from an ethanol–water mixture leads to the formation of: (a) colorless crystals that according to the X-ray analysis contain a 51.2:48.8% co-crystallized mixture of both isomers that have the same H-bonding motif (minority), and (b) a white amorphous material that represents an almost pure anti-isomer (majority). The deprotonation of 2 leads to the formation of a yellow dianion that demonstrated pronounced solvatochromism of its n → π* transition in the nitroso-chromophore. The disodium salt Na2L·4H2O (3) was obtained from 2 using NaOC2H5 in ethanol. The new bis-cyanoxime 2 reacts with Tl2CO3 and AgNO3 in aqueous solutions with the formation of light-stable, sparingly soluble yellow precipitates of M′2L·xH2O composition (M′ = Tl, Ag; Tl = 4, x = 0; Ag = 5, x = 2). The reaction of 3 with Ni2+ or K2M′′Cl4 (M′′ = Pd, Pt) in aqueous solutions leads to NiL·4H2O (6), PdL·4H2O (7) and PtL·5H2O (8). The crystal structure of 4 was determined and revealed the formation of a 3D-coordination polymeric complex in which the bis-cyanoxime acts as a dianionic, bridging, formally decadentate ligand. Each Tl(I) center has two bonds (2.655, 2.769 Å), shorter than the sum of ionic radii Tl–O (oxime group), and three longer

  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. 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

  5. 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

  6. 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

  7. 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)

  8. Structure of the bifunctional aminoglycoside-resistance enzyme AAC(6′)-Ie-APH(2′′)-Ia revealed by crystallographic and small-angle X-ray scattering analysis

    Science.gov (United States)

    Smith, Clyde A.; Toth, Marta; Weiss, Thomas M.; Frase, Hilary; Vakulenko, Sergei B.

    2014-01-01

    Broad-spectrum resistance to aminoglycoside antibiotics in clinically important Gram-positive staphylococcal and entero­coccal pathogens is primarily conferred by the bifunctional enzyme AAC(6′)-Ie-APH(2′′)-Ia. This enzyme possesses an N-terminal coenzyme A-dependent acetyltransferase domain [AAC(6′)-Ie] and a C-terminal GTP-dependent phosphotransferase domain [APH(2′′)-Ia], and together they produce resistance to almost all known aminoglycosides in clinical use. Despite considerable effort over the last two or more decades, structural details of AAC(6′)-Ie-APH(2′′)-Ia have remained elusive. In a recent breakthrough, the structure of the isolated C-terminal APH(2′′)-Ia enzyme was determined as the binary Mg2GDP complex. Here, the high-resolution structure of the N-terminal AAC(6′)-Ie enzyme is reported as a ternary kanamycin/coenzyme A abortive complex. The structure of the full-length bifunctional enzyme has subsequently been elucidated based upon small-angle X-ray scattering data using the two crystallographic models. The AAC(6′)-Ie enzyme is joined to APH(2′′)-Ia by a short, predominantly rigid linker at the N-terminal end of a long α-helix. This α-helix is in turn intrinsically associated with the N-terminus of APH(2′′)-Ia. This structural arrangement supports earlier observations that the presence of the intact α-helix is essential to the activity of both functionalities of the full-length AAC(6′)-Ie-APH(2′′)-Ia enzyme. PMID:25286858

  9. La(0.8)Sr(0.2)MnO(3-δ) decorated with Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ): a bifunctional surface for oxygen electrocatalysis with enhanced stability and activity.

    Science.gov (United States)

    Risch, Marcel; Stoerzinger, Kelsey A; Maruyama, Shingo; Hong, Wesley T; Takeuchi, Ichiro; Shao-Horn, Yang

    2014-04-09

    Developing highly active and stable catalysts based on earth-abundant elements for oxygen electrocatalysis is critical to enable efficient energy storage and conversion. In this work, we took advantage of the high intrinsic oxygen reduction reaction (ORR) activity of La(0.8)Sr(0.2)MnO(3-δ) (LSMO) and the high intrinsic oxygen evolution reaction (OER) activity of Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) to develop a novel bifunctional catalyst. We used pulsed laser deposition to fabricate well-defined surfaces composed of BSCF on thin-film LSMO grown on (001)-oriented Nb-doped SrTiO3. These surfaces exhibit bifunctionality for oxygen electrocatalysis with enhanced activities and stability for both the ORR and OER that rival the state-of-the-art single- and multicomponent catalysts in the literature.

  10. Synthesis of macrocyclic bifunctional chelating agents: 1,4,7 - tri(carboxy-methyl) - 10 - (2-amino-ethyl) - 1,4,7,10 - tetra-aza-cyclo-dodecane and 1,4,8 - tri(carboxy-methyl)- 11 - (2-amino-ethyl) - 1,4,8,11 - tetra-aza-cyclo-tetra-decane

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, A.K. [Institute of Nuclear Medicine and Allied Sciences, Dept. of Radiopharmaceuticals, Delhi (India); Chatal, J.F. [Institut National de la Sante et de la Recherche Medicale (INSERM U-463), Lab. d' Interactions Recepteurs Ligands en Immunocancerologie et immunopathologie, 44 - Nantes (France)

    2001-02-01

    The convenient, synthetically useful bifunctional chelating agents, 1,4,7 - tri(carboxy-methyl) - 10 - (2-amino-ethyl) - 1,4,7,10 - tetra-aza-cyclo-dodecane and 1,4,8 - tri(carboxy-methyl) - 11 - (2-amino-ethyl) - 1,4,8,11 - tetra-aza-cyclo-tetra-decane, were obtained by reaction of ethyl bromo-acetate with 1,4,7,10 - tetra-aza-cyclo-dodecane and 1,4,8,11 - tetra-aza-cyclo-tetra-decane, followed by reaction with N-(2-bromo-ethyl)phthalimide. This method is proven to be more efficient to prepare bifunctional chelating agents with aliphatic side arms in high yields, above 53%. (authors)

  11. Synthesis of macrocyclic bifunctional chelating agents: 1,4,7 - tri(carboxy-methyl) - 10 - (2-amino-ethyl) - 1,4,7,10 - tetra-aza-cyclo-dodecane and 1,4,8 - tri(carboxy-methyl)- 11 - (2-amino-ethyl) - 1,4,8,11 - tetra-aza-cyclo-tetra-decane

    International Nuclear Information System (INIS)

    Mishra, A.K.; Chatal, J.F.

    2001-01-01

    The convenient, synthetically useful bifunctional chelating agents, 1,4,7 - tri(carboxy-methyl) - 10 - (2-amino-ethyl) - 1,4,7,10 - tetra-aza-cyclo-dodecane and 1,4,8 - tri(carboxy-methyl) - 11 - (2-amino-ethyl) - 1,4,8,11 - tetra-aza-cyclo-tetra-decane, were obtained by reaction of ethyl bromo-acetate with 1,4,7,10 - tetra-aza-cyclo-dodecane and 1,4,8,11 - tetra-aza-cyclo-tetra-decane, followed by reaction with N-(2-bromo-ethyl)phthalimide. This method is proven to be more efficient to prepare bifunctional chelating agents with aliphatic side arms in high yields, above 53%. (authors)

  12. 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

  13. A simple approach for the synthesis of bifunctional Fe{sub 3}O{sub 4}-Gd{sub 2}O{sub 3}:Eu{sup 3+} core-shell nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Peng Hongxia [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shanxi Key Laboratory of Physico-Inorganic Chemistry, School of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Cui Bin, E-mail: cuibin@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shanxi Key Laboratory of Physico-Inorganic Chemistry, School of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Li Leilei; Wang Yingsai [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), Shanxi Key Laboratory of Physico-Inorganic Chemistry, School of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China)

    2012-08-05

    Graphical abstract: The TEM images reveal that Fe{sub 3}O{sub 4}-Gd{sub 2}O{sub 3}:Eu{sup 3+} nanoparticles have a particle size ranging from 175 nm to 300 nm and keep the spherical morphology, core-shell structures, non-aggregation and rough surface. The results revealed that the Gd{sub 2}O{sub 3}:Eu{sup 3+} phosphor layer uniformly deposited on Fe{sub 3}O{sub 4} nanoparticles and thicknesses of Gd{sub 2}O{sub 3}:Eu{sup 3+} are 20-30 nm. The selected-area electron diffraction (SAED) reveals the polycrystalline feature of the as-prepared product. Highlights: Black-Right-Pointing-Pointer Bifunctional magnetic-luminescent Fe{sub 3}O{sub 4}-Gd{sub 2}O{sub 3}:Eu{sup 3+} nanoparticles with core-shell structures have been successfully fabricated by a facile, green, and efficient hydrothermal method. Black-Right-Pointing-Pointer Fe{sub 3}O{sub 4}-Gd{sub 2}O{sub 3}:Eu{sup 3+} composites have robust magnetic responsive properties and strong luminescent properties. Black-Right-Pointing-Pointer Fe{sub 3}O{sub 4}-Gd{sub 2}O{sub 3}:Eu{sup 3+} nanoparticles have great potential applications in drug targeting, bioseparation and diagnostic analysis. - Abstract: Bifunctional magnetic-luminescent Fe{sub 3}O{sub 4}-Gd{sub 2}O{sub 3}:Eu{sup 3+} nanoparticles with core-shell structures have been successfully fabricated using a simple, green, and efficient hydrothermal method. These materials were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) spectra, and a superconducting quantum interference device (SQUID) magnetometer. The results showed that the spinel of the Fe{sub 3}O{sub 4} cores was uniformly coated with Gd{sub 2}O{sub 3}:Eu{sup 3+} layers. The inner Fe{sub 3}O{sub 4} cores and the outer Gd{sub 2}O{sub 3}:Eu{sup 3+} layers yielded composites that combine magnetic-responsive and luminescent properties, thus, nanoparticles of the composite may find potential applications in drug targeting, bioseparation, and

  14. 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

  15. 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.

  16. 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

    2016-09-01

    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.

  17. 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.

  18. 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

  19. In Situ Coupling of Strung Co4N and Intertwined N-C Fibers toward Free-Standing Bifunctional Cathode for Robust, Efficient, and Flexible Zn-Air Batteries.

    Science.gov (United States)

    Meng, Fanlu; Zhong, Haixia; Bao, Di; Yan, Junmin; Zhang, Xinbo

    2016-08-17

    Flexible power sources with high energy density are crucial for the realization of next-generation flexible electronics. Theoretically, rechargeable flexible zinc-air (Zn-air) batteries could provide high specific energy, while their large-scale applications are still greatly hindered by high cost and resources scarcity of noble-metal-based oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) electrocatalysts as well as inferior mechanical properties of the air cathode. Combining metallic Co4N with superior OER activity and Co-N-C with perfect ORR activity on a free-standing and flexible electrode could be a good step for flexible Zn-air batteries, while lots of difficulties need to be overcome. Herein, as a proof-of-concept experiment, we first propose a strategy for in situ coupling of strung Co4N and intertwined N-C fibers, by pyrolyzation of the novel pearl-like ZIF-67/polypyrrole nanofibers network rooted on carbon cloth. Originating from the synergistic effect of Co4N and Co-N-C and the stable 3D interconnected conductive network structure, the obtained free-standing and highly flexible bifunctional oxygen electrode exhibits excellent electrocatalytic activity and stability for both OER and ORR in terms of low overpotential (310 mV at 10 mA cm(-2)) for OER, a positive half-wave potential (0.8 V) for ORR, and a stable current density retention for at least 20 h, and especially, the obtained Zn-air batteries exhibit a low discharge-charge voltage gap (1.09 V at 50 mA cm(-2)) and long cycle life (up to 408 cycles). Furthermore, the perfect bendable and twistable and rechargeable properties of the flexible Zn-air battery particularly make it a potentially power portable and wearable electronic device.

  20. Co(II)1-xCo(0)x/3Mn(III)2x/3S Nanoparticles Supported on B/N-Codoped Mesoporous Nanocarbon as a Bifunctional Electrocatalyst of Oxygen Reduction/Evolution for High-Performance Zinc-Air Batteries.

    Science.gov (United States)

    Wang, Zilong; Xiao, Shuang; An, Yiming; Long, Xia; Zheng, Xiaoli; Lu, Xihong; Tong, Yexiang; Yang, Shihe

    2016-06-01

    Rechargeable Zn-air battery is an ideal type of energy storage device due to its high energy and power density, high safety, and economic viability. Its large-scale application rests upon the availability of active, durable, low-cost electrocatalysts for the oxygen reduction reaction (ORR) in the discharge process and oxygen evolution reaction (OER) in the charge process. Herein we developed a novel ORR/OER bifunctional electrocatalyst for rechargeable Zn-air batteries based on the codoping and hybridization strategies. The B/N-codoped mesoporous nanocarbon supported Co(II)1-xCo(0)x/3Mn(III)2x/3S nanoparticles exhibit a superior OER performance compared to that of IrO2 catalyst and comparable Zn-air battery performance to that of the Pt-based battery. The rechargeable Zn-air battery shows high discharge peak power density (over 250 mW cm(-2)) and current density (180 mA cm(-2) at 1 V), specific capacity (∼550 mAh g(-1)), small charge-discharge voltage gap of ∼0.72 V at 20 mA cm(-2) and even higher stability than the Pt-based battery. The advanced performance of the bifunctional catalysts highlights the beneficial role of the simultaneous formation of Mn(III) and Co(0) as well as the dispersed hybridization with the codoped nanocarbon support.

  1. 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

  2. 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

  3. 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.

  4. 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 s...

  5. 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.

  6. Bifunctional Catalysts for CO2 Reduction

    Science.gov (United States)

    2014-09-30

    dioxide reduction catalysis . (SA 1 – Catalyst candidate synthesis) As outlined in the original proposal, ligand platforms have been synthesized to...was limited to outer-sphere electron transfer (necessary oxidation potentials for catalysis > –2.1 V vs. [Cp2Fe] +/0). Thus, we pursued two...high altitude air travel is the transportation of the fuel itself. Our targeted strategy is to transform CO2 into viable building blocks for synthetic

  7. Bifunctional dendronized cellulose surfaces as biosensors.

    Science.gov (United States)

    Montanez, Maria I; Hed, Yvonne; Utsel, Simon; Ropponen, Jarmo; Malmstrom, Eva; Wagberg, Lars; Hult, Anders; Malkoch, Michael

    2011-06-13

    Well-defined dendronized cellulose substrates displaying multiple representations of dual-functionality were constructed by taking advantage of the efficiency of the click reaction combined with traditional anhydride chemistry. First, activated cellulose surfaces were decorated with several generations of dendrons, and their peripheral reactive groups were subsequently reacted with a trifunctional orthogonal monomer. The generated substrate tool box was successfully explored by accurately tuning the surface function using a versatile orthogonal dual postfunctionalization approach. In general, the reactions were monitored by using a click-dye reagent or a quartz crystal microbalance (QCM) technique, and the resulting surfaces were well-characterized using XPS, FT-IR, and contact angle measurements. Utilizing this approach two different surfaces have been obtained; that is, triethylenglycol oligomers and amoxicillin molecules were efficiently introduced to the dendritic surface. As a second example, mannose-decorated hydroxyl functional surfaces illustrated their potential as biosensors by multivalent detection of lectin protein at concentration as low as 5 nM.

  8. Bifunctional Bisphosphonates for Delivering Biomolecules to Bone

    Science.gov (United States)

    2012-01-13

    CTx is generally produced by osteoclasts in the bone degradation process and can be detected in blood or urine . BP treatment also reduces the...therapeutic agents with aldehyde or ketone functional groups could be conjugated to the HBPs and immobilized on bone or HA surface to explore further...1 Time (min) Ti tr an t V ol um e (m L ) 1Alendronate 2 3 Figure 3.1. Plots of HA crystal growth in presence of

  9. Cooperative CO2 Absorption Isotherms from a Bifunctional Guanidine and Bifunctional Alcohol

    OpenAIRE

    Steinhardt, Rachel; Hiew, Stanley C.; Mohapatra, Hemakesh; Nguyen, Du; Oh, Zachary; Truong, Richard; Esser-Kahn, Aaron

    2017-01-01

    Designing new liquids for CO2 absorption is a challenge in CO2 removal. Here, achieving low regeneration energies while keeping high selectivity and large capacity are current challenges. Recent cooperative metal–organic frameworks have shown the potential to address many of these challenges. However, many absorbent systems and designs rely on liquid capture agents. We present herein a liquid absorption system which exhibits cooperative CO2 absorption isotherms. Upon introduction, CO2 uptake ...

  10. 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

  11. 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...

  12. Crystallization of recombinant bifunctional nuclease TBN1 from tomato

    Czech Academy of Sciences Publication Activity Database

    Kovaľ, Tomáš; Lipovová, P.; Podzimek, Tomáš; Matoušek, Jaroslav; Dušková, Jarmila; Skálová, Tereza; Štěpánková, Andrea; Hašek, Jindřich; Dohnálek, Jan

    2011-01-01

    Roč. 67, č. 1 (2011), s. 124-128 ISSN 1744-3091 R&D Projects: GA ČR GA310/09/1407; GA ČR GA202/06/0757; GA ČR GA521/09/1214 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521; CEZ:AV0Z40500505; CEZ:AV0Z50510513 Keywords : plant endonuclease * anti-tumor properties * crystallization * X-ray diffraction Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.506, year: 2011

  13. Catalytic characterization of bi-functional catalysts derived from Pd ...

    Indian Academy of Sciences (India)

    Pd + Mg)/Al ≈ 3 and Mg/Pd ≈ 750 to 35, were prepared by coprecipitation of metal ... with acid, base and hydrogenating sites, were highly active and selective for one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen.

  14. Genetics Home Reference: D-bifunctional protein deficiency

    Science.gov (United States)

    ... shortens the fatty acid molecules by two carbon atoms at a time until the fatty acids are ... direct-to-consumer genetic testing? What is precision medicine? What is newborn screening? New Pages Obstructive sleep ...

  15. 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.

  16. 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)

  17. Apelin/APJ system: A bifunctional target for cardiac hypertrophy.

    Science.gov (United States)

    Lu, Liqun; Wu, Di; Li, Lanfang; Chen, Linxi

    2017-03-01

    Apelin acts as the endogenous ligand of G protein coupled receptors APJ. The apelin/APJ system is responsible for the occurrence and development of cardiovascular diseases. In recent years, apelin/APJ has been considered to play an important role in cardiac hypertrophy, but whether that role is beneficial or aggravating remains controversial. Apelin/APJ alleviates cardiac hypertrophy which is triggered by angiotensin II, oxidative stress and exercise. However, central administration of apelin induces cardiac hypertrophy. Peripheral administration of apelin also promotes the development of cardiac hypertrophy under non-pathological conditions. Furthermore, our laboratory discovers that apelin/APJ is able to induce hypertrophy of cardiomyocytes in vitro. The exact mechanism of apelin/APJ's dual effects in cardiac hypertrophy requires further study. In this paper, we review the controversies associated with apelin/APJ in cardiac hypertrophy and we elaborate the role of apelin/APJ in cardiac hypertrophy related-diseases including obesity, diabetes, hypertension, myocarditis and myocardial infarction. We conclude that further studies should emphasize more about the relationship between apelin/APJ and pathological hypertrophy especially in clinical patients. Moreover, apelin/APJ can be a promising therapeutic target for cardiac hypertrophy. Copyright © 2016. Published by Elsevier B.V.

  18. Bifunctional ammonium compounds as promising extragents of metals

    International Nuclear Information System (INIS)

    Rakhman'ko, E.M.; Polishchuk, S.V.; Tsvirko, G.A.; Starobinets, G.L.; Leshchev, S.M.

    1988-01-01

    Salts of dinonyl-aminoethyl-β-trinonylammonium (DNAE-β-TNA) and methylpentadecylethylenediammonium (MPDEDA) have been synthesized and studied as extractions. Extraction of CdBr 2 and CdI 2 by MPDEDA picrate in toluene and their binary mixture with chloroform, amyl-acetate and octane is investigated. It is shown that Cd is extracted by quaternary ammonium salt in the form of complex anion CdX 4 2- , where X-Br, I. The mechanism and extraction process kinetics are described. Molecular structure of the complexes formed is presented. 2 refs.; 2 figs.; 2 tabs

  19. A Bifunctional Spin Label for Ligand Recognition on Surfaces

    OpenAIRE

    Hollas, Michael A.; Webb, Simon J.; Flitsch, Sabine L.; Fielding, Alistair J.

    2017-01-01

    Abstract In?situ monitoring of biomolecular recognition, especially at surfaces, still presents a significant technical challenge. Electron paramagnetic resonance (EPR) of biomolecules spin?labeled with nitroxides can offer uniquely sensitive and selective insights into these processes, but new spin?labeling strategies are needed. The synthesis and study of a bromoacrylaldehyde spin label (BASL), which features two attachment points with orthogonal reactivity is reported. The first examples o...

  20. 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...

  1. Bifunctional atomic force microscopy probes for molecular screening applications

    Energy Technology Data Exchange (ETDEWEB)

    Wilde, Lisa M.; Allen, Stephanie; Davies, Martyn C.; Tendler, Saul J.B.; Williams, Philip M.; Roberts, Clive J

    2003-03-05

    Force mapping with the atomic force microscope (AFM) allows the simultaneous acquisition of topography and probe-sample interaction data. For example, AFM probes functionalised with an antigen can be employed to map the spatial distribution of recognition events on a substrate functionalised with its specific antibody. However, to date this method has been limited to the detection of single receptor-ligand species. Were the detection of multiple receptor-ligand interactions possible, force mapping would offer great scope as a sensitive tool for bioassay and screening applications. We have developed an immobilisation strategy, which allows two different molecular species (in this case human serum albumin and the {beta} subunit of human chorionic gonadotropin) to be present simultaneously on an AFM probe. Single point force spectroscopy results have revealed the ability of such probes to discriminate between their corresponding recognition points (anti-HSA and anti-{beta}hCG IgG antibodies). As a control, force measurements were re-recorded in the presence of the known antigen (free in solution) for each antibody species and a marked decrease in the frequency of specific interaction is observed. As an additional control interactions between anti-{beta}hCG IgG and the multifunctional probe are taken in the presence of free {beta}hCG ('true' antigen) and free HSA ('false' antigen). It is shown that measurements recorded in the presence of a non-related protein species results in no change in either the force observed or the frequency of specific interactions, further confirmation that the specificity of force observed is due to the separation of antibody-antigen complex.

  2. Independent Manipulation of Heat and Electrical Current via Bifunctional Metamaterials

    Directory of Open Access Journals (Sweden)

    Massimo Moccia

    2014-05-01

    Full Text Available Spatial tailoring of the material constitutive properties is a well-known strategy to mold the local flow of given observables in different physical domains. Coordinate-transformation-based methods (e.g., transformation optics offer a powerful and systematic approach to design anisotropic, spatially inhomogeneous artificial materials (metamaterials capable of precisely manipulating wave-based (electromagnetic, acoustic, elastic as well as diffusion-based (heat phenomena in a desired fashion. However, as versatile as these approaches have been, most designs have thus far been limited to serving single-target functionalities in a given physical domain. Here, we present a step towards a “transformation multiphysics” framework that allows independent and simultaneous manipulation of multiple physical phenomena. As a proof of principle of this new scheme, we design and synthesize (in terms of realistic material constituents a metamaterial shell that simultaneously behaves as a thermal concentrator and an electrical “invisibility cloak.” Our numerical results open up intriguing possibilities in the largely unexplored phase space of multifunctional metadevices, with a wide variety of potential applications to electrical, magnetic, acoustic, and thermal scenarios.

  3. Use of Bifunctional Immunotherapeutic Agents to Target Breast Cancer

    Science.gov (United States)

    2007-07-01

    enhanced effi- cacy and reduced cyto- toxicity (47–49). Therefore, we envisioned that compound 4 could serve as an archetype of a traditional targeted...4313. [54] A. K. Sarkar, K. L. Matta, Carbohydr. Res. 1992, 233, 245. [55] K. H. Jung , M. Hoch, R. R. Schmidt, Liebigs Ann. Chem. 1989, 1099. [56] P

  4. Bifunctional xylanases and their potential use in biotechnology

    Digital Repository Service at National Institute of Oceanography (India)

    Khandeparker, R.; Numan, M.Th.

    ), we could obtain not only economic but also environmental beneWts, such as the reduction of greenhouse gas emission. A critical factor concerning the cost of this process is the presence of eYcient, cheap cellulases and xylanases to achieve this goal... oat and barley cultivars. Cereal Chem 74:476–480 8. Bonnin E, Le GoV A, Saulnier L, Chaurand M, Thibault JF (1998) Preliminary characterisation of endogenous wheat arabinoxylan- degrading enzymic extracts. J Cereal Sci 28:53–62 9. Bulock KG, Beardsley...

  5. Synthesis and characterization of bi-functional magneto-luminescent ...

    Indian Academy of Sciences (India)

    wise method for the preparation of multifunctional magnetic-fluorescent nanocomposites with Fe3O4 na- nospheres as the core and Eu3+ doped sodium lutetium fluoride (NaLuF4:Eu3+) as the shell. Luminescence effi- ciency of Eu3+ doped NaLaF4 nanoparticles present at the surface and super-paramagnetic behavior of ...

  6. Catalytic characterization of bi-functional catalysts derived from Pd ...

    Indian Academy of Sciences (India)

    Unknown

    with JCPDS data base and previously reported data. Thermogravimetric analyses, in the range 20–850°C, ... to the data reported elsewhere (Reiche et al 2000), in order to reach good resolution of the reduction ..... hydrogenation to form DIBK or MIBA, respectively. Self-condensation of MIBK followed by hydrogenation.

  7. 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)

  8. Catalytic characterization of bi-functional catalysts derived from Pd ...

    Indian Academy of Sciences (India)

    Unknown

    from Pd–Mg–Al layered double hydroxides. N N DAS* ... for one-step synthesis of methyl isobutyl ketone (MIBK) from acetone and hydrogen. The results ... this method ensures the maximum utilization of Pd, the homogeneity and reproducibility of the preparation method may be poor. For a catalytic system, whose activity.

  9. Targeting Prostate Cancer with Bifunctional Modulators of the Androgen Receptor

    Science.gov (United States)

    2013-10-01

    A.; Cordon-Cardo, C.; Thaler , H. T.; Rifkind, R. A.; Marks, P. A.; Richon, V. M. Suberoylanilide hydroxamic acid, an inhibitor of histone...three-hybrid system. Analytical Biochemistry 363:160-162 28. Richards SJ, von Geldern TW, Jacobson P, Wilcox D, Nguyen P, Öhman L, Österlund M

  10. Synthesis and characterization of bi-functional magneto-luminescent ...

    Indian Academy of Sciences (India)

    hybrid core/shell nanospheres. JIGMET LADOLa, HEENA KHAJURIAa, HAQ NAWAZ SHEIKHa,∗ and YUGAL KHAJURIAb. aDepartment of Chemistry, University of Jammu, Jammu 180 006, India. bSchool of Physics, Shri Mata Vaishno Devi University, Katra 182 320, India e-mail: hnsheikh@rediffmail.com. MS received 15 ...

  11. Ultrafast SET-LRP with Peptoid Cytostatic Drugs as Monofunctional and Bifunctional Initiators.

    Science.gov (United States)

    Lligadas, Gerard; Enayati, Mojtaba; Grama, Silvia; Smail, Rauan; Sherman, Samuel E; Percec, Virgil

    2017-08-14

    To continue expanding the use of Single Electron Transfer-Living Radical Polymerization (SET-LRP) in applications at the interface between macromolecular science, biomacromolecules, biology and medicine, it is essential to develop novel initiators that do not compromise the structural stability of synthesized polymers in biological environments. Here, we report that stable 2-bromopropionyl peptoid-type initiators such as 1,4-bis(2-bromopropionyl)piperazine and 4-(2-bromopropionyl)morpholine are an alternative that meets the standards reached by the well-known secondary and tertiary α-haloester-type initiators in terms of excellent control over molecular weight evolution and distribution as well as polymer chain ends. SET-LRP methodologies in organic, aqueous, and biphasic organic-aqueous media were evaluated for this purpose.

  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. 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.

  14. Microwave assisted bi-functional activation of β-bromo-tert-alcohols

    Indian Academy of Sciences (India)

    NANDINI KANNAN, MANJUNATHA JAVAGAL RANGASWAMY and. BETTADAIAH BHEEMANAKERE KEMAPAIAH∗. Spice and Flavour Science Department, CSIR-Central Food Technological Research Institute,. Mysore 570 020, India e-mail: bettadaiah@cftri.res.in. MS received 19 September 2014; revised 5 May 2015; ...

  15. 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

    Bimetallic surfaces offer activity benefits derived from synergistic effects among active sites with uniquely different functions, which is particularly important for the development of highly effective heterogeneous catalysts for specific technological applications, such as energy conversion...... 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....

  16. 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.

  17. 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

  18. Microbial production of bi-functional molecules by diversification of the fatty acid pathway.

    Science.gov (United States)

    Garg, Shivani; Rizhsky, Ludmila; Jin, Huanan; Yu, Xiaochen; Jing, Fuyuan; Yandeau-Nelson, Marna D; Nikolau, Basil J

    2016-05-01

    Fatty acids that are chemically functionalized at their ω-ends are rare in nature yet offer unique chemical and physical properties with wide ranging industrial applications as feedstocks for bio-based polymers, lubricants and surfactants. Two enzymatic determinants control this ω-group functionality, the availability of an appropriate acyl-CoA substrate for initiating fatty acid biosynthesis, and a fatty acid synthase (FAS) variant that can accommodate that substrate in the initial condensation reaction of the process. In Type II FAS, 3-ketoacyl-ACP synthase III (KASIII) catalyses this initial condensation reaction. We characterized KASIIIs from diverse bacterial sources, and identified variants with novel substrate specificities towards atypical acyl-CoA substrates, including 3-hydroxybutyryl-CoA. Using Alicyclobacillus acidocaldarius KASIII, we demonstrate the in vivo diversion of FAS to produce novel ω-1 hydroxy-branched fatty acids from glucose in two bioengineered microbial hosts. This study unveils the biocatalytic potential of KASIII for synthesizing diverse ω-functionalized fatty acids. Copyright © 2016 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  19. 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.

  20. Nanoscale determination of antiviral drug acyclovir engaging bifunctionality of single walled carbon nanotubes - nafion film.

    Science.gov (United States)

    Tarlekar, Pravin; Khan, Afsan; Chatterjee, Sanghamitra

    2018-03-20

    An elementary and exemplary approach is proposed for the accurate monitoring of antiviral drug acyclovir (ACV) utilizing glassy carbon electrode (GCE) fabricated with single-walled carbon nanotubes and nafion composite film employing square wave voltammetry for the first time. The developed sensor exhibits effective and sustained electron mediating behavior displaying higher peak currents at lower potential than those obtained at bare GCE. At optimal experimental conditions, oxidation current showed a wide linear response for ACV in the concentration range from 10 nM to 30 μM. The proposed sensor exhibited pronounced analytical performance for the determination of ACV with limit of detection corresponding to 1.8 nM and high sensitivity of 15.4 μA μM -1 . The modified sensor showcased high recognition selectivity, fair reproducibility and long term stability of signal response in the physiological environment. The developed prototype was successfully implemented to quantify ACV in several commercially available pharmaceuticals. The versatile method described herein was efficaciously applied further in detecting ACV in real human urine sample of patient undergoing pharmacological treatment with ACV. The results explicitly demonstrate the applicability of the developed sensor in quality control, pharmacokinetic studies and clinical analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Stability of photochromism in new bifunctional copolymers containing spiropyran and chalcone moiety in the side chain

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Dong Hoon; Ban, Si Young; Kim, Jae Hong [Kyunghee Univ., Suwon (Korea, Republic of)

    2003-04-01

    We synthesized three copolymers bearing photochromic spiropyran dye and chalcone moiety in the side chain for studying the dynamic properties of their photochromism. They contain methacrylate-spiropyran (MA-spiropyran) and methacrylate-chalcone) (MA-chalcone) with the different concentration. The photosensitivity of the newly synthesized copolymers was investigated by using UV-Vis absorption spectroscopy. We absorbed photodimerization and phtochromic behavior under UV irradiation at the same time. The effect of photocrosslink on the rate and stability of photochromism in three copolymers was considered in this study. This study might be helpful to design photochromic materials for irreversible optical memory by virtue of photocrosslinking reaction.

  2. Bifunctional thermoelectric tube made of tilted multilayer material as an alternative to standard heat exchangers.

    Science.gov (United States)

    Takahashi, Kouhei; Kanno, Tsutomu; Sakai, Akihiro; Tamaki, Hiromasa; Kusada, Hideo; Yamada, Yuka

    2013-01-01

    Enormously large amount of heat produced by human activities is now mostly wasted into the environment without use. To realize a sustainable society, it is important to develop practical solutions for waste heat recovery. Here, we demonstrate that a tubular thermoelectric device made of tilted multilayer of Bi(0.5)Sb(1.5)Te3/Ni provides a promising solution. The Bi(0.5)Sb(1.5)Te3/Ni tube allows tightly sealed fluid flow inside itself, and operates in analogy with the standard shell and tube heat exchanger. We show that it achieves perfect balance between efficient heat exchange and high-power generation with a heat transfer coefficient of 4.0 kW/m(2)K and a volume power density of 10 kW/m(3) using low-grade heat sources below 100°C. The Bi(0.5)Sb(1.5)Te3/Ni tube thus serves as a power generator and a heat exchanger within a single unit, which is advantageous for developing new cogeneration systems in factories, vessels, and automobiles where cooling of excess heat is routinely carried out.

  3. 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.

  4. 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...

  5. 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.

  6. 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.

  7. Bifunctional ultraviolet/ultrasound responsive composite TiO2/polyelectrolyte microcapsules

    Science.gov (United States)

    Gao, Hui; Wen, Dongsheng; Tarakina, Nadezda V.; Liang, Jierong; Bushby, Andy J.; Sukhorukov, Gleb B.

    2016-02-01

    Designing and fabricating multifunctional microcapsules are of considerable interest in both academic and industrial research aspects. This work reports an innovative approach to fabricate composite capsules with high UV and ultrasound responsive functionalities that can be used as external triggers for controlled release, yet with enhanced mechanical strength that can make them survive in a harsh environment. Needle-like TiO2 nanoparticles (NPs) were produced in situ into layer-by-layer (LbL) polyelectrolyte (PE) shells through the hydrolysis of titanium butoxide (TIBO). These rigid TiO2 NPs yielded the formed capsules with excellent mechanical strength, showing a free standing structure. A possible mechanism is proposed for the special morphology formation of the TiO2 NPs and their reinforcing effects. Synergistically, their response to UV and ultrasound was visualized via SEM, with the results showing an irreversible shell rapture upon exposure to either UV or ultrasound irradiation. As expected, the release studies revealed that the dextran release from the TiO2/PE capsules was both UV-dependent and ultrasound-dependent. Besides, the biocompatibility of the capsules with the incorporation of amorphous TiO2 NPs was confirmed by an MTT assay experiment. All these pieces of evidence suggested a considerable potential medicinal application of TiO2/PE capsules for controlled drug delivery.Designing and fabricating multifunctional microcapsules are of considerable interest in both academic and industrial research aspects. This work reports an innovative approach to fabricate composite capsules with high UV and ultrasound responsive functionalities that can be used as external triggers for controlled release, yet with enhanced mechanical strength that can make them survive in a harsh environment. Needle-like TiO2 nanoparticles (NPs) were produced in situ into layer-by-layer (LbL) polyelectrolyte (PE) shells through the hydrolysis of titanium butoxide (TIBO). These rigid TiO2 NPs yielded the formed capsules with excellent mechanical strength, showing a free standing structure. A possible mechanism is proposed for the special morphology formation of the TiO2 NPs and their reinforcing effects. Synergistically, their response to UV and ultrasound was visualized via SEM, with the results showing an irreversible shell rapture upon exposure to either UV or ultrasound irradiation. As expected, the release studies revealed that the dextran release from the TiO2/PE capsules was both UV-dependent and ultrasound-dependent. Besides, the biocompatibility of the capsules with the incorporation of amorphous TiO2 NPs was confirmed by an MTT assay experiment. All these pieces of evidence suggested a considerable potential medicinal application of TiO2/PE capsules for controlled drug delivery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06666b

  8. 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...

  9. 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 Scientific, Rockford, USA) and centrifugation (10 000 x g, 10 min), the supernatant was resolved using 12% (sodium dodecyl sulphate) polyacrylamide gel electrophoresis (SDS-PAGE) to determine the expression profile of the two proteins. Following...-Nachel, Germany) and the bound proteins eluted with 250 mM imidazole. Eluted protein was then diafiltered (30 kDa membrane) with sodium phosphate buffer (50 mM, pH 7.5). The protein concentration of the purified sample was determined by a method of Bradford [6...

  10. 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

  11. 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.

  12. 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.

  13. Radiation sterilization of a bifunctional cement formulation of hydroxilapatite-plaster-polymers.

    Science.gov (United States)

    Sainz Vidal, D; Rodriquez Napoles, D; Fuentes Estevez, G; Guerra, M; Arcis Soriano, W; Peon Aves, E; Diaz Argota, J M; Zaldivar Silva, D

    1999-06-18

    A sterilization method based on the use of gamma ionizing radiation was applied to a cement formulation of hydroxilapatite, plaster and polymers to be used in bone restorations in dental, aesthetic, and neurological surgery. After the cement was exposed to a dose of 21.5 kGy it reached the sterility assurance level which was necessary for its employment in surgical applications as specified by International Standard ISO ordinate 11137: Radiation Sterilization of Health Care Products. No variation in the initial cement composition or processing parameters, such as working or setting time and molding quality was observed due to sterilization. Its characteristics as a drug delivery system were also not affected. Therefore, radiation sterilization provides a feasible alternative to conventional sterilization methods such as dry/wet heat and ethylene oxide.

  14. 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.

  15. 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.

  16. 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.

  17. 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...

  18. Enhanced bifunctional fuel cell catalysis via Pd/PtCu core/shell nanoplates.

    Science.gov (United States)

    Lin, Fei; Wang, Kai; Tang, Yonghua; Lai, Jianping; Lou, Mingchuan; Huang, Minghua; Guo, Shaojun

    2018-02-01

    Depositing Pt atoms on nanoscale two-dimensional (2D) substrates resulting in the exposure of specific crystal facets is an effective strategy for reducing the Pt content without compromising the catalytic property. Herein, the Pd/PtCu core/shell nanoplates exhibit substantially improved ORR and MOR mass activities, 8.3 and 3.3 times higher than those of commercial Pt. The present work highlights the important role of designing a 2D core/shell nanostructure in enhancing fuel cell electrocatalysis.

  19. Construction and shuttling of novel bifunctional vectors for Streptomyces spp. and Escherichia coli.

    OpenAIRE

    Neesen, K; Volckaert, G

    1989-01-01

    Shuttle vectors for gene transfer between Streptomyces spp. and Escherichia coli have been constructed by fusion of an artificial multicopy E. coli replicon and DNA fragments of pIJ702. Stable transfer to Streptomyces lividans was obtained. Marked differences in transformation efficiency were observed when plasmid DNA isolated from E. coli GM119 was used instead of that from strain HB101.

  20. Effect of lithium tert-alkoxidess on anionic polymerization of butadiene initiated with a bifunctional initiator

    Czech Academy of Sciences Publication Activity Database

    Toman, Luděk; Vlček, Petr; Sufčák, M.; Pleska, A.; Spěváček, Jiří; Holler, Petr

    2000-01-01

    Roč. 65, č. 3 (2000), s. 352-360 ISSN 0010-0765 Grant - others:CZ(XC) Kaučuk Kralupy Institutional research plan: CEZ:AV0Z4050913 Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.960, year: 2000

  1. Imaging in solution of (Lys)(16)-containing bifunctional synthetic peptide/DNA nanoparticles for gene delivery.

    Science.gov (United States)

    Collins, Louise; Kaszuba, Michael; Fabre, John W

    2004-04-07

    The physical properties of non-viral vector/DNA nanoparticles in physiological aqueous solution are poorly understood. A Fluid Particle Image Analyser (FPIA), normally used for analysis of industrial and environmental fluids, was used to visualise individual (Lys)(16)-containing peptide/DNA particles. Eight (Lys)(16)-containing synthetic peptides were used to generate peptide/DNA particles at a constant + to - charge ratio of 2.8:1 with 10 microg/ml of plasmid DNA in phosphate buffered saline. Dynamic Light Scattering (DLS) and gene delivery studies were also performed. We present the first images of non-viral vector/DNA nanoparticles in physiological aqueous solution, together with precise measurements of individual particle size and shape in solution and, for the first time, an accurate measure of particle number. Particle size and shape, particle number, and efficiency for gene delivery varied markedly with different peptides. Under standard conditions for in vitro gene delivery, we estimate approximately 60 peptide/DNA nanoparticles per target cell, each containing approximately 70,000 plasmids. This novel capacity to image individual vector/DNA nanoparticles in solution and to count them accurately will enable a more precise assessment of non-viral gene delivery systems, and a more quantitative interpretation of gene delivery experiments.

  2. Molecular characterization of the bifunctional VHDL-CP from the hemolymph of white shrimp Penaeus vannamei.

    Science.gov (United States)

    Yepiz-Plascencia, Gloria; Jiménez-Vega, Florinda; Romo-Figueroa, María Gabriela; Sotelo-Mundo, Rogerio R; Vargas-Albores, Francisco

    2002-07-01

    A very high-density lipoprotein (VHDL) purified from the hemolymph of the white shrimp Penaeus vannamei is shown to be identical to the clotting protein (CP) previously reported from the same organism based on size, subunits and N-terminal amino acid sequence. The approximately 440-kDa protein, a homodimer of approximately 200-kDa subunits, was present in KBr gradient fractions ranging in density from 1.155 to 1.212 g/ml. Samples of VHDL after purification by strong cation exchange chromatography were subjected to electrophoresis on native polyacrylamide gels. Lipids associated with the VHDL were detected by Sudan Black and Oil Red O staining and comprise 9-15% of the purified protein. Circular dichroism of VHDL-CP indicates that the alpha-helix content of the VHDL-CP is 32%, while beta-sheets correspond to 33%, closely resembling the secondary structure of CP from the shrimp Penaeus monodon and, remarkably, the secondary structure of very high-density lipophorin E (VHDLpE) from the tobacco hornworm, Manduca sexta.

  3. 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

  4. Bifunctional Porphyrin-Based Nano-Metal-Organic Frameworks: Catalytic and Chemosensing Studies.

    Science.gov (United States)

    Pereira, Carla F; Figueira, Flávio; Mendes, Ricardo F; Rocha, João; Hupp, Joseph T; Farha, Omar K; Simões, Mário M Q; Tomé, João P C; Paz, Filipe A Almeida

    2018-03-13

    The use of 5,10,15,20-tetrakis( p-phenylphosphonic acid)porphyrin (H 10 TPPA) as a linker in the preparation of porphyrin-based metal-organic frameworks (Por-MOFs) through coordination to lanthanides cations is reported. The resulting unprecedented materials, formulated as [M(H 9 TPPA)(H 2 O) x ]Cl 2 · yH 2 O [ x + y = 7; M 3+ = La 3+ (1), Yb 3+ (2), and Y 3+ (3)], prepared using hydrothermal synthesis, were extensively characterized in the solid-state, for both their structure and thermal robustness, using a myriad of solid-state advanced techniques. Materials were evaluated as heterogeneous catalysts in the oxidation of thioanisole by H 2 O 2 and as chemosensors for detection of nitroaromatic compounds (NACs). Nano-Por-MOFs 1-3 proved to be effective as heterogeneous catalysts in the sulfoxidation of thioanisole, with Por-MOF 1 exhibiting the best catalytic performance with a conversion of thioanisole of 89% in the first cycle and with a high selectivity for the sulfoxide derivative (90%). The catalyst maintained its activity roughly constant in three consecutive runs. Por-MOFs 1-3 can be employed as chemosensors because of a measured fluorescence quenching up to 70% for nitrobenzene, 1,4-dinitrobenzene, 4-nitrophenol, and phenol, with 2,4,6-trinitrophenol exhibiting a peculiar fluorescence profile.

  5. Bioethanol Production:Characterisation of a Bifunctional Alcohol Dehydrogenase from Geobacillus thermoglucosidasius

    OpenAIRE

    Extance, Jonathan

    2012-01-01

    Unlike first generation biofuels, those produced from ligno-cellulosic waste material (second generation) have the potential to offer sustainable fuel production without competition for food products, whilst making significant savings in terms of greenhouse gas emissions. Second generation bioethanol has the potential to offer a stop-gap between current vehicle fuelling technologies and future solutions such as biohydrogen.TMO Renewables Ltd, a leading developer of the second-generation conve...

  6. Cobalt Iron Hydroxide as a Precious Metal-Free Bifunctional Electrocatalyst for Efficient Overall Water Splitting.

    Science.gov (United States)

    Babar, Pravin; Lokhande, Abhishek; Shin, Hyeong Ho; Pawar, Bharati; Gang, Myeng Gil; Pawar, Sambhaji; Kim, Jin Hyeok

    2018-02-01

    Highly efficient and stable electrocatalysts from inexpensive and earth-abundant elements are emerging materials in the overall water splitting process. Herein, cobalt iron hydroxide nanosheets are directly deposited on nickel foam by a simple and rapid electrodeposition method. The cobalt iron hydroxide (CoFe/NF) nanosheets not only allow good exposure of the highly active surface area but also facilitate the mass and charge transport capability. As an anode, the CoFe/NF electrocatalyst displays excellent oxygen evolution reaction catalytic activity with an overpotential of 220 mV at a current density of 10 mA cm -2 . As a cathode, it exhibits good performance in the hydrogen evolution reaction with an overpotential of 110 mV, reaching a current density of 10 mA cm -2 . When CoFe/NF electrodes are used as the anode and the cathode for water splitting, a low cell voltage of 1.64 V at 10 mA cm -2 and excellent stability for 50 h are observed. The present work demonstrates a possible pathway to develop a highly active and durable substitute for noble metal electrocatalysts for overall water splitting. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    Science.gov (United States)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  8. Nanoencapsulation strategies for the delivery of novel bifunctional antioxidant/σ1 selective ligands.

    Science.gov (United States)

    Carbone, Claudia; Arena, Emanuela; Pepe, Veronica; Prezzavento, Orazio; Cacciatore, Ivana; Turkez, Hasan; Marrazzo, Agostino; Di Stefano, Antonio; Puglisi, Giovanni

    2017-07-01

    Nowadays sigma-1 receptors are considered as new therapeutic objectives for central nervous system neurodegenerative diseases. Among different molecules, alpha lipoic acid has been identified as a natural potent antioxidant drug, whose therapeutic efficacy is limited by its many drawbacks, such as fast metabolism, poor bioavailability and high physico-chemical instability. Alfa-lipoic acid derivatives have been recently developed demonstrating their neuroprotective activity and effectiveness in different types of oxidative stress. In this work, two derivatives containing an amide or an ester functional group with different lipophilicity, were selected for their important affinity for sigma-1 receptors. Herein, in order to improve the in vitro stability and antioxidant effectiveness of alpha-lipoic acid derivatives, we focused our efforts in the nanoencapsulation strategies. Aqueous-core nanocapsules for the delivery of the hydrophilic compound and nanostructured lipid carrier for the lipophilic derivative, were properly designed and prepared using a direct or inverse eco-friendly organic solvent-free procedure. All nanosystems were characterized in terms of mean size, polydispersity, stability, morphology, encapsulation efficiency and in vitro release profiles. In order to evaluate the nanocarriers biocompatibility and antioxidant effectiveness, in vitro biological studies (cell viability, total antioxidant capacity and total oxidative status) were developed on primary human whole blood cell cultures, on both unloaded and derivatives-loaded nanodevices. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Peroxisomal D-bifunctional protein deficiency Three adults diagnosed by whole-exome sequencing

    NARCIS (Netherlands)

    Lines, Matthew A.; Jobling, Rebekah; Brady, Lauren; Marshall, Christian R.; Scherer, Stephen W.; Rodriguez, Amadeo R.; Lee, Liesly; Lang, Anthony E.; Mestre, Tiago A.; Wanders, Ronald J. A.; Ferdinandusse, Sacha; Tarnopolsky, Mark A.

    2014-01-01

    Objective:To determine the causative genetic lesion in 3 adult siblings with a slowly progressive, juvenile-onset phenotype comprising cerebellar atrophy and ataxia, intellectual decline, hearing loss, hypogonadism, hyperreflexia, a demyelinating sensorimotor neuropathy, and (in 2 of 3 probands)

  10. 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.

  11. 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.

  12. Asymmetric Synthesis of Spirooxindoles via Nucleophilic Epoxidation Promoted by Bifunctional Organocatalysts

    Directory of Open Access Journals (Sweden)

    Martina Miceli

    2018-02-01

    Full Text Available Taking into account the postulated reaction mechanism for the organocatalytic epoxidation of electron-poor olefins developed by our laboratory, we have investigated the key factors able to positively influence the H-bond network installed inside the substrate/catalyst/oxidizing agent. With this aim, we have: (i tested a few catalysts displaying various effects that noticeably differ in terms of steric hindrance and electron demand; (ii employed α-alkylidene oxindoles decorated with different substituents on the aromatic ring (11a–g, the exocylic double bond (11h–l, and the amide moiety (11m–v. The observed results suggest that the modification of the electron-withdrawing group (EWG weakly conditions the overall outcomes, and conversely a strong influence is unambiguously ascribable to either the N-protected or N-unprotected lactam framework. Specifically, when the NH free substrates (11m–u are employed, an inversion of the stereochemical control is observed, while the introduction of a Boc protecting group affords the desired product 12v in excellent enantioselectivity (97:3 er.

  13. Arsenene-Based Heterostructures: Highly Efficient Bifunctional Materials for Photovoltaics and Photocatalytics.

    Science.gov (United States)

    Niu, Xianghong; Li, Yunhai; Zhou, Qionghua; Shu, Huabing; Wang, Jinlan

    2017-12-13

    Constructing suitable type II heterostructures is a reliable solution for high-efficient photovoltaic and photocatalytic materials. Arsenene, as a rising member of monoelemental two-dimensional materials, shows great potential as a building block of heterostructures because of its suitable band gap, high carrier mobility, and good optical properties. On the basis of accurate band structure calculations by combining the many-body perturbation GW method with an extrapolation technique, we demonstrate that arsenene-based heterostructures paired with molybdenum disulfide, tetracyano-quinodimethane, or tetracyanonaphtho-quinodimethane can form type II band alignments. These arsenene-based heterostructures cannot only satisfy all the requirements as photocatalysts for photocatalytic water splitting but can also show an excellent power conversion efficiency of ∼20% as potential photovoltaics.

  14. Development of Novel Bifunctional Compounds that Induce Apoptosis in Prostate Cancer Cells

    Science.gov (United States)

    2005-02-01

    ionization mass spectometry (EIMS). The EIMS technique did not prove sensitive enough to accurately quantify DNA adducts in cell culture experiments...INVESTIGATOR: John M. Essigmann, Ph.D. CONTRACTING ORGANIZATION: Massachusetts Institute of Technology Cambridge, Massachusetts 02139 REPORT DATE : February...AGENCY USE ONLY 2. REPORT DATE 3. REPORT TYPE AND DATES COVERED (Leave blank) February 2005 Annual (1 Feb 2004 - 31 Jan 2005) 4. TITLE AND SUBTITLE 5

  15. 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.

  16. Azidobupramine, an Antidepressant-Derived Bifunctional Neurotransmitter Transporter Ligand Allowing Covalent Labeling and Attachment of Fluorophores.

    Directory of Open Access Journals (Sweden)

    Thomas Kirmeier

    Full Text Available The aim of this study was to design, synthesize and validate a multifunctional antidepressant probe that is modified at two distinct positions. The purpose of these modifications was to allow covalent linkage of the probe to interaction partners, and decoration of probe-target complexes with fluorescent reporter molecules. The strategy for the design of such a probe (i.e., azidobupramine was guided by the need for the introduction of additional functional groups, conveying the required properties while keeping the additional moieties as small as possible. This should minimize the risk of changing antidepressant-like properties of the new probe azidobupramine. To control for this, we evaluated the binding parameters of azidobupramine to known target sites such as the transporters for serotonin (SERT, norepinephrine (NET, and dopamine (DAT. The binding affinities of azidobupramine to SERT, NET, and DAT were in the range of structurally related and clinically active antidepressants. Furthermore, we successfully visualized azidobupramine-SERT complexes not only in SERT-enriched protein material but also in living cells stably overexpressing SERT. To our knowledge, azidobupramine is the first structural analogue of a tricyclic antidepressant that can be covalently linked to target structures and further attached to reporter molecules while preserving antidepressant-like properties and avoiding radioactive isotopes.

  17. 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.

  18. 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...

  19. 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

    Pectins are the most complex polysaccharides of the plant cell wall. Based on the number of methylations, acetylations, and glycosidic linkages present in their structures, it is estimated that up to 67 transferase activities are involved in pectin biosynthesis. Pectic galactans constitute a majo...

  20. 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.)

  1. A General Asymmetric Formal Synthesis of Aza-Baylis-Hillman Type Products under Bifunctional Catalysis.

    Science.gov (United States)

    Frías, María; Carrasco, Ana Cristina; Fraile, Alberto; Alemán, José

    2018-03-02

    A new organocatalytic strategy for the synthesis of enantioenriched aza-Baylis-Hillman type products via a frustrated vinylogous reaction is presented. This process proceeds under mild conditions with good yields, completed Z/E selectivity and excellent enantioselectivities. Moreover, easy derivatizations of the final products led to important building blocks of organic synthesis such as 1,3-aminoalcohols and Lewis base catalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Pluronic-lysozyme conjugates as anti-adhesive and antibacterial bifunctional polymers for surface coating

    NARCIS (Netherlands)

    Muszanska, Agnieszka K.; Busscher, Henk J.; Herrmann, Andreas; van der Mei, Henny C.; Norde, Willem

    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

  3. Pluronic-lysozyme conjugates as anti-adhesive and antibacterial bifunctional polymers for surface coating

    OpenAIRE

    Muszanska, Agnieszka K.; Busscher, Henk J.; Herrmann, Andreas; van der Mei, Henny C.; Norde, Willem

    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 telechelic groups of the PEO chains. Covalent conjugation of lysozyme proceeded via reductive amination of aldehyde functionalized PEO blocks (CHO-Pluronic) and the amine groups of the lysine resid...

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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 exchangers * functionalized resin s * polymers Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.041, year: 2003

  9. 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

  10. Kinetic modelling of the isomerization of N-Hexane using bifunctional Pt-Ni-MOR catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Brito, K.D.; Sousa, B.V.; Rodrigues, M.G.F.; Alves, J.J.N. [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academica de Engenharia Quimica], E-mail: jailson@deq.ufcg.edu.br

    2008-01-15

    The objective of the present work is to realize the kinetic modelling regarding deactivation of Pt-Ni catalysts present in mordenite zeolite and monitor the isomerization reaction of n-hexane. The catalysts have been prepared with different metal ratios for comparison in terms of ion exchange and characterization by the XRD technique, in order to correlate the catalytic behavior of the material with its properties. The catalysts were also evaluated during the isomerization reaction of n-hexane. According to the XRD analyses it was observed that the incorporation of the metals Pt and Ni in the structure of the mordenite zeolite did not change the X-Ray diffractograms after the ionic exchange process and calcination of the catalysts. Based on the results of the catalytic investigation, a kinetic model was proposed to deactivate the catalysts. By means of two correlations, the deactivation parameters were determined, allowing establishing the profile of the activity at any time, when the composition of one of the metals is known. According to the results of this work, there might be the possibility that the proposed model of deactivation is a result of coke formation. (author)

  11. Biosynthesis of the earthy odorant geosmin by a bifunctional Streptomyces coelicolor enzyme

    Science.gov (United States)

    Jiang, Jiaoyang; He, Xiaofei; Cane, David E.

    2010-01-01

    Geosmin (1) is responsible for the characteristic odor of moist soil, as well as off-flavors in drinking water and foodstuffs (ref. 1 and 2). Geosmin is generated from farnesyl diphosphate (FPP, 2) by an enzyme that in the soil organism Streptomyces coelicolor A3(2) is encoded by the SCO6073 gene (ref. 3) We have now shown that the recombinant N-terminal half of this protein catalyzes the Mg2+-dependent cyclization of FPP to germacradienol (3) and germacrene D (4), while the highly homologous C-terminal domain, previously thought to be catalytically silent, catalyzes the Mg2+-dependent conversion of germacradienol to geosmin (1). Site-directed mutagenesis confirmed that the N- and C-terminal domain each harbors a distinct, independently functioning active site. A mutation in the N-terminal domain of germacradienol–geosmin synthase of a catalytically essential serine to alanine results in the conversion of FPP (2) to a mixture of sesquiterpenes that includes an aberrant product identified as isolepidozene (6), previously suggested to be an enzyme-bound intermediate in the cyclization of FPP to germacradienol. PMID:17873868

  12. Cleavage of a RNA analog containing uridine by a bifunctional dinuclear Zn(II) catalyst.

    Science.gov (United States)

    Rossiter, Clifford S; Mathews, Ryan A; del Mundo, Imee Marie A; Morrow, Janet R

    2009-01-01

    The macrocyclic ligand, 1,4-bis((1-oxa-4,7,10-triazacyclododecan-7-yl)methyl)benzene (L1) is prepared. L1 binds two Zn(II) ions at neutral pH to form Zn(2)(L1) as studied by using pH-potentiometric titrations. Zn(2)(L1) binds two uridines at pH 7.0, I=0.100M (NaCl) and the mononuclear analog Zn(L2) (L2=1-oxa-4,7,10-triazacyclododecane) binds a single uridine; dissociation constants for both complexes are in the millimolar range. Both complexes promote the cleavage of a simple RNA analog lacking a nucleobase (HpPNP=2-hydroxypropyl-4-nitrophenylphosphate), and a uridine containing RNA analog UpPNP (uridine-3'-4-nitrophenylphosphate). Plots of the first-order rate constant for cleavage of HpPNP as a function of Zn(L2) concentration from 0.5mM to 20.0mM are linear, consistent with weak complexation to substrate K(d)>20mM. In contrast, first-order rate constants for cleavage of UpPNP by Zn(L2) or Zn(2)(L1) over similar concentration ranges exhibit a downward curvature, consistent with the formation of a complex between catalyst and UpPNP. Comparison of second-order rate constants (k(2)=k(cat)/K(d)) shows that the dinuclear complex Zn(2)(L1) is a better catalyst than Zn(L2) for both HpPNP and UpPNP cleavage.

  13. 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,. Mysore 570 020, India e-mail: bettadaiah@cftri.res.in. MS received 19 September 2014; ..... and 1c is the choice of the metal salt. The formation of 1a was the major product in the presence of ZnS whereas 1c was the major ...

  14. EVALUATION OF DESFERAL AS A BIFUNCTIONAL CHELATING AGENT FOR LABELING ANTIBODIES WITH ZR-89

    NARCIS (Netherlands)

    MEIJS, WE; HERSCHEID, JDM; Haisma, Hidde; PINEDO, HM

    1992-01-01

    Zirconium-desferal was prepared and analysed by TLC, NMR and u.v.-spectroscopy. The stoichiometry of the complex was found to be 1:1. Chelation of desferal, coupled to resin, with Zr-88 appeared to be fast and almost quantitative in various buffer systems in a broad pH-range (4-7). A high in vitro

  15. 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.

  16. Synthesis of amphiphilic copolymers by ATRP initiated with a bifunctional initiator containing trichlomethyl groups

    Czech Academy of Sciences Publication Activity Database

    Ritz, Pavel; Látalová, Petra; Janata, Miroslav; Toman, Luděk; Kříž, Jaroslav; Genzer, J.; Vlček, Petr

    2007-01-01

    Roč. 67, č. 10 (2007), s. 1027-1039 ISSN 1381-5148 R&D Projects: GA MŠk 1P05ME753 Institutional research plan: CEZ:AV0Z40500505 Keywords : ATRP * block copolymer * polyhalogenated initiator * amphiphilic copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.720, year: 2007

  17. 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.

  18. A solution-phase bifunctional catalyst for lithium-oxygen batteries.

    Science.gov (United States)

    Sun, Dan; Shen, Yue; Zhang, Wang; Yu, Ling; Yi, Ziqi; Yin, Wei; Wang, Duo; Huang, Yunhui; Wang, Jie; Wang, Deli; Goodenough, John B

    2014-06-25

    A lithium-oxygen battery would deliver the highest energy density of a rechargeable battery, but the multiphase electrochemical reaction on the air cathode has difficulty proceeding when operated with only solid catalysts. We report here the organic-electrolyte-dissolved iron phthalocyanine (FePc) as a shuttle of (O2)(-) species and electrons between the surface of the electronic conductor and the insulator Li2O2 product of discharge. The Li2O2 is observed to grow and decompose without direct contact with carbon, which greatly enhances the electrochemical performance. Our results signal that the use of molecular shuttles that are catalytically active may prove to be enablers of a practical lithium-air rechargeable battery.

  19. Protein S-thiolation by Glutathionylspermidine (Gsp): the role of Escherichia coli Gsp synthetASE/amidase in redox regulation.

    Science.gov (United States)

    Chiang, Bing-Yu; Chen, Tzu-Chieh; Pai, Chien-Hua; Chou, Chi-Chi; Chen, Hsuan-He; Ko, Tzu-Ping; Hsu, Wen-Hung; Chang, Chun-Yang; Wu, Whei-Fen; Wang, Andrew H-J; Lin, Chun-Hung

    2010-08-13

    Certain bacteria synthesize glutathionylspermidine (Gsp), from GSH and spermidine. Escherichia coli Gsp synthetase/amidase (GspSA) catalyzes both the synthesis and hydrolysis of Gsp. Prior to the work reported herein, the physiological role(s) of Gsp or how the two opposing GspSA activities are regulated had not been elucidated. We report that Gsp-modified proteins from E. coli contain mixed disulfides of Gsp and protein thiols, representing a new type of post-translational modification formerly undocumented. The level of these proteins is increased by oxidative stress. We attribute the accumulation of such proteins to the selective inactivation of GspSA amidase activity. X-ray crystallography and a chemical modification study indicated that the catalytic cysteine thiol of the GspSA amidase domain is transiently inactivated by H(2)O(2) oxidation to sulfenic acid, which is stabilized by a very short hydrogen bond with a water molecule. We propose a set of reactions that explains how the levels of Gsp and Gsp S-thiolated proteins are modulated in response to oxidative stress. The hypersensitivities of GspSA and GspSA/glutaredoxin null mutants to H(2)O(2) support the idea that GspSA and glutaredoxin act synergistically to regulate the redox environment of E. coli.

  20. Protein S-Thiolation by Glutathionylspermidine (Gsp)

    Science.gov (United States)

    Chiang, Bing-Yu; Chen, Tzu-Chieh; Pai, Chien-Hua; Chou, Chi-Chi; Chen, Hsuan-He; Ko, Tzu-Ping; Hsu, Wen-Hung; Chang, Chun-Yang; Wu, Whei-Fen; Wang, Andrew H.-J.; Lin, Chun-Hung

    2010-01-01

    Certain bacteria synthesize glutathionylspermidine (Gsp), from GSH and spermidine. Escherichia coli Gsp synthetase/amidase (GspSA) catalyzes both the synthesis and hydrolysis of Gsp. Prior to the work reported herein, the physiological role(s) of Gsp or how the two opposing GspSA activities are regulated had not been elucidated. We report that Gsp-modified proteins from E. coli contain mixed disulfides of Gsp and protein thiols, representing a new type of post-translational modification formerly undocumented. The level of these proteins is increased by oxidative stress. We attribute the accumulation of such proteins to the selective inactivation of GspSA amidase activity. X-ray crystallography and a chemical modification study indicated that the catalytic cysteine thiol of the GspSA amidase domain is transiently inactivated by H2O2 oxidation to sulfenic acid, which is stabilized by a very short hydrogen bond with a water molecule. We propose a set of reactions that explains how the levels of Gsp and Gsp S-thiolated proteins are modulated in response to oxidative stress. The hypersensitivities of GspSA and GspSA/glutaredoxin null mutants to H2O2 support the idea that GspSA and glutaredoxin act synergistically to regulate the redox environment of E. coli. PMID:20530482

  1. Purification, crystallization and preliminary X-ray diffraction analysis of the glyoxalase II from Leishmania infantum

    Energy Technology Data Exchange (ETDEWEB)

    Trincão, José [REQUIMTE-CQFB, Departamento Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica (Portugal); Sousa Silva, Marta [Centro de Química e Bioquímica, Departamento Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, Edifício C8, Lisboa (Portugal); Barata, Lídia [REQUIMTE-CQFB, Departamento Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica (Portugal); Centro de Química e Bioquímica, Departamento Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, Edifício C8, Lisboa (Portugal); Bonifácio, Cecília [REQUIMTE-CQFB, Departamento Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica (Portugal); Carvalho, Sandra; Tomás, Ana Maria [IBMC - Instituto de Biologia Molecular e Celular, Universidade do Porto, Porto (Portugal); ICBAS - Instituto de Ciências Biomédicas Abel Salazar, Universidade do Porto, Porto (Portugal); Ferreira, António E. N.; Cordeiro, Carlos; Ponces Freire, Ana [Centro de Química e Bioquímica, Departamento Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, Edifício C8, Lisboa (Portugal); Romão, Maria João, E-mail: mromao@dq.fct.unl.pt [REQUIMTE-CQFB, Departamento Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica (Portugal)

    2006-08-01

    A glyoxalase II from L. infantum was cloned, purified and crystallized and its structure was solved by X-ray crystallography. In trypanosomatids, trypanothione replaces glutathione in all glutathione-dependent processes. Of the two enzymes involved in the glyoxalase pathway, glyoxalase I and glyoxalase II, the latter shows absolute specificity towards trypanothione thioester, making this enzyme an excellent model to understand the molecular basis of trypanothione binding. Cloned glyoxalase II from Leishmania infantum was overexpressed in Escherichia coli, purified and crystallized. Crystals belong to space group C222{sub 1} (unit-cell parameters a = 65.6, b = 88.3, c = 85.2 Å) and diffract beyond 2.15 Å using synchrotron radiation. The structure was solved by molecular replacement using the human glyoxalase II structure as a search model. These results, together with future detailed kinetic characterization using lactoyltrypanothione, should shed light on the evolutionary selection of trypanothione instead of glutathione by trypano-somatids.

  2. A subcomplex of human mitochondrial RNase P is a bifunctional methyltransferase--extensive moonlighting in mitochondrial tRNA biogenesis.

    Science.gov (United States)

    Vilardo, Elisa; Nachbagauer, Christa; Buzet, Aurélie; Taschner, Andreas; Holzmann, Johann; Rossmanith, Walter

    2012-12-01

    Transfer RNAs (tRNAs) reach their mature functional form through several steps of processing and modification. Some nucleotide modifications affect the proper folding of tRNAs, and they are crucial in case of the non-canonically structured animal mitochondrial tRNAs, as exemplified by the apparently ubiquitous methylation of purines at position 9. Here, we show that a subcomplex of human mitochondrial RNase P, the endonuclease removing tRNA 5' extensions, is the methyltransferase responsible for m(1)G9 and m(1)A9 formation. The ability of the mitochondrial tRNA:m(1)R9 methyltransferase to modify both purines is uncommon among nucleic acid modification enzymes. In contrast to all the related methyltransferases, the human mitochondrial enzyme, moreover, requires a short-chain dehydrogenase as a partner protein. Human mitochondrial RNase P, thus, constitutes a multifunctional complex, whose subunits moonlight in cascade: a fatty and amino acid degradation enzyme in tRNA methylation and the methyltransferase, in turn, in tRNA 5' end processing.

  3. An improved bifunctional oxygen (air) electrode for reversible alkaline fuel cell systems and for rechargeable metal-air batteries

    Science.gov (United States)

    Kordesch, K.; Steininger, K.-H.; Tomantschger, K.

    1988-10-01

    Electrodes with a nickel layer of dual pore structure on the electrolyte side and a PTFE-bonded carbon layer on the oxygen (air) side are discussed, with application to space energy storage. During the electrolyis stage, the oxygen fills the large pores of the porous Ni structure with gas. During the discharge cycle, the iron/air or zinc/air cell of the carbon layer operates as a regular oxygen electrode.

  4. 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.

  5. Identification of a Plastid-Localized Bifunctional Nerolidol/Linalool Synthase in Relation to Linalool Biosynthesis in Young Grape Berries

    Science.gov (United States)

    Zhu, Bao-Qing; Cai, Jian; Wang, Zhi-Qun; Xu, Xiao-Qing; Duan, Chang-Qing; Pan, Qiu-Hong

    2014-01-01

    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. PMID:25470020

  6. Detoxification of the explosive 2,4,6-trinitrotoluene in Arabidopsis: discovery of bifunctional O- and C-glucosyltransferases

    Science.gov (United States)

    2008-08-01

    2 MS + sucrose media in 100-ml flasks were treated with 100 lM TNT for 6 h. The freeze -dried, ground, plant tissue was extracted twice with MeOH and...resistance to Pseudo- monas syringae pv tomato in Arabidopsis. Plant Physiol. 139, 1890–1901. Lao, S.H., Loutre, C., Brazier, M., Coleman, J.O., Cole, D.J

  7. Bifunctional Ag@Pd-Ag Nanocubes for Highly Sensitive Monitoring of Catalytic Reactions by Surface-Enhanced Raman Spectroscopy.

    Science.gov (United States)

    Li, Jumei; Liu, Jingyue; Yang, Yin; Qin, Dong

    2015-06-10

    We report a route to the facile synthesis of Ag@Pd-Ag nanocubes by cotitrating Na2PdCl4 and AgNO3 into an aqueous suspension of Ag nanocubes at room temperature in the presence of ascorbic acid and poly(vinylpyrrolidone). With an increase in the total titration volume, we observed the codeposition of Pd and Ag atoms onto the edges, corners, and side faces of the Ag nanocubes in a site-by-site fashion. By maneuvering the Pd/Ag ratio, we could optimize the SERS and catalytic activities of the Ag@Pd-Ag nanocubes for in situ SERS monitoring of the Pd-catalyzed reduction of 4-nitrothiophenol by NaBH4.

  8. Synthesis of optically active bifunctional building blocks through enantioselective copper-catalyzed allylic alkylation using Grignard reagents

    NARCIS (Netherlands)

    van Zijl, Anthoni W.; Lopez, Fernando; Minnaard, Adriaan J.; Feringa, Ben L.

    2007-01-01

    Enantioselective copper-catalyzed allylic alkylations were performed on allylic bromides with a protected hydroxyl or amine functional group using several Grignard reagents and Taniaphos L1 as a ligand. The terminal olefin moiety in the products was transformed into various functional groups without

  9. Selective extraction of plutonium from nitric acid medium by bifunctional polyethersulfone beads for quantification with thermal ionisation mass spectrometry

    International Nuclear Information System (INIS)

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

    2015-01-01

    Polyethersulfone (PES) magnetic beads were prepared by phase inversion technique. The beads were grafted with two monomers, viz. 2-hydroxyethylmethacrylate phosphoric acid (HEMP) and (3-acrylamidopropyl)trimethyl ammonium chloride (AMAC), by photo-induced free radical polymerization. Effect of different HNO 3 concentrations on the sorption profiles of Am(III) and Pu(IV) was studied using the grafted PES beads. The beads were found to extract plutonium quantitatively from high nitric acid medium (3-8 M). The effect of presence of competing actinide, e.g. U(VI), on the sorption of Pu(IV) was also studied. (author)

  10. Nanocomposite multilayer films containing Dawson-type polyoxometalate and cationic phthalocyanine: Fabrication, characterization and bifunctional electrocatalytic properties

    International Nuclear Information System (INIS)

    Jin Yana; Xu Lin; Zhu Liande; An Wenjia; Gao Guanggang

    2007-01-01

    Water-soluble cationic phthalocyanine - Alcian blue (AB) and 2:18 tungstophosphate anions (P 2 W 18 ) were alternately deposited on a -aminopropyltriethoxysilane-modified indium tin oxide-coated glass electrodes or quartz substrate through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by ultraviolet-visible absorption spectra, cyclic voltammetry and X-ray photoelectron spectra. A stepwise and regular deposition of AB and P 2 W 18 in both pure water and 0.01 M poly(styrenesulfonate) (PSS) were investigated. Differences in linear growth were observed between pure water and 0.01 M PSS-based solutions. The voltammetric curves show well-defined anodic and cathodic peaks, which is indicative of both electrocatalytic oxidation and reduction of nitrite

  11. Bifunctional cyclam-based ligands with phosphorus acid pendant moieties for radiocopper separation: thermodynamic and kinetic studies.

    Science.gov (United States)

    Paúrová, Monika; Havlíčková, Jana; Pospíšilová, Aneta; Vetrík, Miroslav; Císařová, Ivana; Stephan, Holger; Pietzsch, Hans-Jürgen; Hrubý, Martin; Hermann, Petr; Kotek, Jan

    2015-03-16

    Two macrocyclic ligands based on cyclam with trans-disposed N-methyl and N-(4-aminobenzyl) substituents as well as two methylphosphinic (H2L1) or methylphosphonic (H4L2) acid pendant arms were synthesised and investigated in solution. The ligands form stable complexes with transition metal ions. Both ligands show high thermodynamic selectivity for divalent copper over nickel(II) and zinc(II)-K(CuL) is larger than K(Ni/ZnL) by about seven orders of magnitude. Complexation is significantly faster for the phosphonate ligand H4L2, probably due to the stronger coordination ability of the more basic phosphonate groups, which efficiently bind the metal ion in an "out-of-cage" complex and thus accelerate its "in-cage" binding. The rate of Cu(II) complexation by the phosphinate ligand H2L1 is comparable to that of cyclam itself and its derivatives with non-coordinating substituents. Acid-assisted decomplexation of the copper(II) complexes is relatively fast (τ1/2 = 44 and 42 s in 1 M aq. HClO4 at 25 °C for H2L1 and H4L2, respectively). This combination of properties is convenient for selective copper removal/purification. Thus, the title ligands were employed in the preparation of ion-selective resins for radiocopper(II) separation. Glycidyl methacrylate copolymer beads were modified with the ligands through a diazotisation reaction. The separation ability of the modified polymers was tested with cold copper(II) and non-carrier-added (64)Cu in the presence of a large excess of both nickel(II) and zinc(II). The experiments exhibited high overall separation efficiency leading to 60-70% recovery of radiocopper with high selectivity over the other metal ions, which were originally present in 900-fold molar excess. The results showed that chelating resins with properly tuned selectivity of their complexing moieties can be employed for radiocopper separation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. New data on the reaction of 1,4-bifunctional derivatives of hydrazine with 1,3-diketones

    International Nuclear Information System (INIS)

    Zelenin, K.N.; Solod, O.V.; Tomchin, A.B.

    1987-01-01

    As a function of the conditions of the reaction and the structure of the reagents, mono- and bis-adducts of different structure - 5-hydroxy- and 5-hydrazino-2-pyrazolines, mono- and bis(hydrazones), and the corresponding pyrazoles - are formed in the reaction of hydrazine derivatives - aminoguanidine nitrate, 4-phenylsemicarbazide, amidrazonium iodides, and some thiosemicarbazides - with acetylacetone and dibenzoylmethane. The conditions of the formation of these products and the features of their structure were examined

  13. Complexation and biodistribution study of 111In and 90Y complexes of bifunctional phosphinic acid analogs of H4dota

    Czech Academy of Sciences Publication Activity Database

    Forsterová, Michaela; Petřík, M.; Lázničková, A.; Lázníček, M.

    2009-01-01

    Roč. 67, č. 1 (2009), s. 21-29 ISSN 0969-8043 R&D Projects: GA AV ČR 1QS100480501 Institutional research plan: CEZ:AV0Z10480505 Keywords : Biodistribution * Cyclen derivatives * DOTA Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 1.094, year: 2009

  14. Bifunctional Probes of Cathepsin Protease Activity and pH Reveal Alterations in Endolysosomal pH during Bacterial Infection

    NARCIS (Netherlands)

    Sanman, L.E.; Linden, W.A. van der; Verdoes, M.; Bogyo, M.

    2016-01-01

    Cysteine cathepsins are lysosomal proteases involved in regulation of both normal cellular processes and disease. Biochemical studies with peptide substrates indicate that cathepsins have optimal activity at acidic pH and highly attenuated activity at neutral pH. In contrast, there is mounting

  15. Watt-Level Continuous-Wave Emission from a Bi-Functional Quantum Cascade Laser/Detector

    Science.gov (United States)

    2017-04-18

    ed em is si on sp ec tra Wavenumbers (cm−1) Wavelength (µm) subthreshold 1480 mA 1530 mA 1600 mA 2000 mA 2500 mA 3000 mA Figure 3: Emission spectra of...cally authorized by the U.S. Government may violate any copyrights that exist in this work. Watt-level continuous-wave emission from a bi-functional...facet continuous wave emission at 15◦C. Apart from the general performance benets, this enables sensing techiques which rely on continuous wave

  16. Bifunctional acyclic nucleoside phosphonates: 2. Symmetrical 2-{[bis(phosphono)methoxy]methyl}ethyl derivatives of purines and pyrimidines

    Czech Academy of Sciences Publication Activity Database

    Vrbková, Silvie; Dračínský, Martin; Holý, Antonín

    2007-01-01

    Roč. 72, č. 7 (2007), s. 965-983 ISSN 0010-0765 R&D Projects: GA MŠk 1M0508; GA AV ČR 1QS400550501 Grant - others:Gilead Sciences(US) HPAW-2002-10096 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * ANPs * acyclic nucleoside bisphosphonates * ANbPs * phosphonomethyl ethers Subject RIV: CC - Organic Chemistry Impact factor: 0.879, year: 2007

  17. {sup 188}Re-labeled bisphosphonates as potential bifunctional agents for therapy in patients with bone metastases

    Energy Technology Data Exchange (ETDEWEB)

    El-Mabhouh, Amal [Faculty of Pharmacy and Pharmaceutical Sciences, 3118 Dentistry Pharmacy Center, University of Alberta, Edmonton Alta, T6G-2N8 (Canada); Mercer, John R. [Faculty of Pharmacy and Pharmaceutical Sciences, 3118 Dentistry Pharmacy Center, University of Alberta, Edmonton Alta, T6G-2N8 (Canada); Faculty of Medicine, 3118 Dentistry Pharmacy Center, University of Alberta, Edmonton Alta, T6G-2N8 (Canada)]. E-mail: john.mercer@ualberta.ca

    2005-04-01

    Two new bisphosphonates have been examined for their ability to bind {sup 188}Re and deliver it selectively to bone. The bisphosphonates are prototype compounds with potential to deliver rhenium radionuclides and a second therapy modality to bone metastases. A conjugate between diethylenetriaminepentaacetic acid and bisphosphonate (DTPA/BP) and a conjugate between 5-fluorouracil and bisphosphonate (5-FU/BP) were prepared and labeled at high radiochemical purity with {sup 188}Re and biodistribution studies were carried out in normal Balb/C mice. The compounds showed rapid blood clearance and elimination from soft tissues with substantial retention of activity in the bone comparable to {sup 188}Re-hydroxyethylidine diphosphonate used as a control. At 8 h bone activity was 3.51% of injected dose for {sup 188}Re-DTPA/BP and 6.38% of injected dose for {sup 188}Re-5-FU/BP representing 69.6% and 80.6% of total body radioactivity, respectively. The two compounds show the potential for combination therapy of painful bone metastases.

  18. Mouse interleukin-12/FasTI: A novel bi-functional fusion protein for cancer immuno/gene therapy.

    Science.gov (United States)

    Yang, Xi; Tietje, Ashlee H; Yu, Xianzhong; Wei, Yanzhang

    2016-06-01

    Whereas cancer immunotherapy with cytokines in recent research was demonstrated effective in activating immune response against tumor cells, one major obstacle with the use of these cytokines is their severe side effects when delivered systemically at high doses. Another challenge is that advanced tumor cells often evade immunosurveillance of the immune system as well as of the Fas-mediated apoptosis by various mechanisms. We report the design and preliminary evaluation of the antitumor activity of a novel fusion protein-mIL-12/FasTI, consisting of mouse interleukin-12 and the transmembrane and intracellular domains of mouse Fas. The fusion construct (pmIL-12/FasTI) was transfected into mouse lung carcinoma cell line TC-1. Stable cell clones expressing the fusion protein were established as assayed by RT-PCR and immunohistochemistry. ELISA and cell proliferation analyses demonstrated that NK cells were effectively activated by the fusion protein with increased IFN-γ production and cytotoxicity. Enhanced caspase-3 activity of the clones when co-cultured with NK cells indicated that apoptosis was induced through Fas/FasL signaling pathway. The preliminary results suggest a synergized anticancer activity of the fusion protein. It may represent a promising therapeutic agent for cancer treatment.

  19. Acid-Base Bifunctional Zirconium N-Alkyltriphosphate Nanohybrid for Hydrogen Transfer of Biomass-Derived Carboxides

    DEFF Research Database (Denmark)

    Li, Hu; He, Jian; Riisager, Anders

    2016-01-01

    sites, and their catalytic activity in converting biomass-derived carbonyl compounds to corresponding alcohols in 2-propanol. Particularly, a quantitative yield of furfuryl alcohol (FFA) was obtained from furfural (FUR) over organotriphosphate-zirconium hybrid (ZrPN) under mild conditions. The presence...... of Lewis basic sites adjacent to acid sites with an appropriate base/acid site ratio (1:0.7) in ZrPN significantly improved the yield of FFA. Mechanistic studies for the transformation of FUR to FFA with ZrPN in 2-propanol-d(8) evidently indicate CTH reaction proceeding via a direct intermolecular hydrogen...

  20. Molecular Modeling of Bifunctional Chelate Peptide Conjugates. 1. Copper and Indium Parameters for the AMBER Force Field

    DEFF Research Database (Denmark)

    Reichert, David E.; Norrby, Per-Ola; Welch, Michael J.

    2001-01-01

    In this work we describe the development of parameters for In(III) and Cu(II) for the AMBER* force field as found in the modeling package MacroModel. These parameters were developed using automated procedures from a combination of crystallographic structures and ab initio calculations. The new pa...