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Sample records for bifunctional cyclic disulfide

  1. Computational design of disulfide cyclic peptide as potential ...

    African Journals Online (AJOL)

    Development of genomic and proteomic studies coupled with computational sciences could facilitate the discovery of various target proteins and potential inhibitor to be developed as drugs. Several researches by molecular docking method have been conducted to design disulfide cyclic peptide ligand as potential inhibitors ...

  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. 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.

  4. Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides.

    Science.gov (United States)

    Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

    2018-02-16

    Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

  5. Cell surface protein disulfide isomerase regulates natriuretic peptide generation of cyclic guanosine monophosphate.

    Directory of Open Access Journals (Sweden)

    Shuchong Pan

    Full Text Available The family of natriuretic peptides (NPs, including atrial natriuretic peptide (ANP, B-type natriuretic peptide (BNP, and C-type natriuretic peptide (CNP, exert important and diverse actions for cardiovascular and renal homeostasis. The autocrine and paracrine functions of the NPs are primarily mediated through the cellular membrane bound guanylyl cyclase-linked receptors GC-A (NPR-A and GC-B (NPR-B. As the ligands and receptors each contain disulfide bonds, a regulatory role for the cell surface protein disulfide isomerase (PDI was investigated.We utilized complementary in vitro and in vivo models to determine the potential role of PDI in regulating the ability of the NPs to generate its second messenger, cyclic guanosine monophosphate.Inhibition of PDI attenuated the ability of ANP, BNP and CNP to generate cGMP in human mesangial cells (HMCs, human umbilical vein endothelial cells (HUVECs, and human aortic smooth muscle cells (HASMCs, each of which were shown to express PDI. In LLC-PK1 cells, where PDI expression was undetectable by immunoblotting, PDI inhibition had a minimal effect on cGMP generation. Addition of PDI to cultured LLC-PK1 cells increased intracellular cGMP generation mediated by ANP. Inhibition of PDI in vivo attenuated NP-mediated generation of cGMP by ANP. Surface Plasmon Resonance demonstrated modest and differential binding of the natriuretic peptides with immobilized PDI in a cell free system. However, PDI was shown to co-localize on the surface of cells with GC-A and GC-B by co-immunoprecpitation and immunohistochemistry.These data demonstrate for the first time that cell surface PDI expression and function regulate the capacity of natriuretic peptides to generate cGMP through interaction with their receptors.

  6. Crystal structure of the platelet activator convulxin, a disulfide-linked alpha4beta4 cyclic tetramer from the venom of Crotalus durissus terrificus.

    Science.gov (United States)

    Murakami, M T; Zela, S P; Gava, L M; Michelan-Duarte, S; Cintra, A C O; Arni, R K

    2003-10-17

    Convulxin (CVX), a C-type lectin, isolated from the venom of the South American rattlesnake Crotalus durissus terrificus, causes cardiovascular and respiratory disturbances and is a potent platelet activator which binds to platelet glycoprotein GPVI. The structure of CVX has been solved at 2.4A resolution to a crystallographic residual of 18.6% (R(free)=26.4%). CVX is a disulfide linked heterodimer consisting of homologous alpha and beta chains. The heterodimers are additionally linked by disulfide bridges to form cyclic alpha(4)beta(4)heterotetramers. These domains exhibit significant homology to the carbohydrate-binding domains of C-type lectins, to the factor IX-binding protein (IX-bp), and to flavocetin-A (Fl-A) but sequence and structural differences are observed in both the domains in the putative Ca(2+)and carbohydrate binding regions.

  7. Strategy to improve the quantitative LC-MS analysis of molecular ions resistant to gas-phase collision induced dissociation: application to disulfide-rich cyclic peptides.

    Science.gov (United States)

    Ciccimaro, Eugene; Ranasinghe, Asoka; D'Arienzo, Celia; Xu, Carrie; Onorato, Joelle; Drexler, Dieter M; Josephs, Jonathan L; Poss, Michael; Olah, Timothy

    2014-12-02

    Due to observed collision induced dissociation (CID) fragmentation inefficiency, developing sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) assays for CID resistant compounds is especially challenging. As an alternative to traditional LC-MS/MS, we present here a methodology that preserves the intact analyte ion for quantification by selectively filtering ions while reducing chemical noise. Utilizing a quadrupole-Orbitrap MS, the target ion is selectively isolated while interfering matrix components undergo MS/MS fragmentation by CID, allowing noise-free detection of the analyte's surviving molecular ion. In this manner, CID affords additional selectivity during high resolution accurate mass analysis by elimination of isobaric interferences, a fundamentally different concept than the traditional approach of monitoring a target analyte's unique fragment following CID. This survivor-selected ion monitoring (survivor-SIM) approach has allowed sensitive and specific detection of disulfide-rich cyclic peptides extracted from plasma.

  8. Robust bifunctional aluminium–salen catalysts for the preparation of cyclic carbonates from carbon dioxide and epoxides

    Directory of Open Access Journals (Sweden)

    Yuri A. Rulev

    2015-09-01

    Full Text Available Two new one-component aluminium-based catalysts for the reaction between epoxides and carbon dioxide have been prepared. The catalysts are composed of aluminium–salen chloride complexes with trialkylammonium groups directly attached to the aromatic rings of the salen ligand. With terminal epoxides, the catalysts induced the formation of cyclic carbonates under mild reaction conditions (25–35 °C; 1–10 bar carbon dioxide pressure. However, with cyclohexene oxide under the same reaction conditions, the same catalysts induced the formation of polycarbonate. The catalysts could be recovered from the reaction mixture and reused.

  9. 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.

  10. 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.

  11. Multiple ways to make disulfides

    DEFF Research Database (Denmark)

    Bulleid, Neil J; Ellgaard, Lars

    2011-01-01

    Our concept of how disulfides form in proteins entering the secretory pathway has changed dramatically in recent years. The discovery of endoplasmic reticulum (ER) oxidoreductin 1 (ERO1) was followed by the demonstration that this enzyme couples oxygen reduction to de novo formation of disulfides....... However, mammals deficient in ERO1 survive and form disulfides, which suggests the presence of alternative pathways. It has recently been shown that peroxiredoxin 4 is involved in peroxide removal and disulfide formation. Other less well-characterized pathways involving quiescin sulfhydryl oxidase, ER......-localized protein disulfide isomerase peroxidases and vitamin K epoxide reductase might all contribute to disulfide formation. Here we discuss these various pathways for disulfide formation in the mammalian ER and highlight the central role played by glutathione in regulating this process....

  12. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar affinities. Thus...

  13. Air oxidation method employed for the disulfide bond formation of natural and synthetic peptides.

    Science.gov (United States)

    Calce, Enrica; Vitale, Rosa Maria; Scaloni, Andrea; Amodeo, Pietro; De Luca, Stefania

    2015-08-01

    Among the available protocols, chemically driven approaches to oxidize cysteine may not be required for molecules that, under the native-like conditions, naturally fold in conformations ensuring an effective pairing of the right disulfide bridge pattern. In this contest, we successfully prepared the distinctin, a natural heterodimeric peptide, and some synthetic cyclic peptides that are inhibitors of the CXCR4 receptor. In the first case, the air oxidation reaction allowed to connect two peptide chains via disulfide bridge, while in the second case allowed the cyclization of rationally designed peptides by an intramolecular disulfide bridge. Computational approaches helped to either drive de-novo design or suggest structural modifications and optimal oxidization protocols for disulfide-containing molecules. They are able to both predict and to rationalize the propensity of molecules to spontaneously fold in suitable conformations to achieve the right disulfide bridges.

  14. Dynamic Combinatorial Chemistry with Diselenides, Disulfides, Imines and Metal Coordination

    DEFF Research Database (Denmark)

    Sørensen, Anne

    The design and preparation of strong and selective artificial receptors, especially biomi-metic receptors that function in aqueous solution, has proved truly challenging. In this thesis it will be described how the strengths of dynamic combinatorial chemistry can be used to great advantage...... in this field. The aim of this project has therefore been to develop new ways of using dynamic combinatorial libraries for molecular recognition in aqueous media. The focus has been on using what has been learned from the well-established di-sulfide exchange chemistry to incorporate a new reaction into dynamic...... experimentally and theoretically and found to be unique in organoselenium chemistry by proceeding through a four-membered cyclic transition state following first-order kinetics. Subsequently, this thesis illustrates how an aliphatic diselenide could be used to catalyse the formation of a disulfide based dynamic...

  15. Analysis of Disulfide Bond Formation

    NARCIS (Netherlands)

    Braakman, Ineke; Lamriben, Lydia; van Zadelhoff, Guus; Hebert, Daniel N.

    2017-01-01

    In this unit, protocols are provided for detection of disulfide bond formation in cultures of intact cells and in an in vitro translation system containing isolated microsomes or semi-permeabilized cells. First, the newly synthesized protein of interest is biosynthetically labeled with radioactive

  16. Cyclic Vitalism

    DEFF Research Database (Denmark)

    Halse, Sven

    2014-01-01

    an enthusiastic worshipping of life, one that holds youth, health, strength and beauty as its primary attributes, and which was prevalent in all aspects of cultural life around 1900. But even the post war founders of the Vitalist re-conceptualisation of this era, Wolfdietrich Rasch and Gunter Martens, warned...... that also encompasses notions of destruction, decay and death. “All life symbols in literature around 1900 are at the same time symbols of death”. (Rasch, W. 1967:24) Through the analyses of three poems, this article aims to show concrete examples of how cyclic Vitalist thinking is embedded in poetry...

  17. Cyclic multiverses

    Science.gov (United States)

    Marosek, Konrad; Dąbrowski, Mariusz P.; Balcerzak, Adam

    2016-09-01

    Using the idea of regularization of singularities due to the variability of the fundamental constants in cosmology we study the cyclic universe models. We find two models of oscillating and non-singular mass density and pressure (`non-singular' bounce) regularized by varying gravitational constant G despite the scale factor evolution is oscillating and having sharp turning points (`singular' bounce). Both violating (big-bang) and non-violating (phantom) null energy condition models appear. Then, we extend this idea on to the multiverse containing cyclic individual universes with either growing or decreasing entropy though leaving the net entropy constant. In order to get an insight into the key idea, we consider the doubleverse with the same geometrical evolution of the two `parallel' universes with their physical evolution [physical coupling constants c(t) and G(t)] being different. An interesting point is that there is a possibility to exchange the universes at the point of maximum expansion - the fact which was already noticed in quantum cosmology. Similar scenario is also possible within the framework of Brans-Dicke theory where varying G(t) is replaced by the dynamical Brans-Dicke field φ(t) though these theories are slightly different.

  18. Multicomponent Synthesis of Cyclic Depsipeptide Mimics by Ugi Reaction Including Cyclic Hemiacetals Derived from Asymmetric Organocatalysis.

    Science.gov (United States)

    de la Torre, Alexander F; Rivera, Daniel G; Concepción, Odette; Echemendia, Radell; Correa, Arlene G; Paixão, Márcio W

    2016-02-05

    The synthesis of novel cyclic depsipeptide mimics by means of an organocatalytic conjugate addition, leading to chiral cyclic hemiacetals, followed by a multicomponent reaction with α-amino acids and isocyanides, is described. The initial organocatalytic step is employed for the asymmetric derivatization of α,β-unsaturated aldehydes to 4,5-disubstituted 2-hydroxytetrahydropyrans, which are next used as chiral bifunctional substrates on the Ugi five-center three-component reaction, giving rise to nine-membered-ring lactones. This sequential approach proved to be suitable for the rapid generation of molecular complexity through the combination of aliphatic, dipeptidic, glucosidic, and lipidic isocyanides with several amino acids, thus giving access to amido-, glyco-, and lipo-depsipeptide scaffolds featuring natural product-like structures.

  19. Thiol-Disulfide Exchange in Peptides Derived from Human Growth Hormone during Lyophilization and Storage in the Solid State

    Science.gov (United States)

    Chandrasekhar, Saradha; Topp, Elizabeth M.

    2015-01-01

    Lyophilization (freeze-drying) is frequently used to stabilize protein therapeutics. However, covalent modifications such as thiol-disulfide exchange and disulfide scrambling can occur even in the solid state. The effects of lyophilization and storage of lyophilized powders on the mechanism and kinetics of thioldisulfide exchange have not been elucidated and are explored here. Reaction kinetics were monitored in peptides corresponding to tryptic fragments of human growth hormone (T20 + T20-T21 or T20 + cT20-T21) during different stages of lyophilization and during storage of the lyophilized powders at 22 °C and ambient RH. The concentrations of reactants and products were determined using RP-HPLC and product identity confirmed using LC-MS. Loss of native disulfide was observed for the reaction of T20 with both linear (T20-T21) and cyclic (cT20-T21) peptides during the primary drying step, however, the native disulfides were regenerated during secondary drying with no further change till the end of lyophilization. Deviations from Arrhenius parameters predicted from solution studies and the absence of buffer effects during lyophilization suggest that factors such as temperature, initial peptide concentration, buffer type and concentration do not influence thiol-disulfide exchange during lyophilization. Results from a ‘cold finger’ method used to study peptide adsorption to ice indicate that there is no preferential adsorption to the ice surface and that its presence may not influence disulfide reactivity during primary drying. Overall, reaction rates and product distribution differ for the reaction of T20 with T20-T21 or cT20-T21 in the solid state and aqueous solution, while the mechanism of thiol-disulfide remains unchanged. Increased reactivity of the cyclic peptide in the solid state suggests that peptide cyclization does not offer protection against lyophilization and that damage induced by a process stress further affects storage stability at 22 °C and

  20. 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.

  1. 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.

  2. Green polymer chemistry: Synthesis of poly(disulfide) polymers and networks

    Science.gov (United States)

    Rosenthal-Kim, Emily Quinn

    distribution of around 1.15. However, the majority of the product consists of low molecular weight cyclic poly(disulfide) oligomers. In reactions maintained below 18°C, the organic components were miscible in the aqueous hydrogen peroxide and a milky emulsion was produced. The polymers were degraded using the disulfide-specific reducing agent, dithiothreitol. Poly(disulfide) polymer networks were also synthesized in a two-phase system. Due to the poor solubility of the crosslinker, trimethylolpropane tris(2-mercaptopropionate, organic solvents were required to obtain consistent networks. The networks were degraded using dithiothreitol in tetrahydrofuran. The networks were stable under aqueous reducing conditions. The disulfide-bearing biochemical, alpha-lipoic acid, was investigated as monomer for the new method of poly(disulfide) polymer synthesis. It was also polymerized thermally and by a new interfacial method that proceeds at the air-water interface. Polymer products were often too large to be characterized by SEC (Mn > 1,000,000 g/mol). A poly(alpha-LA) polymer sample showed mass loss in aqueous solutions of glutathione at pH = 5.2 which was used to model cytosolic conditions. Poly(alpha-LA) was decorated with PEG (2,000 g/mol) in an esterification reaction catalyzed by Candida antarctica lipase B (CALB). The decorated polymers were imaged using AFM which revealed branch-like structures. To make new alpha-lipoic acid based monomers and macromonomers, CALB-catalyzed esterification, was used to conjugate alpha-lipoic acid to a variety of glycols including: diethylene glycol monomethyl ether, tetraethylene glycol, hexaethylene glycol, and poly(ethylene glycol). The products were verified using NMR spectroscopy and mass spectrometry.

  3. Thiol/disulfide homeostasis in postmenopausal osteoporosis.

    Science.gov (United States)

    Korkmaz, V; Kurdoglu, Z; Alisik, M; Turgut, E; Sezgın, O O; Korkmaz, H; Ergun, Y; Erel, O

    2017-04-01

    To evaluate the impact of postmenopausal osteoporosis on thiol/disulfide homeostasis. A total of 75 participants were divided into two groups: Group 1 (n = 40) was composed of healthy postmenopausal women, and group 2 (n = 35) was composed of women with postmenopausal osteoporosis. Clinical findings and thiol/disulfide homeostasis were compared between the two groups. The disulfide/native thiol ratio was 8.6% ± 3.6 in group 1 and 12.7% ± 8.4 in group 2 (p = 0.04). The disulfide/native thiol percent ratio was significantly higher in group 2 after adjustment for the years since menopause and age (p menopause and age (p menopause in postmenopausal osteoporosis.

  4. 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.

  5. Identification, activity and disulfide connectivity of C-di-GMP regulating proteins in Mycobacterium tuberculosis.

    Directory of Open Access Journals (Sweden)

    Kajal Gupta

    2010-11-01

    Full Text Available C-di-GMP, a bacterial second messenger plays a key role in survival and adaptation of bacteria under different environmental conditions. The level of c-di-GMP is regulated by two opposing activities, namely diguanylate cyclase (DGC and phosphodiesterase (PDE-A exhibited by GGDEF and EAL domain, respectively in the same protein. Previously, we reported a bifunctional GGDEF-EAL domain protein, MSDGC-1 from Mycobacterium smegmatis showing both these activities (Kumar and Chatterji, 2008. In this current report, we have identified and characterized the homologous protein from Mycobacterium tuberculosis (Rv 1354c named as MtbDGC. MtbDGC is also a bifunctional protein, which can synthesize and degrade c-di-GMP in vitro. Further we expressed Mtbdgc in M. smegmatis and it was able to complement the MSDGC-1 knock out strain by restoring the long term survival of M. smegmatis. Another protein Rv 1357c, named as MtbPDE, is an EAL domain protein and degrades c-di-GMP to pGpG in vitro. Rv1354c and 1357c have seven cysteine amino acids in their sequence, distributed along the full length of the protein. Disulfide bonds play an important role in stabilizing protein structure and regulating protein function. By proteolytic digestion and mass spectrometric analysis of MtbDGC, connectivity between cysteine pairs Cys94-Cys584, Cys2-Cys479 and Cys429-Cys614 was determined, whereas the third cysteine (Cys406 from N terminal was found to be free in MtbDGC protein, which was further confirmed by alkylation with iodoacetamide labeling. Bioinformatics modeling investigations also supported the pattern of disulfide connectivity obtained by Mass spectrometric analysis. Cys406 was mutated to serine by site directed mutagenesis and the mutant MtbC406S was not found to be active and was not able to synthesize or degrade c-di-GMP. The disulfide connectivity established here would help further in understanding the structure - function relationship in MtbDGC.

  6. Cyclic and Macrocyclic Organic Compounds - a Personal Review in Honor of Professor Leopold Ružička

    Directory of Open Access Journals (Sweden)

    Höcker¸, H.

    2009-02-01

    Full Text Available Ružička opened the field of cyclic molecules such as cyclic terpenes and cyclic ketones with up to 17 ring atoms. This work until now was extended in many directions such as cyclic paraffins, crown ethers and cryptands and cyclic ester amides. Cyclic molecules are formed upon electron transfer and intramolecular association of polymers with two active ends and they are synthesized by directed cyclization of bifunctional macromolecules. In the course of step growth polymerization and ring opening polymerization, ring chain equilibria may be established; the larger the monomer unit the easier is the separation of pure oligomers such as the heptamer of cyclododecene with 84 carbon atoms in the ring. Still many questions remain open, in particular whether there are macrocyclic catenanes in commercial polycondensates.

  7. 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

  8. Cyclic Railway Timetable Optimization

    NARCIS (Netherlands)

    L.W.P. Peeters (Leon)

    2003-01-01

    textabstractCyclic Railway Timetable Optimization describes mathematical models and solution methods for constructing high quality cyclic railway timetables. In a cyclic timetable, a train for a certain destination leaves a certain station at the same time every cycle time, say every half an hour,

  9. Measurement of glutathione-protein mixed disulfides

    International Nuclear Information System (INIS)

    Livesey, J.C.; Reed, D.J.

    1984-01-01

    The development of a sensitive and highly specific assay for the presence of mixed disulfides between protein thiol groups and endogenous thiols has been undertaken. Previous investigations on the concentrations of glutathione (GSH), glutathione disulfide (GSSG) and protein glutathione mixed disulfides (ProSSG) have been of limited usefulness because of the poor specificity of the assays used. Our assay for these forms of glutathione is based on high performance liquid chromatography (HPLC) and is an extension of an earlier method. After perchloric acid precipitation, the protein sample is washed with an organic solvent to fully denature the protein. Up to a 10-fold increase in GSH released from fetal bovine serum (FBS) protein has been found when the protein precipitate is washed with ethanol rather than ether, as earlier suggested. Similar effects have been observed with an as yet unidentified thiol which elutes in the chromatography system with a retention volume similar to cysteine

  10. Brain MRI findings of carbon disulfide poisoning

    International Nuclear Information System (INIS)

    Cha, Joo Hee; Kim, Mi Jung; Yim, Sang Hyuk; Kim, Sam Soo; Han, Heon; Kim, Rok Ho

    2002-01-01

    To evaluate the findings of brain MRI in patients with carbon disulfide poisoning. Ninety-one patients who had suffered carbon disulfide poisoning [male:female=87:4; age, 32-74 (mean 53.3) years] were included in this study. To determine the extent of white matter hyperintensity (Grade 0-V) and lacunar infarction, T2-weighted MR imaging of the brain was performed. T2-weighted images depicted white matter hyperintensity in 70 patients (76.9%) and lacunar infarcts in 27 (29.7%). In these patients, the prevalent findings at T2-weighted MR imaging of the brain were white matter hyperintensity and lacunar infarcts. Disturbance of the cardiovascular system by carbon disulfide might account for these results

  11. Dynamic combinatorial chemistry with diselenides and disulfides in water

    DEFF Research Database (Denmark)

    Rasmussen, Brian; Sørensen, Anne; Gotfredsen, Henrik

    2014-01-01

    Diselenide exchange is introduced as a reversible reaction in dynamic combinatorial chemistry in water. At neutral pH, diselenides are found to mix with disulfides and form dynamic combinatorial libraries of diselenides, disulfides, and selenenylsulfides. This journal is...

  12. 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.

  13. Why is DsbA such an oxidizing disulfide catalyst?

    DEFF Research Database (Denmark)

    Grauschopf, U; Winther, Jakob R.; Korber, P

    1995-01-01

    DsbA, a member of the thioredoxin family of disulfide oxidoreductases, acts in catalyzing disulfide bond formation by donating its disulfide to newly translocated proteins. We have found that the two central residues within the active site Cys-30-Pro-31-His-32-Cys-33 motif are critical in determi...

  14. The human protein disulfide isomerase gene family

    Directory of Open Access Journals (Sweden)

    Galligan James J

    2012-07-01

    Full Text Available Abstract Enzyme-mediated disulfide bond formation is a highly conserved process affecting over one-third of all eukaryotic proteins. The enzymes primarily responsible for facilitating thiol-disulfide exchange are members of an expanding family of proteins known as protein disulfide isomerases (PDIs. These proteins are part of a larger superfamily of proteins known as the thioredoxin protein family (TRX. As members of the PDI family of proteins, all proteins contain a TRX-like structural domain and are predominantly expressed in the endoplasmic reticulum. Subcellular localization and the presence of a TRX domain, however, comprise the short list of distinguishing features required for gene family classification. To date, the PDI gene family contains 21 members, varying in domain composition, molecular weight, tissue expression, and cellular processing. Given their vital role in protein-folding, loss of PDI activity has been associated with the pathogenesis of numerous disease states, most commonly related to the unfolded protein response (UPR. Over the past decade, UPR has become a very attractive therapeutic target for multiple pathologies including Alzheimer disease, Parkinson disease, alcoholic and non-alcoholic liver disease, and type-2 diabetes. Understanding the mechanisms of protein-folding, specifically thiol-disulfide exchange, may lead to development of a novel class of therapeutics that would help alleviate a wide range of diseases by targeting the UPR.

  15. Functional differences in yeast protein disulfide isomerases

    DEFF Research Database (Denmark)

    Nørgaard, P; Westphal, V; Tachibana, C

    2001-01-01

    PDI1 is the essential gene encoding protein disulfide isomerase in yeast. The Saccharomyces cerevisiae genome, however, contains four other nonessential genes with homology to PDI1: MPD1, MPD2, EUG1, and EPS1. We have investigated the effects of simultaneous deletions of these genes. In several...

  16. Assigning Peptide Disulfide Linkage Pattern Among Regio-Isomers via Methoxy Addition to Disulfide and Tandem Mass Spectrometry

    Science.gov (United States)

    Durand, Kirt L.; Tan, Lei; Stinson, Craig A.; Love-Nkansah, Chasity B.; Ma, Xiaoxiao; Xia, Yu

    2017-06-01

    Pinpointing disulfide linkage pattern is critical in the characterization of proteins and peptides consisting of multiple disulfide bonds. Herein, we report a method based on coupling online disulfide modification and tandem mass spectrometry (MS/MS) to distinguish peptide disulfide regio-isomers. Such a method relies on a new disulfide bond cleavage reaction in solution, involving methanol as a reactant and 254 nm ultraviolet (UV) irradiation. This reaction leads to selective cleavage of a disulfide bond and formation of sulfenic methyl ester (-SOCH3) at one cysteine residue and a thiol (-SH) at the other. Under low energy collision-induced dissociation (CID), cysteine sulfenic methyl ester motif produces a signature methanol loss (-32 Da), allowing its identification from other possible isomeric structures such as S-hydroxylmethyl (-SCH2OH) and methyl sulfoxide (-S(O)-CH3). Since disulfide bond can be selectively cleaved and modified upon methoxy addition, subsequent MS2 CID of the methoxy addition product provides enhanced sequence coverage as demonstrated by the analysis of bovine insulin. More importantly, this reaction does not induce disulfide scrambling, likely due to the fact that radical intermediates are not involved in the process. An approach based on methoxy addition followed by MS3 CID has been developed for assigning disulfide linkage patterns in peptide disulfide regio-isomers. This methodology was successfully applied to characterizing peptide systems having two disulfide bonds and three disulfide linkage isomers: side-by-side, overlapped, and looped-within-a-loop configurations. [Figure not available: see fulltext.

  17. Abiotic synthesis of organic compounds from carbon disulfide under hydrothermal conditions.

    Science.gov (United States)

    Rushdi, Ahmed I; Simoneit, Bernd R T

    2005-12-01

    Abiotic formation of organic compounds under hydrothermal conditions is of interest to bio, geo-, and cosmochemists. Oceanic sulfur-rich hydrothermal systems have been proposed as settings for the abiotic synthesis of organic compounds. Carbon disulfide is a common component of magmatic and hot spring gases, and is present in marine and terrestrial hydrothermal systems. Thus, its reactivity should be considered as another carbon source in addition to carbon dioxide in reductive aqueous thermosynthesis. We have examined the formation of organic compounds in aqueous solutions of carbon disulfide and oxalic acid at 175 degrees C for 5 and 72 h. The synthesis products from carbon disulfide in acidic aqueous solutions yielded a series of organic sulfur compounds. The major compounds after 5 h of reaction included dimethyl polysulfides (54.5%), methyl perthioacetate (27.6%), dimethyl trithiocarbonate (6.8%), trithianes (2.7%), hexathiepane (1.4%), trithiolanes (0.8%), and trithiacycloheptanes (0.3%). The main compounds after 72 h of reaction consisted of trithiacycloheptanes (39.4%), pentathiepane (11.6%), tetrathiocyclooctanes (11.5%), trithiolanes (10.6%), tetrathianes (4.4%), trithianes (1.2%), dimethyl trisulfide (1.1%), and numerous minor compounds. It is concluded that the abiotic formation of aliphatic straight-chain and cyclic polysulfides is possible under hydrothermal conditions and warrants further studies.

  18. Display of disulfide-rich proteins by complementary DNA display and disulfide shuffling assisted by protein disulfide isomerase.

    Science.gov (United States)

    Naimuddin, Mohammed; Kubo, Tai

    2011-12-01

    We report an efficient system to produce and display properly folded disulfide-rich proteins facilitated by coupled complementary DNA (cDNA) display and protein disulfide isomerase-assisted folding. The results show that a neurotoxin protein containing four disulfide linkages can be displayed in the folded state. Furthermore, it can be refolded on a solid support that binds efficiently to its natural acetylcholine receptor. Probing the efficiency of the display proteins prepared by these methods provided up to 8-fold higher enrichment by the selective enrichment method compared with cDNA display alone, more than 10-fold higher binding to its receptor by the binding assays, and more than 10-fold higher affinities by affinity measurements. Cotranslational folding was found to have better efficiency than posttranslational refolding between the two investigated methods. We discuss the utilities of efficient display of such proteins in the preparation of superior quality proteins and protein libraries for directed evolution leading to ligand discovery. Copyright © 2011 Elsevier Inc. All rights reserved.

  19. No Arithmetic Cyclic Quadrilaterals

    Science.gov (United States)

    Beauregard, Raymond A.

    2006-01-01

    A quadrilateral is arithmetic if its area is an integer and its sides are integers in an arithmetic progression, and it is cyclic if it can be inscribed in a circle. The author shows that no quadrilateral is both arithmetic and cyclic.

  20. 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.

  1. Combining reactive triblock copolymers with functional cross-linkers: A versatile pathway to disulfide stabilized-polyplex libraries and their application as pDNA vaccines.

    Science.gov (United States)

    Heller, Philipp; Hobernik, Dominika; Lächelt, Ulrich; Schinnerer, Meike; Weber, Benjamin; Schmidt, Manfred; Wagner, Ernst; Bros, Matthias; Barz, Matthias

    2017-07-28

    Therapeutic nucleic acids such as pDNA hold great promise for the treatment of multiple diseases. These therapeutic interventions are, however, compromised by the lack of efficient and safe non-viral delivery systems, which guarantee stability during blood circulation together with high transfection efficiency. To provide these desired properties within one system, we propose the use of reactive triblock copolypept(o)ides, which include a stealth-like block for efficient shielding, a hydrophobic block based on reactive disulfides for cross-linking and a cationic block for complexation of pDNA. After the complexation step, bifunctional cross-linkers can be employed to bio-reversibly stabilize derived polyplexes by disulfide bond formation and to introduce endosomolytic moieties at the same time. Cross-linked polyplexes show no aggregation in human blood serum. Upon cellular uptake and cleavage of disulfide bonds, the cross-linkers can interact with the endosomal membrane, leading to lysis and efficient endosomal translocation. In principal, the approach allows for the combination of one polymer with various different cross-linkers and thus enables the fast forward creation of a polyplex library. Here, we provide a first insight into the potential of this concept and use a screening strategy to identify a lead candidate, which is able to transfect dendritic cells with a model DNA vaccine. Copyright © 2017. Published by Elsevier B.V.

  2. Widespread Disulfide Bonding in Proteins from Thermophilic Archaea

    Directory of Open Access Journals (Sweden)

    Julien Jorda

    2011-01-01

    Full Text Available Disulfide bonds are generally not used to stabilize proteins in the cytosolic compartments of bacteria or eukaryotic cells, owing to the chemically reducing nature of those environments. In contrast, certain thermophilic archaea use disulfide bonding as a major mechanism for protein stabilization. Here, we provide a current survey of completely sequenced genomes, applying computational methods to estimate the use of disulfide bonding across the Archaea. Microbes belonging to the Crenarchaeal branch, which are essentially all hyperthermophilic, are universally rich in disulfide bonding while lesser degrees of disulfide bonding are found among the thermophilic Euryarchaea, excluding those that are methanogenic. The results help clarify which parts of the archaeal lineage are likely to yield more examples and additional specific data on protein disulfide bonding, as increasing genomic sequencing efforts are brought to bear.

  3. Widespread disulfide bonding in proteins from thermophilic archaea.

    Science.gov (United States)

    Jorda, Julien; Yeates, Todd O

    2011-01-01

    Disulfide bonds are generally not used to stabilize proteins in the cytosolic compartments of bacteria or eukaryotic cells, owing to the chemically reducing nature of those environments. In contrast, certain thermophilic archaea use disulfide bonding as a major mechanism for protein stabilization. Here, we provide a current survey of completely sequenced genomes, applying computational methods to estimate the use of disulfide bonding across the Archaea. Microbes belonging to the Crenarchaeal branch, which are essentially all hyperthermophilic, are universally rich in disulfide bonding while lesser degrees of disulfide bonding are found among the thermophilic Euryarchaea, excluding those that are methanogenic. The results help clarify which parts of the archaeal lineage are likely to yield more examples and additional specific data on protein disulfide bonding, as increasing genomic sequencing efforts are brought to bear.

  4. 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

  5. Widespread Disulfide Bonding in Proteins from Thermophilic Archaea

    OpenAIRE

    Jorda, Julien; Yeates, Todd O.

    2011-01-01

    Disulfide bonds are generally not used to stabilize proteins in the cytosolic compartments of bacteria or eukaryotic cells, owing to the chemically reducing nature of those environments. In contrast, certain thermophilic archaea use disulfide bonding as a major mechanism for protein stabilization. Here, we provide a current survey of completely sequenced genomes, applying computational methods to estimate the use of disulfide bonding across the Archaea. Microbes belonging to the Crenarchaea...

  6. Real Topological Cyclic Homology

    DEFF Research Database (Denmark)

    Høgenhaven, Amalie

    The main topics of this thesis are real topological Hochschild homology and real topological cyclic homology. If a ring or a ring spectrum is equipped with an anti-involution, then it induces additional structure on the topological Hochschild homology spectrum. The group O(2) acts on the spectrum......, where O(2) is the semi-direct product of T, the multiplicative group of complex number of modulus 1, by the group G=Gal(C/R). We refer to this O(2)-spectrum as the real topological Hochschild homology. This generalization leads to a G-equivariant version of topological cyclic homology, which we call...... real topological cyclic homology. The first part of the thesis computes the G-equivariant homotopy type of the real topological cyclic homology of spherical group rings at a prime p with anti-involution induced by taking inverses in the group. The second part of the thesis investigates the derived G...

  7. Cyclical innovations and production

    OpenAIRE

    Greiner, Alfred

    1994-01-01

    Cyclical innovations and production : a formal model of the firm reflecting Schumpeterian ideas / Alfred Greiner and Horst Hanusch. - In: Innovation in technology, industries, and institutions / ed. by Yuichi Shionoya ... - Ann Arbor : Univ. of Michigan Press, 1994. - S. 157-169

  8. Cyclic nucleotides and radioresistnace

    International Nuclear Information System (INIS)

    Kulinskij, V.I.; Mikheeva, G.A.; Zel'manovich, B.M.

    1982-01-01

    The addition of glucose to meat-peptone broth does not change the radiosensitizing effect (RSE) of cAMP at the logarithmic phase (LP) and the radioprotective effect (RPE) at the stationary phase (SP), but sensitization, characteristic of cGMP, disappears in SP and turns into RPE in LP. Introduction of glucose into the broth for 20 min eliminates all the effects of both cyclic nucleotides in the cya + strain while cya - mutant exhibits RSE. RSE of both cyclic nucleotides is only manifested on minimal media. These data brought confirmation of the dependence of the influence of cyclic media. These data brought confirmation of the dependence of the influence of cyclic nucleotides on radioresistance upon the metabolic status of the cell [ru

  9. Cyclic Biphalin Analogues Incorporating a Xylene Bridge: Synthesis, Characterization, and Biological Profile.

    Science.gov (United States)

    Stefanucci, Azzurra; Carotenuto, Alfonso; Macedonio, Giorgia; Novellino, Ettore; Pieretti, Stefano; Marzoli, Francesca; Szűcs, Edina; Erdei, Anna I; Zádor, Ferenc; Benyhe, Sándor; Mollica, Adriano

    2017-08-10

    In this work we enhanced the ring lipophilicity of biphalin introducing a xylene moiety, thus obtaining three cyclic regioisomers. Novel compounds have similar in vitro activity as the parent compound, but one of these ( 6a ) shows a remarkable increase of in vivo antinociceptive effect. Nociception tests have disclosed its significant high potency and the more prolonged effect in eliciting analgesia, higher than that of biphalin and of the disulfide-bridge-containing analogue ( 7 ).

  10. Disulfide Chromophore and Its Optical Activity

    Czech Academy of Sciences Publication Activity Database

    Maloň, Petr; Bednárová, Lucie; Straka, Michal; Krejčí, Lucie; Kumprecht, Lukáš; Kraus, Tomáš; Kubáňová, M.; Baumruk, V.

    2010-01-01

    Roč. 22, 1E (2010), E47-E55 ISSN 0899-0042 R&D Projects: GA ČR(CZ) GA203/07/1335; GA ČR GA203/06/1550; GA ČR GA203/09/2037; GA ČR GAP208/10/0376; GA AV ČR IAA400550810 Institutional research plan: CEZ:AV0Z40550506 Keywords : disulfide chromophore * Raman optical activity * vibrational optical activity * circular dichroism Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.892, year: 2010

  11. Single-layer Molybdenum disulfide photodetectors

    OpenAIRE

    López Sánchez, Oriol

    2012-01-01

    Projecte realitzat mitjançant programa de mobilitat. École polytechnique fédérale de Lausanne [ANGLÈS] Two-dimensional (2D) materials are very attractive candidates for use in next-generation nanoelectronic devices. Compared to one-dimensional materials, with 2D materials is relatively easy to fabricate complex structures. 2D materials, such as molybdenum disulfide (MoS2), have attracted increasing attention for their electronic and optoelectronic particular properties and size. MoS2 is a...

  12. 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)

  13. 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

  14. 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 ...

  15. 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.

  16. 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.

  17. Compact conformations of human protein disulfide isomerase.

    Directory of Open Access Journals (Sweden)

    Shang Yang

    Full Text Available Protein disulfide isomerase (PDI composed of four thioredoxin-like domains a, b, b', and a', is a key enzyme catalyzing oxidative protein folding in the endoplasmic reticulum. Large scale molecular dynamics simulations starting from the crystal structures of human PDI (hPDI in the oxidized and reduced states were performed. The results indicate that hPDI adopts more compact conformations in solution than in the crystal structures, which are stabilized primarily by inter-domain interactions, including the salt bridges between domains a and b' observed for the first time. A prominent feature of the compact conformations is that the two catalytic domains a and a' can locate close enough for intra-molecular electron transfer, which was confirmed by the characterization of an intermediate with a disulfide between the two domains. Mutations, which disrupt the inter-domain interactions, lead to decreased reductase activity of hPDI. Our molecular dynamics simulations and biochemical experiments reveal the intrinsic conformational dynamics of hPDI and its biological impact.

  18. Generalized Wideband Cyclic MUSIC

    Directory of Open Access Journals (Sweden)

    Zhang-Meng Liu

    2009-01-01

    Full Text Available The method of Spectral Correlation-Signal Subspace Fitting (SC-SSF fails to separate wideband cyclostationary signals with coherent second-order cyclic statistics (SOCS. Averaged Cyclic MUSIC (ACM method made up for the drawback to some degree via temporally averaging the cyclic cross-correlation of the array output. This paper interprets ACM from another perspective and proposes a new DOA estimation method by generalizing ACM for wideband cyclostationary signals. The proposed method successfully makes up for the aforementioned drawback of SC-SSF and obtains a more satisfying performance than ACM. It is also demonstrated that ACM is a simplified form of the proposed method when only a single spectral frequency is exploited, and the integration of the frequencies within the signal bandwidth helps the new method to outperform ACM.

  19. Disulfide Linkage Characterization of Disulfide Bond-Containing Proteins and Peptides by Reducing Electrochemistry and Mass Spectrometry

    DEFF Research Database (Denmark)

    Cramer, Christian N; Haselmann, Kim F; Olsen, Jesper V

    2016-01-01

    to avoid disulfide scrambled and incorrectly folded forms in the final product. Mass spectrometry (MS) is a highly utilized analytical tool for this due to fast and accurate characterization. However, disulfide bonds being an additional covalent bond in the protein structure represent a challenge...... link between parent disulfide-linked fragments and free reduced peptides in an LC-EC-MS platform of nonreduced proteolytic protein digestions. Here we report the successful use of EC as a partial reduction approach in mapping of disulfide bonds of intact human insulin (HI) and lysozyme. In addition, we......Unravelling of disulfide linkage patterns is a crucial part of protein characterization, whether it is for a previously uncharacterized protein in basic research or a recombinant pharmaceutical protein. In the biopharmaceutical industry, elucidation of the cysteine connectivities is a necessity...

  20. Thiol/disulfide homeostasis in untreated schizophrenia patients.

    Science.gov (United States)

    Topcuoglu, Canan; Bakirhan, Abdurrahim; Yilmaz, Fatma Meric; Neselioglu, Salim; Erel, Ozcan; Sahiner, Safak Yalcin

    2017-05-01

    The aim of the study was to investigate dynamic thiol/disulfide (SH/SS) homeostasis in untreated schizophrenia. Blood thiol/disulfide homeostasis status, which reflects native thiol-disulfide exchanges, was investigated in 87 untreated patients (52 males, 35 females), and the obtained results were compared with 86 healthy controls. Blood serum native thiol and total thiol (ToSH) concentrations were measured in a paired test. The half value of the difference between native thiol and ToSH concentrations was calculated as the disulfide bond amount. SH and ToSH concentrations were found to be significantly lower (pschizophrenia compared with the control group, whereas disulfide levels were significantly higher (pSchizophrenia patients had significantly higher SS/ToSH and SS/SH ratios and a significantly lower SH/ToSH ratio compared to those of healthy individuals. SH and ToSH amounts were found to be insufficient in untreated schizophrenia patients. Additionally, according to the results of the study, thiol/disulfide homeostasis was also disturbed by a shift to the disulfide bond formation side. This might affect the neurotransmission processes, which are known to be related with many symptoms observed in schizophrenia. The replacement of the thiol gap and the reduction of excess SS amounts might have a positive effect in supporting therapy for schizophrenia patients. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

  1. Chemoreactomic analysis of thiamine disulfide, thiamine hydrochloride, and benfotiamine molecules

    Directory of Open Access Journals (Sweden)

    O. A. Gromova

    2017-01-01

    Full Text Available Objective: to analyze the interactions that could indicate the potential pharmacological properties of the molecules of thiamin, thiamine disulfide, and others.Material and methods. The investigators simulated the properties of thiamine disulfide (bistiamin versus those of the reference molecules of thiamin hydrochloride and benfotiamine. The study was performed using chemoreactomic simulation that is the newest area in post-genome pharmacology.Results and discussion. Chemoreactomic analysis has shown that thiamine disulfide can inhibit the molecular receptors involved in blood pressure regulation: adrenoceptors, vasopressin receptor, and angiotensin receptor. Thiamine disulfide can inhibit the reuptake of serotonin, increase its levels, inhibit benzodiazepine receptor and dopamine reuptake, and enhance neuronal acetylcholine release to a large extent than benfotiamine. These molecular effects are consistent with the sedative and anticonvulsant action profile of thiamine disulfide. Simulation has indicated that thiamine disulfide has neuroprotective, anti-inflammatory, normolipidemic, and antitumor activities.Conclusion. The simulation results are confirmed by the available clinical and experimental findings and indicate the virtually unstudied molecular mechanisms of action of thiamine disulfide, benfotiamine, and thiamin hydrochloride. 

  2. Protein disulfide bond formation in the cytoplasm during oxidative stress.

    Science.gov (United States)

    Cumming, Robert C; Andon, Nancy L; Haynes, Paul A; Park, Minkyu; Fischer, Wolfgang H; Schubert, David

    2004-05-21

    The majority of disulfide-linked cytosolic proteins are thought to be enzymes that transiently form disulfide bonds while catalyzing oxidation-reduction (redox) processes. Recent evidence indicates that reactive oxygen species can act as signaling molecules by promoting the formation of disulfide bonds within or between select redox-sensitive proteins. However, few studies have attempted to examine global changes in disulfide bond formation following reactive oxygen species exposure. Here we isolate and identify disulfide-bonded proteins (DSBP) in a mammalian neuronal cell line (HT22) exposed to various oxidative insults by sequential nonreducing/reducing two-dimensional SDS-PAGE combined with mass spectrometry. By using this strategy, several known cytosolic DSBP, such as peroxiredoxins, thioredoxin reductase, nucleoside-diphosphate kinase, and ribonucleotide-diphosphate reductase, were identified. Unexpectedly, a large number of previously unknown DSBP were also found, including those involved in molecular chaperoning, translation, glycolysis, cytoskeletal structure, cell growth, and signal transduction. Treatment of cells with a wide range of hydrogen peroxide concentrations either promoted or inhibited disulfide bonding of select DSBP in a concentration-dependent manner. Decreasing the ratio of reduced to oxidized glutathione also promoted select disulfide bond formation within proteins from cytoplasmic extracts. In addition, an epitope-tagged version of the molecular chaperone HSP70 forms mixed disulfides with both beta4-spectrin and adenomatous polyposis coli protein in the cytosol. Our findings indicate that disulfide bond formation within families of cytoplasmic proteins is dependent on the nature of the oxidative insult and may provide a common mechanism used to control multiple physiological processes.

  3. Steric effects in peptide and protein exchange with activated disulfides.

    Science.gov (United States)

    Kerr, Jason; Schlosser, Jessica L; Griffin, Donald R; Wong, Darice Y; Kasko, Andrea M

    2013-08-12

    Disulfide exchange is an important bioconjugation tool, enabling chemical modification of peptides and proteins containing free cysteines. We previously reported the synthesis of a macromer bearing an activated disulfide and its incorporation into hydrogels. Despite their ability to diffuse freely into hydrogels, larger proteins were unable to undergo in-gel disulfide exchange. In order to understand this phenomenon, we synthesized four different activated disulfide-bearing model compounds (Mn = 300 Da to 10 kDa) and quantified their rate of disulfide exchange with a small peptide (glutathione), a moderate-sized protein (β-lactoglobulin), and a large protein (bovine serum albumin) in four different pH solutions (6.0, 7.0, 7.4, and 8.0) to mimic biological systems. Rate constants of exchange depend significantly on the size and accessibility of the thiolate. pH also significantly affects the rate of reaction, with the faster reactions occurring at higher pH. Surprisingly, little difference in exchange rates is seen between macromolecular disulfides of varying size (Mn = 2 kDa - 10 kDa), although all undergo exchange more slowly than their small molecule analogue (MW = 300 g/mol). The maximum exchange efficiencies (% disulfides exchanged after 24 h) are not siginificantly affected by thiol size or pH, but somewhat affected by disulfide size. Therefore, while all three factors investigated (pH, disulfide size, and thiolate size) can influence the exchange kinetics and extent of reaction, the size of the thiolate and its accessibility plays the most significant role.

  4. Catalysis of Protein Disulfide Bond Isomerization in a Homogeneous Substrate†

    Science.gov (United States)

    Kersteen, Elizabeth A.; Barrows, Seth R.; Raines, Ronald T.

    2008-01-01

    Protein disulfide isomerase (PDI) catalyzes the rearrangement of nonnative disulfide bonds in the endoplasmic reticulum of eukaryotic cells, a process that often limits the rate at which polypeptide chains fold into a native protein conformation. The mechanism of the reaction catalyzed by PDI is unclear. In assays involving protein substrates, the reaction appears to involve the complete reduction of some or all of its nonnative disulfide bonds followed by oxidation of the resulting dithiols. The substrates in these assays are, however, heterogeneous, which complicates mechanistic analyses. Here, we report the first analysis of disulfide bond isomerization in a homogeneous substrate. Our substrate is based on tachyplesin I, a 17-mer peptide that folds into a _-hairpin stabilized by two disulfide bonds. We describe the chemical synthesis of a variant of tachyplesin I in which its two disulfide bonds are in a nonnative state and side chains near its N-and C-terminus contain a fluorescence donor (tryptophan) and acceptor (N_-dansyllysine). Fluorescence resonance energy transfer from 280 to 465 nm increases by 28-fold upon isomerization of the disulfide bonds into their native state (which has a lower E°_ = -0.313 V than does PDI). We use this continuous assay to analyze catalysis by wild-type human PDI and a variant in which the C-terminal cysteine residue within each Cys—Gly—His—Cys active site is replaced with alanine. We find that wild-type PDI catalyzes the isomerization of the substrate with kcat/KM = 1.7 _ 105 M–1M s–1, which is the largest value yet reported for catalysis of disulfide bond isomerization. The variant, which is a poor catalyst of disulfide bond reduction and dithiol oxidation, retains virtually all of the activity of wild-type PDI in catalysis of disulfide bond isomerization. Thus, the C-terminal cysteine residues play an insignificant role in the isomerization of the disulfide bonds in nonnative tachyplesin I. We conclude that

  5. Catalysis of protein disulfide bond isomerization in a homogeneous substrate.

    Science.gov (United States)

    Kersteen, Elizabeth A; Barrows, Seth R; Raines, Ronald T

    2005-09-13

    Protein disulfide isomerase (PDI) catalyzes the rearrangement of nonnative disulfide bonds in the endoplasmic reticulum of eukaryotic cells, a process that often limits the rate at which polypeptide chains fold into a native protein conformation. The mechanism of the reaction catalyzed by PDI is unclear. In assays involving protein substrates, the reaction appears to involve the complete reduction of some or all of its nonnative disulfide bonds followed by oxidation of the resulting dithiols. The substrates in these assays are, however, heterogeneous, which complicates mechanistic analyses. Here, we report the first analysis of disulfide bond isomerization in a homogeneous substrate. Our substrate is based on tachyplesin I, a 17-mer peptide that folds into a beta hairpin stabilized by two disulfide bonds. We describe the chemical synthesis of a variant of tachyplesin I in which its two disulfide bonds are in a nonnative state and side chains near its N and C terminus contain a fluorescence donor (tryptophan) and acceptor (N(epsilon)-dansyllysine). Fluorescence resonance energy transfer from 280 to 465 nm increases by 28-fold upon isomerization of the disulfide bonds into their native state (which has a lower E(o') = -0.313 V than does PDI). We use this continuous assay to analyze catalysis by wild-type human PDI and a variant in which the C-terminal cysteine residue within each Cys-Gly-His-Cys active site is replaced with alanine. We find that wild-type PDI catalyzes the isomerization of the substrate with kcat/K(M) = 1.7 x 10(5) M(-1) s(-1), which is the largest value yet reported for catalysis of disulfide bond isomerization. The variant, which is a poor catalyst of disulfide bond reduction and dithiol oxidation, retains virtually all of the activity of wild-type PDI in catalysis of disulfide bond isomerization. Thus, the C-terminal cysteine residues play an insignificant role in the isomerization of the disulfide bonds in nonnative tachyplesin I. We conclude

  6. Reactivity of disulfide bonds is markedly affected by structure and environment

    DEFF Research Database (Denmark)

    Karimi, Maryam; Ignasiak, Marta T; Chan, Bun

    2016-01-01

    that selected disulfides react extremely rapidly, with a variation of 10(4) in rate constants. Five-membered ring disulfides are particularly reactive compared with acyclic (linear) disulfides or six-membered rings. Particular disulfides in proteins also show enhanced reactivity. This variation occurs...

  7. Cyclic Voltammograms from First Principles

    DEFF Research Database (Denmark)

    Karlberg, Gustav; Jaramillo, Thomas; Skulason, Egill

    2007-01-01

    Cyclic voltammetry is a fundamental experimental tool for characterizing electrochemical surfaces. Whereas cyclic voltammetry is widely used within the field of electrochemistry, a way to quantitatively and directly relate the cyclic voltammogram to ab initio calculations has been lacking, even f...

  8. 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

  9. (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).

  10. [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).

  11. 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.

  12. 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.

  13. 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

  14. Dynamics of cyclic machines

    CERN Document Server

    Vulfson, Iosif

    2015-01-01

    This book focuses on modern methods of oscillation analysis in machines, including cyclic action mechanisms (linkages, cams, steppers, etc.). It presents schematization techniques and mathematical descriptions of oscillating systems, taking into account the variability of the parameters and nonlinearities, engineering evaluations of dynamic errors, and oscillation suppression methods. The majority of the book is devoted to the development of new methods of dynamic analysis and synthesis for cyclic machines that form regular oscillatory systems with multiple duplicate modules.  There are also sections examining aspects of general engineering interest (nonlinear dissipative forces, systems with non-stationary constraints, impacts and pseudo-impacts in clearances, etc.)  The examples in the book are based on the widely used results of theoretical and experimental studies as well as engineering calculations carried out in relation to machines used in the textile, light, polygraphic and other industries. Particu...

  15. 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.

  16. HOST liner cyclic facilities

    Science.gov (United States)

    Schultz, D.

    1983-01-01

    The HOST Liner Cyclic Program is utilizing two types of test apparatus, rectangular box rigs and a full annular rig. To date two quartz lamp cyclic box rigs have been tested and a third is to begin testing in late October 1983. The box rigs are used to evaluate 5x8 inch rectangular linear samples. A 21 inch diameter outer liner simulator is also being built up for testing beginning in April 1984. All rigs are atmospheric rigs. The first box rig, a three 6-kVA lamp installation, was operated under adverse conditions to determine feasibility of using quartz lamps for cyclic testing. This work was done in December 1981 and looked promising. The second box rig, again using three 6-kVA lamps, was operated to obtain instrumentation durability information and initial data input to a Finite Element Model. This limited test program was conducted in August 1983. Five test plates were run. Instrumentation consisted of strain gages, thermocouples and thermal paint. The strain gages were found to fail at 1200 F as expected though plates were heated to 1700 F. The third box rig, containing four 6-kVA lamps, is in build up for testing to begin in late October 1983. In addition to 33 percent greater power input, this rig has provision for 400 F backside line cooling air and a viewing port suitable for IR camera viewing. The casing is also water cooled for extended durability.

  17. Thiol-Disulfide Exchange between Glutaredoxin and Glutathione

    DEFF Research Database (Denmark)

    Iversen, Rasmus; Andersen, Peter Anders; Jensen, Kristine Steen

    2010-01-01

    Glutaredoxins are ubiquitous thiol-disulfide oxidoreductases which catalyze the reduction of glutathione-protein mixed disulfides. Belonging to the thioredoxin family, they contain a conserved active site CXXC motif. The N-proximal active site cysteine can form a mixed disulfide with glutathione ...... has been replaced with serine. The exchange reaction between the reduced protein and oxidized glutathione leading to formation of the mixed disulfide could readily be monitored by isothermal titration calorimetry (ITC) due to the enthalpic contributions from the noncovalent interactions...... and the protonation of glutathione thiolate. An algorithm for the analysis of this type of reaction by ITC was developed and showed that the interaction is enthalpy driven with a large entropy penalty. The applicability of the method was verified by a mass spectrometry-based approach, which gave a standard reduction...

  18. Chemoreactomic analysis of thiamine disulfide, thiamine hydrochloride, and benfotiamine molecules

    OpenAIRE

    O. A. Gromova; I. Yu. Torshin; L. V. Stakhovskaya; L. E. Fedotova

    2017-01-01

    Objective: to analyze the interactions that could indicate the potential pharmacological properties of the molecules of thiamin, thiamine disulfide, and others.Material and methods. The investigators simulated the properties of thiamine disulfide (bistiamin) versus those of the reference molecules of thiamin hydrochloride and benfotiamine. The study was performed using chemoreactomic simulation that is the newest area in post-genome pharmacology.Results and discussion. Chemoreactomic analysis...

  19. Regulation of a phage endolysin by disulfide caging.

    Science.gov (United States)

    Kuty, Gabriel F; Xu, Min; Struck, Douglas K; Summer, Elizabeth J; Young, Ry

    2010-11-01

    In contrast to canonical phage endolysins, which require holin-mediated disruption of the membrane to gain access to attack the cell wall, signal anchor release (SAR) endolysins are secreted by the host sec system, where they accumulate in an inactive form tethered to the membrane by their N-terminal SAR domains. SAR endolysins become activated by various mechanisms upon release from the membrane. In its inactive form, the prototype SAR endolysin, Lyz(P1), of coliphage P1, has an active-site Cys covalently blocked by a disulfide bond; activation involves a disulfide bond isomerization driven by a thiol in the newly released SAR domain, unblocking the active-site Cys. Here, we report that Lyz(103), the endolysin of Erwinia phage ERA103, is also a SAR endolysin. Although Lyz(103) does not have a catalytic Cys, genetic evidence suggests that it also is activated by a thiol-disulfide isomerization triggered by a thiol in the SAR domain. In this case, the inhibitory disulfide in nascent Lyz(103) is formed between cysteine residues flanking a catalytic glutamate, caging the active site. Thus, Lyz(P1) and Lyz(103) define subclasses of SAR endolysins that differ in the nature of their inhibitory disulfide, and Lyz(103) is the first enzyme found to be regulated by disulfide bond caging of its active site.

  20. 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 ...

  1. Cyclic approximation to stasis

    Directory of Open Access Journals (Sweden)

    Stewart D. Johnson

    2009-06-01

    Full Text Available Neighborhoods of points in $mathbb{R}^n$ where a positive linear combination of $C^1$ vector fields sum to zero contain, generically, cyclic trajectories that switch between the vector fields. Such points are called stasis points, and the approximating switching cycle can be chosen so that the timing of the switches exactly matches the positive linear weighting. In the case of two vector fields, the stasis points form one-dimensional $C^1$ manifolds containing nearby families of two-cycles. The generic case of two flows in $mathbb{R}^3$ can be diffeomorphed to a standard form with cubic curves as trajectories.

  2. Accelerated cyclic corrosion tests

    Directory of Open Access Journals (Sweden)

    Prošek T.

    2016-06-01

    Full Text Available Accelerated corrosion testing is indispensable for material selection, quality control and both initial and residual life time prediction for bare and painted metallic, polymeric, adhesive and other materials in atmospheric exposure conditions. The best known Neutral Salt Spray (NSS test provides unrealistic conditions and poor correlation to exposures in atmosphere. Modern cyclic accelerated corrosion tests include intermittent salt spray, wet and dry phases and eventually other technical phases. They are able to predict the material performance in service more correctly as documented on several examples. The use of NSS should thus be restricted for quality control.

  3. 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.

  4. Ekpyrotic and cyclic cosmology

    International Nuclear Information System (INIS)

    Lehners, Jean-Luc

    2008-01-01

    Ekpyrotic and cyclic cosmologies provide theories of the very early and of the very late universe. In these models, the big bang is described as a collision of branes - and thus the big bang is not the beginning of time. Before the big bang, there is an ekpyrotic phase with equation of state w=P/(ρ) >>1 (where P is the average pressure and ρ the average energy density) during which the universe slowly contracts. This phase resolves the standard cosmological puzzles and generates a nearly scale-invariant spectrum of cosmological perturbations containing a significant non-Gaussian component. At the same time it produces small-amplitude gravitational waves with a blue spectrum. The dark energy dominating the present-day cosmological evolution is reinterpreted as a small attractive force between our brane and a parallel one. This force eventually induces a new ekpyrotic phase and a new brane collision, leading to the idea of a cyclic universe. This review discusses the detailed properties of these models, their embedding in M-theory and their viability, with an emphasis on open issues and observational signatures

  5. Cyclic generalized projection MRI.

    Science.gov (United States)

    Sarty, Gordon E

    2015-04-01

    Progress in the development of portable MRI hinges on the ability to use lightweight magnets that have non-uniform magnetic fields. An image encoding method and mathematical procedure for recovering the image from the NMR signal from non-uniform magnets with closed isomagnetic contours is given. Individual frequencies in an NMR signal from an object in a non-uniform magnetic field give rise to integrals of the object along contours of constant magnetic field: generalized projections. With closed isomagnetic field contours a simple, cyclic, direct reconstruction of the image from the generalized projections is possible when the magnet and RF transmit coil are held fixed relative to the imaged object while the RF receive coil moves. Numerical simulations, using the Shepp and Logan mathematical phantom, were completed to show that the mathematical method works and to illustrate numerical limitations. The method is numerically verified and exact reconstruction demonstrated for discrete mathematical image phantoms. Correct knowledge of the RF receive field is necessary or severe image distortions will result. The cyclic mathematical reconstruction method presented here will be useful for portable MRI schemes that use non-uniform magnets with closed isomagnetic contours along with mechanically or electronically moving the RF receive coils. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. 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.

  7. The influence of zinc(II) on thioredoxin/glutathione disulfide exchange: QM/MM studies to explore how zinc(II) accelerates exchange in higher dielectric environments.

    Science.gov (United States)

    Kurian, Roby; Bruce, Mitchell R M; Bruce, Alice E; Amar, François G

    2015-08-01

    QM/MM studies were performed to explore the energetics of exchange reactions of glutathione disulfide (GSSG) and the active site of thioredoxin [Cys32-Gly33-Pro34-Cys35] with and without zinc(II), in vacuum and solvated models. The activation energy for exchange, in the absence of zinc, is 29.7 kcal mol(-1) for the solvated model. This is 3.3 kcal mol(-1) higher than the activation energy for exchange in the gas phase, due to ground state stabilization of the active site Cys-32 thiolate in a polar environment. In the presence of zinc, the activation energy for exchange is 4.9 kcal mol(-1) lower than in the absence of zinc (solvated models). The decrease in activation energy is attributed to stabilization of the charge-separated transition state, which has a 4-centered, cyclic arrangement of Zn-S-S-S with an estimated dipole moment of 4.2 D. A difference of 4.9 kcal mol(-1) in activation energy would translate to an increase in rate by a factor of about 4000 for zinc-assisted thiol-disulfide exchange. The calculations are consistent with previously reported experimental results, which indicate that metal-thiolate, disulfide exchange rates increase as a function of solvent dielectric. This trend is opposite to that observed for the influence of the dielectric environment on the rate of thiol-disulfide exchange in the absence of metal. The results suggest a dynamic role for zinc in thiol-disulfide exchange reactions, involving accessible cysteine sites on proteins, which may contribute to redox regulation and mechanistic pathways during oxidative stress.

  8. 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.

  9. 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.

  10. The arabidopsis cyclic nucleotide interactome

    KAUST Repository

    Donaldson, Lara Elizabeth

    2016-05-11

    Background Cyclic nucleotides have been shown to play important signaling roles in many physiological processes in plants including photosynthesis and defence. Despite this, little is known about cyclic nucleotide-dependent signaling mechanisms in plants since the downstream target proteins remain unknown. This is largely due to the fact that bioinformatics searches fail to identify plant homologs of protein kinases and phosphodiesterases that are the main targets of cyclic nucleotides in animals. Methods An affinity purification technique was used to identify cyclic nucleotide binding proteins in Arabidopsis thaliana. The identified proteins were subjected to a computational analysis that included a sequence, transcriptional co-expression and functional annotation analysis in order to assess their potential role in plant cyclic nucleotide signaling. Results A total of twelve cyclic nucleotide binding proteins were identified experimentally including key enzymes in the Calvin cycle and photorespiration pathway. Importantly, eight of the twelve proteins were shown to contain putative cyclic nucleotide binding domains. Moreover, the identified proteins are post-translationally modified by nitric oxide, transcriptionally co-expressed and annotated to function in hydrogen peroxide signaling and the defence response. The activity of one of these proteins, GLYGOLATE OXIDASE 1, a photorespiratory enzyme that produces hydrogen peroxide in response to Pseudomonas, was shown to be repressed by a combination of cGMP and nitric oxide treatment. Conclusions We propose that the identified proteins function together as points of cross-talk between cyclic nucleotide, nitric oxide and reactive oxygen species signaling during the defence response.

  11. Cyclic transfers in school timetabling

    NARCIS (Netherlands)

    Post, Gerhard F.; Ahmadi, Samad; Geertsema, Frederik

    2012-01-01

    In this paper we propose a neighbourhood structure based on sequential/cyclic moves and a cyclic transfer algorithm for the high school timetabling problem. This method enables execution of complex moves for improving an existing solution, while dealing with the challenge of exploring the

  12. Cyclic transfers in school timetabling

    NARCIS (Netherlands)

    Post, Gerhard F.; Ahmadi, Samad; Geertsema, Frederik

    In this paper we propose a neighbourhood structure based on sequential/cyclic moves and a Cyclic Transfer algorithm for the high school timetabling problem. This method enables execution of complex moves for improving an existing solution, while dealing with the challenge of exploring the

  13. Production of Disulfide-Bonded Proteins in Escherichia coli.

    Science.gov (United States)

    Ke, Na; Berkmen, Mehmet

    2014-10-01

    Production of recombinant proteins at high yields in Escherichia coli requires extensive optimization of expression conditions. Production is further complicated for proteins that require specific post-translational modifications for their eventual folding. One common and particularly important post-translational modification is oxidation of the correct pair of cysteines to form a disulfide bond. This unit describes methods to produce disulfide-bonded proteins in E. coli in either the naturally oxidizing periplasm or the cytoplasm of appropriately engineered cells. The focus is on variables key to improving the oxidative folding of disulfide-bonded proteins, with the aim of helping the researcher optimize expression conditions for a protein of interest. Copyright © 2014 John Wiley & Sons, Inc.

  14. A molybdenum disulfide/carbon nanotube heterogeneous complementary inverter.

    Science.gov (United States)

    Huang, Jun; Somu, Sivasubramanian; Busnaina, Ahmed

    2012-08-24

    We report a simple, bottom-up/top-down approach for integrating drastically different nanoscale building blocks to form a heterogeneous complementary inverter circuit based on layered molybdenum disulfide and carbon nanotube (CNT) bundles. The fabricated CNT/MoS(2) inverter is composed of n-type molybdenum disulfide (MOS(2)) and p-type CNT transistors, with a high voltage gain of 1.3. The CNT channels are fabricated using directed assembly while the layered molybdenum disulfide channels are fabricated by mechanical exfoliation. This bottom-up fabrication approach for integrating various nanoscale elements with unique characteristics provides an alternative cost-effective methodology to complementary metal-oxide-semiconductors, laying the foundation for the realization of high performance logic circuits.

  15. 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.

  16. Manual for Cyclic Triaxial Test

    DEFF Research Database (Denmark)

    Shajarati, Amir; Sørensen, Kris Wessel; Nielsen, Søren Kjær

    This manual describes the different steps that is included in the procedure for conducting a cyclic triaxial test at the geotechnical Laboratory at Aalborg University. Furthermore it contains a chapter concerning some of the background theory for the static triaxial tests. The cyclic/dynamic tria......This manual describes the different steps that is included in the procedure for conducting a cyclic triaxial test at the geotechnical Laboratory at Aalborg University. Furthermore it contains a chapter concerning some of the background theory for the static triaxial tests. The cyclic....../dynamic triaxial cell is overall constructed in the same way as the static triaxial cell at Aalborg University, but with the ability to apply any kind of load sequence to the test sample. When conducting cyclic triaxial tests, it is recommended that the manual is followed very tediously since there are many steps...

  17. Identification of Disulfides from the Biodegradation of Dibenzothiophene

    Science.gov (United States)

    Bressler, David C.; Fedorak, Phillip M.

    2001-01-01

    Several investigations have identified benzothiophene-2,3-dione in the organic solvent extracts of acidified cultures degrading dibenzothiophene via the Kodama pathway. In solution at neutral pH, the 2,3-dione exists as 2-mercaptophenylglyoxylate, which cyclizes upon acidification and is extracted as the 2,3-dione. The fate of these compounds in microbial cultures has never been determined. This study investigated the abiotic reactions of 2-mercaptophenylglyoxylate incubated aerobically in mineral salts medium at neutral pH. Oxidation led to the formation of 2-oxo-2-(2-thiophenyl)ethanoic acid disulfide, formed from two molecules of 2-mercaptophenylglyoxylate. Two sequential abiotic, net losses of both a carbon and an oxygen atom produced two additional disulfides, 2-oxo-2-(2-thiophenyl)ethanoic acid 2-benzoic acid disulfide and 2,2′-dithiosalicylic acid. The methods developed to extract and detect these three disulfides were then used for the analysis of a culture of Pseudomonas sp. strain BT1d grown on dibenzothiophene as its sole carbon and energy source. All three of the disulfides were detected, indicating that 2-mercaptophenylglyoxylate is an important, short-lived intermediate in the breakdown of dibenzothiophene via the Kodama pathway. The disulfides eluded previous investigations because of (i) their high polarity, being dicarboxylic acids; (ii) the need to lower the pH of the aqueous medium to <1 to extract them into an organic solvent such as dichloromethane; (iii) their poor solubility in organic solvents, (iv) their removal from organic extracts of cultures during filtration through the commonly used drying agent anhydrous sodium sulfate; and (v) their high molecular masses (362, 334, and 306 Da) compared to that of dibenzothiophene (184 Da). PMID:11679330

  18. Electrostatic influence of local cysteine environments on disulfide exchange kinetics.

    Science.gov (United States)

    Snyder, G H; Cennerazzo, M J; Karalis, A J; Field, D

    1981-11-10

    The ionic strength dependence of the bimolecular rate constant for reaction of the negative disulfide 5,5'-dithiobis (2-nitrobenzoic acid) with cysteines in fragments of naturally occurring proteins was determined by stopped-flow spectroscopy. The Debye-Hückel relationship was applied to determine the effective charge at the cysteine and thereby determine the extent to which nearby neighbors in the primary sequence influence the kinetics. Corrections for the secondary salt effect on cysteine pKs were determined by direct spectrometric pH titration of sulfhydryl groups or by observation of the ionic strength dependence of kinetics of cysteine reaction with the neutral disulfide 2,2'-dithiodipyridine. Quantitative expressions was verified by model studies with N-acetyl-cystein. At ionic strengths equal to or greater than 20 mM, the net charge at the polypeptide cysteine site is the sum of the single negative charge of the thiolate anion and the charges of the amino acids immediately preceding and following the cysteine in the primary sequence. At lower ionic strengths, more distant residues influence kinetics. At pH 7.0, 23 degree C, and an ionic strength of 20 mM, rate constants for reaction of the negative disulfide with a cysteine having two positive neighbors, one positive and one neutral neighbor, or two neutral neighbors are 132000, 3350, and 367 s-1 M-1, respectively. This corresponds to a contribution to the activation energy of 0.65- 1.1 kcal/mol per ion pair involved in collision between the cysteine and disulfide regions. The results permit the estimation that cysteine local environments may provide a means of achieving a 10(6)-fold range in rate constants in disulfide exchange reactions in random-coil proteins. This range may prove useful in developing strategies for directing disulfide pairing in synthetic proteins.

  19. Structures and related properties of helical, disulfide-stabilized peptides

    Energy Technology Data Exchange (ETDEWEB)

    Pagel, Mark D. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1993-11-01

    The three dimensional structure of several peptides were determined by NMR spectroscopy and distance geometry calculations. Each peptide formed a predictable, rigid structure, consisting of an α-helix, a "scaffold" region which packed along one face of the helix, and two disulfide bridges which covalently connect the helix and scaffold regions. The peptide Apa-M5 was designed to constrain the M5 peptide from MLCK in a helical geometry using the apamin disulfide scaffold. This scaffold constrains the N- terminal end of the helix with two disulfide bridges and a reverse turn. Like the M5 peptide, Apa-M5 was found to bind calmodulin in a Ca2+-dependent 1:1 stoichiometry. However, the dissociation constant of the (Apa-M5)-calmodulin complex, 107 nM, was 100-fold higher than the dissociation constant of the M5-calmodulin complex. This difference was due to a putative steric overlap between the Apa-M5 scaffold and calmodulin. The peptide Apa-Cro was designed to replace the large structural protein matrix of λ Cro with the apamin disulfide scaffold. However, Apa-Cro did not bind the consensus DNA operator half-site of λ Cro, probably due to a steric overlap between the Apa-Cro disulfide framework and the DNA. The amino acid sequence of the scaffold-disulfide bridge arrangement of the peptide Max was derived from the core sequence of scyllatoxin, which contains an α-helix constrained at the C-terminal end by two disulfide bridges and a two-stranded βsheet scaffold. Max was shown to fold with >84% yield to form a predictable, stable structure that is similar to scyllatoxin. The folding and stability properties of Max make this scaffold and disulfide bridge arrangement an ideal candidate for the development of hybrid sequence peptides. The dynamics of a fraying C-terminal end of the helix of the peptide Apa-AlaN was determined by analysis of 15N NMR relaxation properties.

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

    Science.gov (United States)

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

    2012-01-01

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

  1. Chemical and Photochemical Reactions of Thioctic Acid and RelatedDisulfides

    Energy Technology Data Exchange (ETDEWEB)

    Calvin, Melvin

    1954-06-10

    The carbon cycle of photosynthesis is briefly reviewed in its entirety and the experiments involving it which led to the implication of disulfide rupture in photosynthesis are indicated. A review of the organic, physical and photochemistry of disulfides, with particular reference to the five-membered disulfide rings as they appear in thioctic acid, is given.

  2. Ada and cyclic runtime scheduling

    Science.gov (United States)

    Hood, Philip E.

    1986-01-01

    An important issue that must be faced while introducing Ada into the real time world is efficient and prodictable runtime behavior. One of the most effective methods employed during the traditional design of a real time system is the cyclic executive. The role cyclic scheduling might play in an Ada application in terms of currently available implementations and in terms of implementations that might be developed especially to support real time system development is examined. The cyclic executive solves many of the problems faced by real time designers, resulting in a system for which it is relatively easy to achieve approporiate timing behavior. Unfortunately a cyclic executive carries with it a very high maintenance penalty over the lifetime of the software that is schedules. Additionally, these cyclic systems tend to be quite fragil when any aspect of the system changes. The findings are presented of an ongoing SofTech investigation into Ada methods for real time system development. The topics covered include a description of the costs involved in using cyclic schedulers, the sources of these costs, and measures for future systems to avoid these costs without giving up the runtime performance of a cyclic system.

  3. Metal-free oxidative coupling of thiols to disulfides using ...

    Indian Academy of Sciences (India)

    Abstract. Efficient combination of nitro urea or guanidinium nitrate and silica sulfuric acid (SiO2OSO3H) as a new oxidizing system is able to oxidize a variety of aliphatic or aromatic thiols to the corresponding disulfides. The process reported here is operationally simple, environmentally benign and reactions have been ...

  4. Alpha-cyclodextrins reversibly capped with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Kumprecht, Lukáš; Buděšínský, Miloš; Bouř, Petr; Kraus, Tomáš

    2010-01-01

    Roč. 34, č. 10 (2010), s. 2254-2260 ISSN 1144-0546 R&D Projects: GA AV ČR IAA400550810 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclodextrin s * disulfide bond * dynamic covalent bond Subject RIV: CC - Organic Chemistry Impact factor: 2.631, year: 2010

  5. Metal-free oxidative coupling of thiols to disulfides using ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 4. Metal-free oxidative coupling of thiols to disulfides using guanidinium nitrate or nitro urea in the presence of silica sulfuric acid. Arash Ghorbani-Choghamarani Mohsen Nikoorazm Hamid Goudarziafshar Alireza Shokr Hosein Almasi. Volume 123 Issue 4 ...

  6. Dynamic thiol-disulfide homeostasis in hyperemesis gravidarum.

    Science.gov (United States)

    Ergin, M; Cendek, B D; Neselioglu, S; Avsar, A F; Erel, O

    2015-10-01

    To determine serum thiol-disulfide homeostasis in hyperemesis gravidarum. Twenty-six pregnant women with hyperemesis gravidarum and 37 healthy pregnant women were included in the study. Native thiol, disulfide and total thiol concentrations were measured with a novel automated method. Serum disulfide levels were 15.68±4.41 μmol l(-1) in the hyperemesis gravidarum group and 13.49±2.81 μmol l(-1) in the healthy group (P=0.031). Native thiol levels were 213.86±26.29 μmol l(-1) in the hyperemesis gravidarum group and 232.18±19.21 μmol l(-1) in healthy group (P=0.004), and total thiol levels were 245.23±28.58 μmol l(-1) in the hyperemesis gravidarum group and 259.17±19.94 μmol l(-1) in the healthy group (P=0.038). Native and total thiol were deficient in the hyperemesis gravidarum group and this deficiency was correlated with the severity of the disease. The thiol-disulfide balance has shifted to the oxidative side. This metabolic disturbance may have a role in the pathogenesis of hyperemesis gravidarum.

  7. Impaired Thiol-Disulfide Balance in Acute Brucellosis.

    Science.gov (United States)

    Kolgelier, Servet; Ergin, Merve; Demir, Lutfi Saltuk; Inkaya, Ahmet Cagkan; Aktug Demir, Nazlim; Alisik, Murat; Erel, Ozcan

    2017-05-24

    The objective of this study was to examine a novel profile: thiol-disulfide homeostasis in acute brucellosis. The study included 90 patients with acute brucellosis, and 27 healthy controls. Thiol-disulfide profile tests were analyzed by a recently developed method, and ceruloplasmin levels were determined. Native thiol levels were 256.72 ± 48.20 μmol/L in the acute brucellosis group and 461.13 ± 45.37 μmol/L in the healthy group, and total thiol levels were 298.58 ± 51.78 μmol/L in the acute brucellosis group and 504.83 ± 51.05 μmol/L in the healthy group (p brucellosis than in the healthy controls (p brucellosis. The strong associations between thiol-disulfide parameters and a positive acute-phase reactant reflected the disruption of the balance between the antioxidant and oxidant systems. Since thiol groups act as anti-inflammatory mediators, the alteration in the thiol-disulfide homeostasis may be involved in brucellosis.

  8. Domain architecture of protein-disulfide isomerase facilitates its dual role as an oxidase and an isomerase in Ero1p-mediated disulfide formation

    DEFF Research Database (Denmark)

    Kulp, M. S.; Frickel, E. M.; Ellgaard, Lars

    2006-01-01

    catalytic (A) domain. The specific order of thioredoxin domains in PDI is important in establishing the asymmetry in the rate of oxidation of the two active sites thus allowing A and A', two thioredoxin domains that are similar in sequence and structure, to serve opposing functional roles as a disulfide...... isomerase and disulfide oxidase, respectively. These findings reveal how native disulfide folding is accomplished in the endoplasmic reticulum and provide a context for understanding the proliferation of PDI homologs with combinatorial arrangements of thioredoxin domains.......Native disulfide bond formation in eukaryotes is dependent on protein-disulfide isomerase (PDI) and its homologs, which contain varying combinations of catalytically active and inactive thioredoxin domains. However, the specific contribution of PDI to the formation of new disulfides versus...

  9. 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...

  10. 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.

  11. Prognosis of Cyclic Vomiting Syndrome

    Directory of Open Access Journals (Sweden)

    J. Gordon Millichap

    2016-03-01

    Full Text Available Investigators from Teikyo University School of Medicine, Tokyo, Japan, evaluated the clinical features, prognosis, and prophylaxis of cyclic vomiting syndrome and the relationship between the syndrome and levels of adrenocorticotropic/antidiuretic hormones (ACTH/ADH.

  12. Transcriptional regulation by cyclic AMP.

    Science.gov (United States)

    Montminy, M

    1997-01-01

    A number of hormones and growth factors have been shown to stimulate target cells via second messenger pathways that in turn regulate the phosphorylation of specific nuclear factors. The second messenger cyclic AMP, for example, regulates a striking number of physiologic processes, including intermediary metabolism, cellular proliferation, and neuronal signaling, by altering basic patterns of gene expression. Our understanding of cyclic AMP signaling in the nucleus has expanded considerably over the past decade, owing in large part to the characterization of cyclic AMP-responsive promoter elements, transcription factors that bind them, and signal-dependent coactivators that mediate target gene induction. More importantly, these studies have revealed new insights into biological problems as diverse as biological clocks and long-term memory. The purpose of this review is to describe the components of the cyclic AMP response unit and to analyze how these components cooperate to induce target gene expression in response to hormonal stimulation.

  13. Functionalized linear and cyclic polyolefins

    Science.gov (United States)

    Tuba, Robert; Grubbs, Robert H.

    2018-02-13

    This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

  14. Optimal expression of a Fab-effector fusion protein in Escherichia coli by removing the cysteine residues responsible for an interchain disulfide bond of a Fab molecule.

    Science.gov (United States)

    Kang, Hyeon-Ju; Kim, Hye-Jin; Jung, Mun-Sik; Han, Jae-Kyu; Cha, Sang-Hoon

    2017-04-01

    Development of novel bi-functional or even tri-functional Fab-effector fusion proteins would have a great potential in the biomedical sciences. However, the expression of Fab-effector fusion proteins in Escherichia coli is problematic especially when a eukaryotic effector moiety is genetically linked to a Fab due to the lack of proper chaperone proteins and an inappropriate physicochemical environment intrinsic to the microbial hosts. We previously reported that a human Fab molecule, referred to as SL335, reactive to human serum albumin has a prolonged in vivo serum half-life in rats. We, herein, tested six discrete SL335-human growth hormone (hGH) fusion constructs as a model system to define an optimal Fab-effector fusion format for E. coli expression. We found that one variant, referred to as HserG/Lser, outperformed the others in terms of a soluble expression yield and functionality in that HserG/Lser has a functional hGH bioactivity and possesses an serum albumin-binding affinity comparable to SL335. Our results clearly demonstrated that the genetic linkage of an effector domain to the C-terminus of Fd (V H +C H1 ) and the removal of cysteine (Cys) residues responsible for an interchain disulfide bond (IDB) ina Fab molecule optimize the periplasmic expression of a Fab-effector fusion protein in E. coli. We believe that our approach can contribute the development of diverse bi-functional Fab-effector fusion proteins by providing a simple strategy that enables the reliable expression of a functional fusion proteins in E. coli. Copyright © 2017 European Federation of Immunological Societies. Published by Elsevier B.V. All rights reserved.

  15. Modulation of Thiol-Disulfide Oxidoreductases for Increased Production of Disulfide-Bond-Containing Proteins in Bacillus subtilis

    NARCIS (Netherlands)

    Kouwen, Thijs R. H. M.; Dubois, Jean-Yves F.; Freudl, Roland; Quax, Wim J.; van Dijl, Jan Maarten

    2008-01-01

    Disulfide bonds are important for the correct folding, structural integrity, and activity of many biotechnologically relevant proteins. For synthesis and subsequent secretion of these proteins in bacteria, such as the well-known "cell factory" Bacillus subtilis, it is often the correct formation of

  16. 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.

  17. Cathode based on molybdenum disulfide nanoflakes for lithium-oxygen batteries.

    Energy Technology Data Exchange (ETDEWEB)

    Asadi, Mohammad; Kumar, Bijandra; Liu, Cong; Phillips, Patrick; Yasaei, Poya; Behranginia, Amirhossein; Zapol, Peter; Klie, Robert F.; Curtiss, Larry A.; Salehi-Khojin, Amin

    2016-02-01

    Lithium-oxygen (Li-O-2) batteries have been recognized as an emerging technology for energy storage systems owing to their high theoretical specific energy. One challenge is to find an electrolyte/cathode system that is efficient, stable, and cost-effective. We present such a system based on molybdenum disulfide (MoS2) nanoflakes combined with an ionic liquid (IL) that work together as an effective cocatalyst for discharge and charge in a Li-O-2 battery. Cyclic voltammetry results show superior catalytic performance for this cocatalyst for both oxygen reduction and evolution reactions compared to Au and Pt catalysts. It also performs remarkably well in the Li-O-2 battery system with 85% round-trip efficiency and reversibility up to 50 cycles. Density functional calculations provide a mechanistic understanding of the MoS2 nanoflakes/IL system. cocatalyst reported in this work could open the way for exploiting the unique properties of ionic liquids in Li-air batteries in combination with nanostructured MoS2 as a cathode material.

  18. Mapping Soluble Guanylyl Cyclase and Protein Disulfide Isomerase Regions of Interaction.

    Directory of Open Access Journals (Sweden)

    Erin J Heckler

    Full Text Available Soluble guanylyl cyclase (sGC is a heterodimeric nitric oxide (NO receptor that produces cyclic GMP. This signaling mechanism is a key component in the cardiovascular system. NO binds to heme in the β subunit and stimulates the catalytic conversion of GTP to cGMP several hundred fold. Several endogenous factors have been identified that modulate sGC function in vitro and in vivo. In previous work, we determined that protein disulfide isomerase (PDI interacts with sGC in a redox-dependent manner in vitro and that PDI inhibited NO-stimulated activity in cells. To our knowledge, this was the first report of a physical interaction between sGC and a thiol-redox protein. To characterize this interaction between sGC and PDI, we first identified peptide linkages between sGC and PDI, using a lysine cross-linking reagent and recently developed mass spectrometry analysis. Together with Flag-immunoprecipitation using sGC domain deletions, wild-type (WT and mutated PDI, regions of sGC involved in this interaction were identified. The observed data were further explored with computational modeling to gain insight into the interaction mechanism between sGC and oxidized PDI. Our results indicate that PDI interacts preferentially with the catalytic domain of sGC, thus providing a mechanism for PDI inhibition of sGC. A model in which PDI interacts with either the α or the β catalytic domain is proposed.

  19. Sodium and Lithium Storage Properties of Spray-Dried Molybdenum Disulfide-Graphene Hierarchical Microspheres

    Science.gov (United States)

    Kalluri, Sujith; Seng, Kuok Hau; Guo, Zaiping; Du, Aijun; Konstantinov, Konstantin; Liu, Hua Kun; Dou, Shi Xue

    2015-07-01

    Developing nano/micro-structures which can effectively upgrade the intriguing properties of electrode materials for energy storage devices is always a key research topic. Ultrathin nanosheets were proved to be one of the potential nanostructures due to their high specific surface area, good active contact areas and porous channels. Herein, we report a unique hierarchical micro-spherical morphology of well-stacked and completely miscible molybdenum disulfide (MoS2) nanosheets and graphene sheets, were successfully synthesized via a simple and industrial scale spray-drying technique to take the advantages of both MoS2 and graphene in terms of their high practical capacity values and high electronic conductivity, respectively. Computational studies were performed to understand the interfacial behaviour of MoS2 and graphene, which proves high stability of the composite with high interfacial binding energy (-2.02 eV) among them. Further, the lithium and sodium storage properties have been tested and reveal excellent cyclic stability over 250 and 500 cycles, respectively, with the highest initial capacity values of 1300 mAh g-1 and 640 mAh g-1 at 0.1 A g-1.

  20. Adsorption and desorption of bis-(3-sulfopropyl) disulfide during Cu electrodeposition and stripping at Au electrodes.

    Science.gov (United States)

    Chiu, Yong-Da; Dow, Wei-Ping; Krug, Klaus; Liu, Yung-Fang; Lee, Yuh-Lang; Yau, Shueh-Lin

    2012-10-09

    The adsorption and desorption of bis-(3-sulfopropyl) disulfide (SPS) on Cu and Au electrodes and its electrochemical effect on Cu deposition and dissolution were examined using cyclic voltammetry stripping (CVS), field-emission scanning electron microscopy (FESEM), and X-ray photoelectron spectroscopy (XPS). SPS dissociates into 3-mercapto-1-propanesulfonate when it is contacted with Au and Cu electrodes, producing Cu(I)- and Au(I)-thiolate species. These thiolates couple with chloride ions and promote not only the reduction of Cu(2+) in Cu deposition but also the oxidation of Cu(0) to Cu(+) in Cu stripping. During Cu electrodeposition on the SPS-modified Au electrode, thiolates transfer from Au onto the Cu underpotential deposition (UPD) layer. The Cu UPD layer stabilizes a large part of the transferred thiolates which subsequently is buried by the Cu overpotential deposition (OPD) layer. The buried thiolates reappear on the Au electrode after the copper deposit is electrochemically stripped off. A much smaller part of thiolates transfers to the top of the Cu OPD layer. In contrast, when SPS preadsorbs on a Cu-coated Au electrode, almost all of the adsorbed SPS leaves the Cu surface during Cu electrochemical stripping and does not return to the uncovered Au surface. A reaction mechanism is proposed to explain these results.

  1. An olfactory subsystem that detects carbon disulfide and mediates food-related social learning.

    Science.gov (United States)

    Munger, Steven D; Leinders-Zufall, Trese; McDougall, Lisa M; Cockerham, Renee E; Schmid, Andreas; Wandernoth, Petra; Wennemuth, Gunther; Biel, Martin; Zufall, Frank; Kelliher, Kevin R

    2010-08-24

    Olfactory signals influence social interactions in a variety of species. In mammals, pheromones and other social cues can promote mating or aggression behaviors; can communicate information about social hierarchies, genetic identity and health status; and can contribute to associative learning. However, the molecular, cellular, and neural mechanisms underlying many olfactory-mediated social interactions remain poorly understood. Here, we report that a specialized olfactory subsystem that includes olfactory sensory neurons (OSNs) expressing the receptor guanylyl cyclase GC-D, the cyclic nucleotide-gated channel subunit CNGA3, and the carbonic anhydrase isoform CAII (GC-D(+) OSNs) is required for the acquisition of socially transmitted food preferences (STFPs) in mice. Using electrophysiological recordings from gene-targeted mice, we show that GC-D(+) OSNs are highly sensitive to the volatile semiochemical carbon disulfide (CS(2)), a component of rodent breath and a known social signal mediating the acquisition of STFPs. Olfactory responses to CS(2) are drastically reduced in mice lacking GC-D, CNGA3, or CAII. Disruption of this sensory transduction cascade also results in a failure to acquire STFPs from either live or surrogate demonstrator mice or to exhibit hippocampal correlates of STFP retrieval. Our findings indicate that GC-D(+) OSNs detect chemosignals that facilitate food-related social interactions. Copyright 2010 Elsevier Ltd. All rights reserved.

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

    OpenAIRE

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

    2011-01-01

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

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

    DEFF Research Database (Denmark)

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

    2008-01-01

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

  4. Reactive copolymers based on N-vinyl lactams with pyridyl disulfide side groups via RAFT polymerization and postmodification via thiol-disulfide exchange reaction

    NARCIS (Netherlands)

    Peng, Huan; Rübsam, Kristin; Huang, Xiaobin; Jakob, Felix; Karperien, Marcel; Schwaneberg, Ulrich; Pich, Andrij

    2016-01-01

    Herein, we report the synthesis of a series of novel pyridyl disulfide (PDS)-functionalized statistical reactive copolymers that enable facile access to complex polymeric architectures through highly selective thiol-disulfide exchange reaction with thiol-containing ligands or proteins. Functional

  5. A structural model of pestivirus E(rns) based on disulfide bond connectivity and homology modeling reveals an extremely rare vicinal disulfide

    NARCIS (Netherlands)

    Langedijk, J.P.M.; Veelen, van P.A.; Schaaper, W.M.M.; Ru, de A.H.; Meloen, R.H.; Hulst, M.M.

    2002-01-01

    Erns is a pestivirus envelope glycoprotein and is the only known viral surface protein with RNase activity. Erns is a disulfide-linked homodimer of 100 kDa; it is found on the surface of pestivirus-infected cells and is secreted into the medium. In this study, the disulfide arrangement of the nine

  6. Nature of solar cyclicity. I

    Energy Technology Data Exchange (ETDEWEB)

    Romanchuk, P.R.

    1981-01-01

    The report contains a critical survey of work devoted to the study of the nature of solar cyclicity. The inconsistency of the representation of cyclic curves using a frequency spectrum is indicated. The useful contribution of the ideas of Wolf, Newcomb, and Waldmeier to the solution of the problem is noted. Data are cited in favor of the theory of the tidal nature of solar cyclicity developed by the author, which also takes into account the ideas of the above-mentioned authors: the continuous paired and single tidal actions of the planets and the resonance character of this action, thanks to which the approximately 10-year period of action of Jupiter and Saturn is transformed into the 11-year activity cycle.

  7. On Improvements of Cyclic MUSIC

    Directory of Open Access Journals (Sweden)

    H. Howard Fan

    2005-01-01

    Full Text Available Many man-made signals encountered in communications exhibit cyclostationarity. By exploiting cyclostationarity, cyclic MUSIC has been shown to be able to separate signals with different cycle frequencies, thus, to be able to perform signal selective direction of-arrival (DOA estimation. However, as will be shown in this paper, the DOA estimation of cyclic MUSIC is actually biased. We show in this paper that by properly choosing the frequency for evaluating the steering vector, the bias of DOA estimation can be substantially reduced and the performance can be improved. Furthermore, we propose another algorithm exploiting cyclic conjugate correlation to further improve the performance of DOA estimation. Simulation results show the effectiveness of both of our methods.

  8. Design of a cyclic multiverse

    Energy Technology Data Exchange (ETDEWEB)

    Piao Yunsong, E-mail: yspiao@gucas.ac.c [College of Physical Sciences, Graduate School of Chinese Academy of Sciences, Beijing 100049 (China)

    2010-08-09

    Recently, it has been noticed that the amplification of the amplitude of curvature perturbation cycle by cycle can lead to a cyclic multiverse scenario, in which the number of universes increases cycle by cycle. However, this amplification will also inevitably induce either the ultimate end of corresponding cycle, or the resulting spectrum of perturbations inside corresponding universe is not scale invariant, which baffles the existence of observable universes. In this Letter, we propose a design of a cyclic multiverse, in which the observable universe can emerges naturally. The significance of a long period of dark energy before the turnaround of each cycle for this implementing is shown.

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

    Science.gov (United States)

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

    2015-02-01

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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Cyclic Processing for Context Fusion

    DEFF Research Database (Denmark)

    Kjærgaard, Mikkel Baun

    2007-01-01

    Many machine-learning techniques use feedback information. However, current context fusion systems do not support this because they constrain processing to be structured as acyclic processing. This paper proposes a generalization which enables the use of cyclic processing in context fusion systems...

  15. Cyclic codes of length 2

    Indian Academy of Sciences (India)

    Springer Verlag Heidelberg #4 2048 1996 Dec 15 10:16:45

    [X]/〈X2m. − 1〉 are given. Cyclic codes of length 2m over the finite field Fq, of odd characteristic, are defined in terms of their generator polynomials. The exact minimum distance and the dimension of the codes are obtained. Keywords.

  16. Color visualization of cyclic magnitudes

    Science.gov (United States)

    Restrepo, Alfredo; Estupiñán, Viviana

    2014-02-01

    We exploit the perceptual, circular ordering of the hues in a technique for the visualization of cyclic variables. The hue is thus meaningfully used for the indication of variables such as the azimuth and the units of the measurement of time. The cyclic (or circular) variables may be both of the continuous type or the discrete type; among the first there is azimuth and among the last you find the musical notes and the days of the week. A correspondence between the values of a cyclic variable and the chromatic hues, where the natural circular ordering of the variable is respected, is called a color code for the variable. We base such a choice of hues on an assignment of of the unique hues red, yellow, green and blue, or one of the 8 even permutations of this ordered list, to 4 cardinal values of the cyclic variable, suitably ordered; color codes based on only 3 cardinal points are also possible. Color codes, being intuitive, are easy to remember. A possible low accuracy when reading instruments that use this technique is compensated by fast, ludic and intuitive readings; also, the use of a referential frame makes readings precise. An achromatic version of the technique, that can be used by dichromatic people, is proposed.

  17. Cyclic theory of Lie algebroids

    NARCIS (Netherlands)

    Blom, A.

    2017-01-01

    In this thesis we study the cyclic theory of universal enveloping algebras of Lie algebroids. Lie algebroids are geometrical objects that encode infinitesimal symmetries, and the concept encompasses many classical objects from geometry, such as Poisson manifolds, foliations and actions of Lie

  18. Cyclic peptide therapeutics: past, present and future.

    Science.gov (United States)

    Zorzi, Alessandro; Deyle, Kaycie; Heinis, Christian

    2017-06-01

    Cyclic peptides combine several favorable properties such as good binding affinity, target selectivity and low toxicity that make them an attractive modality for the development of therapeutics. Over 40 cyclic peptide drugs are currently in clinical use and around one new cyclic peptide drug enters the market every year on average. The vast majority of clinically approved cyclic peptides are derived from natural products, such as antimicrobials or human peptide hormones. New powerful techniques based on rational design and in vitro evolution have enabled the de novo development of cyclic peptide ligands to targets for which nature does not offer solutions. A look at the cyclic peptides currently under clinical evaluation shows that several have been developed using such techniques. This new source for cyclic peptide ligands introduces a freshness to the field, and it is likely that de novo developed cyclic peptides will be in clinical use in the near future. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Deformation mechanisms in cyclic creep and fatigue

    International Nuclear Information System (INIS)

    Laird, C.

    1979-01-01

    Service conditions in which static and cyclic loading occur in conjunction are numerous. It is argued that an understanding of cyclic creep and cyclic deformation are necessary both for design and for understanding creep-fatigue fracture. Accordingly a brief, and selective, review of cyclic creep and cyclic deformation at both low and high strain amplitudes is provided. Cyclic loading in conjunction with static loading can lead to creep retardation if cyclic hardening occurs, or creep acceleration if softening occurs. Low strain amplitude cyclic deformation is understood in terms of dislocation loop patch and persistent slip band behavior, high strain deformation in terms of dislocation cell-shuttling models. While interesting advances in these fields have been made in the last few years, the deformation mechanisms are generally poorly understood

  20. 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.

  1. Monopod bucket foundations under cyclic lateral loading

    DEFF Research Database (Denmark)

    Foglia, Aligi; Ibsen, Lars Bo

    on bucket foundations under lateral cyclic loading. The test setup is described in detail and a comprehensive experimental campaign is presented. The foundation is subjected to cyclic overturning moment, cyclic horizontal loading and constant vertical loading, acting on the same plane for thousands...

  2. 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.

  3. 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...

  4. 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

  5. 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

  6. In situ TEM observations of the lithiation of molybdenum disulfide

    International Nuclear Information System (INIS)

    Janish, Matthew T.; Carter, C. Barry

    2015-01-01

    The lithiation of molybdenum disulfide (MoS 2 ) has been directly studied in situ in the TEM by observing specimens with the viewing direction parallel to the basal planes. The MoS 2 lamella was characterized by bright-field imaging during the lithiation, and both selected-area diffraction and high-resolution imaging before and after. An overall expansion of ∼5% along the c-direction was observed with concurrent local contraction. The contraction can be related to the expulsion of Mo as Li reduces it to form Li 2 S

  7. Quantifying the global cellular thiol-disulfide status

    DEFF Research Database (Denmark)

    Hansen, Rosa E; Roth, Doris; Winther, Jakob R

    2009-01-01

    It is widely accepted that the redox status of protein thiols is of central importance to protein structure and folding and that glutathione is an important low-molecular-mass redox regulator. However, the total cellular pools of thiols and disulfides and their relative abundance have never been...... cell types. However, when cells are exposed to a sublethal dose of the thiol-specific oxidant diamide, PSSG levels increase to >15% of all protein cysteine. Glutathione is typically characterized as the "cellular redox buffer"; nevertheless, our data show that protein thiols represent a larger active...

  8. 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.

  9. Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

    International Nuclear Information System (INIS)

    Silvestrini, M.; Schiavuta, P.; Scopece, P.; Pecchielan, G.; Moretto, L.M.; Ugo, P.

    2011-01-01

    Highlights: → Complex nanostructures are built on the gold surface of ensembles of nanoelectrodes. → Gold surface of nanoelectrodes was functionalized with SAM of organic sulphurs. → The polycarbonate surrounding nanoelectrodes was functionalized with proteins. → SAMs protect the nanoelectrodes from undesired proteins adsorption. - Abstract: The possibility to functionalize selectively with thiols or disulfides the surface of the gold nanoelectrodes of polycarbonate templated nanoelectrode ensembles (NEEs) is studied. It is shown that the Au nanoelectrodes can be coated by a self assembled monolayer (SAM) of thioctic acid (TA) or 2-mercaptoethanesulfonic (MES) acid. The study of the electrochemical behavior of SAM-modified NEEs by cyclic voltammetry (CV) at different solution pH, using ferrocenecarboxylate as an anionic redox probe (FcCOO - ) and (ferrocenylmethyl)trimethylammonium (FA + ) as a cationic redox probe, demonstrate that the SAM-modified nanoelectrodes are permselective, in that only cationic or neutral probes can access the SAM-coated nanoelectrode surface. CV, AFM and FTIR-ATR data indicate that proteins such as casein or bovine serum albumin, which are polyanionic at pH 7, adsorb on the surface of NEEs untreated with thiols, tending to block the electron transfer of the ferrocenyl redox probes. On the contrary, the pre-treatment of the NEE with an anionic SAM protects the nanoelectrodes from protein fouling, allowing the detection of well shaped voltammetric patterns for the redox probe. Experimental results indicate that, in the case of MES treated NEEs, the protein is bound only onto the polycarbonate surface which surrounds the nanoelectrodes, while the tips of the gold nanoelectrodes remain protein free.

  10. Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins

    Energy Technology Data Exchange (ETDEWEB)

    Silvestrini, M. [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy); Schiavuta, P.; Scopece, P. [Associazione CIVEN, via delle Industrie 5, 30175 Marghera - Venice (Italy); Pecchielan, G.; Moretto, L.M. [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy); Ugo, P., E-mail: ugo@unive.it [Department of Molecular Sciences and Nanosystems, University Ca' Foscari of Venice, Santa Marta 2137, 30123 Venice (Italy)

    2011-09-01

    Highlights: > Complex nanostructures are built on the gold surface of ensembles of nanoelectrodes. > Gold surface of nanoelectrodes was functionalized with SAM of organic sulphurs. > The polycarbonate surrounding nanoelectrodes was functionalized with proteins. > SAMs protect the nanoelectrodes from undesired proteins adsorption. - Abstract: The possibility to functionalize selectively with thiols or disulfides the surface of the gold nanoelectrodes of polycarbonate templated nanoelectrode ensembles (NEEs) is studied. It is shown that the Au nanoelectrodes can be coated by a self assembled monolayer (SAM) of thioctic acid (TA) or 2-mercaptoethanesulfonic (MES) acid. The study of the electrochemical behavior of SAM-modified NEEs by cyclic voltammetry (CV) at different solution pH, using ferrocenecarboxylate as an anionic redox probe (FcCOO{sup -}) and (ferrocenylmethyl)trimethylammonium (FA{sup +}) as a cationic redox probe, demonstrate that the SAM-modified nanoelectrodes are permselective, in that only cationic or neutral probes can access the SAM-coated nanoelectrode surface. CV, AFM and FTIR-ATR data indicate that proteins such as casein or bovine serum albumin, which are polyanionic at pH 7, adsorb on the surface of NEEs untreated with thiols, tending to block the electron transfer of the ferrocenyl redox probes. On the contrary, the pre-treatment of the NEE with an anionic SAM protects the nanoelectrodes from protein fouling, allowing the detection of well shaped voltammetric patterns for the redox probe. Experimental results indicate that, in the case of MES treated NEEs, the protein is bound only onto the polycarbonate surface which surrounds the nanoelectrodes, while the tips of the gold nanoelectrodes remain protein free.

  11. Cyclic homology and group actions

    Science.gov (United States)

    Ponge, Raphaël

    2018-01-01

    In this paper we present the construction of explicit quasi-isomorphisms that compute the cyclic homology and periodic cyclic homology of crossed-product algebras associated with (discrete) group actions. In the first part we deal with algebraic crossed-products associated with group actions on unital algebras over any ring k ⊃ Q. In the second part, we extend the results to actions on locally convex algebras. We then deal with crossed-products associated with group actions on manifolds and smooth varieties. For the finite order components, the results are expressed in terms of what we call "mixed equivariant cohomology". This "mixed" theory mediates between group homology and de Rham cohomology. It is naturally related to equivariant cohomology, and so we obtain explicit constructions of cyclic cycles out of equivariant characteristic classes. For the infinite order components, we simplify and correct the misidentification of Crainic (1999). An important new homological tool is the notion of "triangular S-module". This is a natural generalization of the cylindrical complexes of Getzler-Jones. It combines the mixed complexes of Burghelea-Kassel and parachain complexes of Getzler-Jones with the S-modules of Kassel-Jones. There are spectral sequences naturally associated with triangular S-modules. In particular, this allows us to recover spectral sequences of Feigin-Tsygan and Getzler-Jones and leads us to a new spectral sequence.

  12. 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.

  13. Complete Mapping of Complex Disulfide Patterns with Closely-Spaced Cysteines by In-Source Reduction and Data-Dependent Mass Spectrometry

    DEFF Research Database (Denmark)

    Cramer, Christian N; Kelstrup, Christian D; Olsen, Jesper V

    2017-01-01

    Mapping of disulfide bonds is an essential part of protein characterization to ensure correct cysteine pairings. For this, mass spectrometry (MS) is the most widely used technique due to fast and accurate characterization. However, MS-based disulfide mapping is challenged when multiple disulfide...... of individual disulfide bonds could be done in species containing closely spaced disulfide bonds. The strength of this methodology was demonstrated by complete mapping of all four disulfide bonds in lysozyme and all 17 disulfide bonds in human serum albumin, including nested disulfide bonds and motifs...

  14. Cyclic Peptides as Novel Therapeutic Microbicides: Engineering of Human Defensin Mimetics.

    Science.gov (United States)

    Falanga, Annarita; Nigro, Ersilia; De Biasi, Margherita Gabriella; Daniele, Aurora; Morelli, Giancarlo; Galdiero, Stefania; Scudiero, Olga

    2017-07-20

    Cyclic peptides are receiving significant attention thanks to their antimicrobial activity and high serum stability, which is useful to develop and design novel antimicrobial agents. Antimicrobial peptides appear to be key components of innate defences against bacteria, viruses, and fungi. Among the others, defensins possess a strong microbicidial activity. Defensins are cationic and amphipathic peptides with six cysteine residues connected by three disulfide bonds found in plants, insects, and mammals; they are divided in three families: α-, β-, and θ-defensins. α-Defensins are contained in the primary granules of human neutrophils; β-defensins are expressed in human epithelia; and θ-defensins are pseudo-cyclic defensins not found in humans, but in rhesus macaques. The structural diversities among the three families are reflected in a different antimicrobial action as well as in serum stability. The engineering of these peptides is an exciting opportunity to obtain more functional antimicrobial molecules highlighting their potential as therapeutic agents. The present review reports the most recent advances in the field of cyclic peptides with a specific regard to defensin analogs.

  15. Cyclic Peptides as Novel Therapeutic Microbicides: Engineering of Human Defensin Mimetics

    Directory of Open Access Journals (Sweden)

    Annarita Falanga

    2017-07-01

    Full Text Available Cyclic peptides are receiving significant attention thanks to their antimicrobial activity and high serum stability, which is useful to develop and design novel antimicrobial agents. Antimicrobial peptides appear to be key components of innate defences against bacteria, viruses, and fungi. Among the others, defensins possess a strong microbicidial activity. Defensins are cationic and amphipathic peptides with six cysteine residues connected by three disulfide bonds found in plants, insects, and mammals; they are divided in three families: α-, β-, and θ-defensins. α-Defensins are contained in the primary granules of human neutrophils; β-defensins are expressed in human epithelia; and θ-defensins are pseudo-cyclic defensins not found in humans, but in rhesus macaques. The structural diversities among the three families are reflected in a different antimicrobial action as well as in serum stability. The engineering of these peptides is an exciting opportunity to obtain more functional antimicrobial molecules highlighting their potential as therapeutic agents. The present review reports the most recent advances in the field of cyclic peptides with a specific regard to defensin analogs.

  16. The Chemistry of Alk-1-yn-1-yl DisulfidesA Review

    DEFF Research Database (Denmark)

    Senning, Alexander Erich Eugen

    2009-01-01

    The preparation and the properties of the elusive alk-1-yn-1-yl disulfides are reviewed, including the most recent quantum chemical findings with regard to their reactivity.......The preparation and the properties of the elusive alk-1-yn-1-yl disulfides are reviewed, including the most recent quantum chemical findings with regard to their reactivity....

  17. Inhibition of carbon disulfide on bio-desulfurization in the process of ...

    African Journals Online (AJOL)

    Biological desulfurization is a novel technology for the removal of hydrogen sulfide from some biogas or sour gas, in which there are always a certain amounts of carbon disulfide together with much hydrogen sulfide. Nowadays, carbon disulfide is found to have negative effect on the biological desulfurization, but seldom ...

  18. Selective inhibition of nicotinamide adenine dinucleotide kinases by dinucleoside disulfide mimics of nicotinamide adenine dinucleotide analogues.

    Science.gov (United States)

    Petrelli, Riccardo; Sham, Yuk Yin; Chen, Liqiang; Felczak, Krzysztof; Bennett, Eric; Wilson, Daniel; Aldrich, Courtney; Yu, Jose S; Cappellacci, Loredana; Franchetti, Palmarisa; Grifantini, Mario; Mazzola, Francesca; Di Stefano, Michele; Magni, Giulio; Pankiewicz, Krzysztof W

    2009-08-01

    Diadenosine disulfide (5) was reported to inhibit NAD kinase from Listeria monocytogenes and the crystal structure of the enzyme-inhibitor complex has been solved. We have synthesized tiazofurin adenosine disulfide (4) and the disulfide 5, and found that these compounds were moderate inhibitors of human NAD kinase (IC(50)=110 microM and IC(50)=87 microM, respectively) and Mycobacterium tuberculosis NAD kinase (IC(50)=80 microM and IC(50)=45 microM, respectively). We also found that NAD mimics with a short disulfide (-S-S-) moiety were able to bind in the folded (compact) conformation but not in the common extended conformation, which requires the presence of a longer pyrophosphate (-O-P-O-P-O-) linkage. Since majority of NAD-dependent enzymes bind NAD in the extended conformation, selective inhibition of NAD kinases by disulfide analogues has been observed. Introduction of bromine at the C8 of the adenine ring restricted the adenosine moiety of diadenosine disulfides to the syn conformation making it even more compact. The 8-bromoadenosine adenosine disulfide (14) and its di(8-bromoadenosine) analogue (15) were found to be the most potent inhibitors of human (IC(50)=6 microM) and mycobacterium NAD kinase (IC(50)=14-19 microM reported so far. None of the disulfide analogues showed inhibition of lactate-, and inosine monophosphate-dehydrogenase (IMPDH), enzymes that bind NAD in the extended conformation.

  19. Identification of thioredoxin target disulfides in proteins released from barley aleurone layers

    DEFF Research Database (Denmark)

    Hägglund, Per; Bunkenborg, J.; Yang, Fen

    2010-01-01

    Thioredoxins are ubiquitous disulfide reductases involved in a wide range of cellular processes including DNA synthesis, oxidative stress response and apoptosis. In cereal seeds thioredoxins are proposed to facilitate the germination process by reducing disulfide bonds in storage proteins and other...

  20. Kinetic and Thermodynamic Aspects of Cellular Thiol-Disulfide Redox Regulation

    DEFF Research Database (Denmark)

    Jensen, Kristine Steen; Hansen, Rosa Erritzøe; Winther, Jakob R

    2009-01-01

    that affect the rate of thiol-disulfide exchange and stability of disulfide bonds are discussed within the framework of the underlying chemical foundations. This includes the effect of thiol acidity (pKa), the local electrostatic environment, molecular strain and entropy. Even though a thiol...

  1. Folding and activity of hybrid sequence, disulfide-stabilized peptides

    Energy Technology Data Exchange (ETDEWEB)

    Pease, J.H.B.; Storrs, R.W.; Wemmer, D.E. (Univ. of California, Berkeley (USA))

    1990-08-01

    Peptides have been synthesized that have hybrid sequences, partially derived from the bee venom peptide apamin and partially from the S peptide of ribonuclease A. The hybrid peptides were demonstrated by NMR spectroscopy to fold, forming the same disulfides and basic three-dimensional structure as native apamin, containing a {beta}-turn and an {alpha}-helix. These hybrids were active in complementing S protein, reactivating nuclease activity. In addition, the hybrid peptide was effective in inducing antibodies that cross-react with the RNase, without conjugation to a carrier protein. The stability of the folded structure of this peptide suggests that it should be possible to elicit antibodies that will react not only with a specific sequence, but also with a specific secondary structure. Hybrid sequence peptides also provide opportunities to study separately nucleation and propagation steps in formation of secondary structure. The authors show that in S peptide the {alpha}-helix does not end abruptly but rather terminates gradually over four or five residues. In general, these hybrid sequence peptides, which fold predictably because of disulfide bond formation, can provide opportunities for examining structure - function relationships for many biologically active sequences.

  2. Folding and activity of hybrid sequence, disulfide-stabilized peptides

    International Nuclear Information System (INIS)

    Pease, J.H.B.; Storrs, R.W.; Wemmer, D.E.

    1990-01-01

    Peptides have been synthesized that have hybrid sequences, partially derived from the bee venom peptide apamin and partially from the S peptide of ribonuclease A. The hybrid peptides were demonstrated by NMR spectroscopy to fold, forming the same disulfides and basic three-dimensional structure as native apamin, containing a β-turn and an α-helix. These hybrids were active in complementing S protein, reactivating nuclease activity. In addition, the hybrid peptide was effective in inducing antibodies that cross-react with the RNase, without conjugation to a carrier protein. The stability of the folded structure of this peptide suggests that it should be possible to elicit antibodies that will react not only with a specific sequence, but also with a specific secondary structure. Hybrid sequence peptides also provide opportunities to study separately nucleation and propagation steps in formation of secondary structure. The authors show that in S peptide the α-helix does not end abruptly but rather terminates gradually over four or five residues. In general, these hybrid sequence peptides, which fold predictably because of disulfide bond formation, can provide opportunities for examining structure - function relationships for many biologically active sequences

  3. 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...

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. 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)

  9. 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

  10. 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...

  11. 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.

  12. 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

  13. 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

  14. 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 ...

  15. 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

  16. 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

  17. In-Depth Characterization of Protein Disulfide Bonds by Online Liquid Chromatography-Electrochemistry-Mass Spectrometry

    Science.gov (United States)

    Switzar, Linda; Nicolardi, Simone; Rutten, Julie W.; Oberstein, Saskia A. J. Lesnik; Aartsma-Rus, Annemieke; van der Burgt, Yuri E. M.

    2016-01-01

    Disulfide bonds are an important class of protein post-translational modifications, yet this structurally crucial modification type is commonly overlooked in mass spectrometry (MS)-based proteomics approaches. Recently, the benefits of online electrochemistry-assisted reduction of protein S-S bonds prior to MS analysis were exemplified by successful characterization of disulfide bonds in peptides and small proteins. In the current study, we have combined liquid chromatography (LC) with electrochemistry (EC) and mass analysis by Fourier transform ion cyclotron resonance (FTICR) MS in an online LC-EC-MS platform to characterize protein disulfide bonds in a bottom-up proteomics workflow. A key advantage of a LC-based strategy is the use of the retention time in identifying both intra- and interpeptide disulfide bonds. This is demonstrated by performing two sequential analyses of a certain protein digest, once without and once with electrochemical reduction. In this way, the "parent" disulfide-linked peptide detected in the first run has a retention time-based correlation with the EC-reduced peptides detected in the second run, thus simplifying disulfide bond mapping. Using this platform, both inter- and intra-disulfide-linked peptides were characterized in two different proteins, ß-lactoglobulin and ribonuclease B. In order to prevent disulfide reshuffling during the digestion process, proteins were digested at a relatively low pH, using (a combination of) the high specificity proteases trypsin and Glu-C. With this approach, disulfide bonds in ß-lactoglobulin and ribonuclease B were comprehensively identified and localized, showing that online LC-EC-MS is a useful tool for the characterization of protein disulfide bonds.

  18. Peptídeos cíclicos de biomassa vegetal: características, diversidade, biossíntese e atividades biológicas Cyclic peptide from plant biomass: chemical features and diversity, biosynthesis and biological activities

    Directory of Open Access Journals (Sweden)

    Douglas Gatte Picchi

    2009-01-01

    Full Text Available Natural peptides are outstanding as the most promising macromolecules in the search for new drugs, especially those of cyclic nature. The higher plants revealed a very peculiar composition of their cyclic peptides, which distinguish themselves by a "head-to-tail" cyclization. It is possible to define two groups of cyclic peptides from plant biomass. Those called in this review as Eucyclopeptides formed by 2-12 amino acid, and Cyclotides considered as circular polypeptides, composed of 29-37 amino acid that retain three disulfides bridges in an arrangement known as cyclic cystine knot. Searching for plant peptides should form into a subject for scientific research in the forefront of great importance for bioprospecting natural products macromolecular.

  19. Cyclic voltammetry of dental amalgams.

    Science.gov (United States)

    Horasawa, N; Nakajima, H; Ferracane, J L; Takahashi, S; Okabe, T

    1996-05-01

    This study used cyclic voltammetry to examine the effect of the composition of dental amalgams on their electrochemical behavior, including reactions occurring outside of oral conditions. Amalgams (residual mercury 47.5%) were prepared using two low-copper (3 wt% Cu) powders and five high-copper powders (40-80 wt% Ag, 12-30 wt% Cu) with and without zinc (1.5 wt%). Cyclic voltammograms were obtained at 37 degrees C in 1.0% NaCl scanning at 2 mV/s in the potential range from -1.5 V to +0.8 V vs. Ag/AgCl. During the anodic scans, AgCl and Hg2Cl2 films were formed on all amalgams except the one with only 40 wt% Ag. In all high-copper amalgams, a prominent Cu (oxidation) peak was found at -0.1 V, indicating the release of copper during corrosion. Zinc affected the oxidation process for both low- and high-copper amalgams. When zinc was absent, a peak for Sn2+ oxidation appeared at -0.4 V. When zinc was present, a Sn4+ oxidation peak was revealed at -0.6 V. In some amalgams, there was evidence of the selective corrosion (pitting corrosion) of tin and copper. In the lowest silver-content amalgam, no protective films were formed, which is indicative of its poor corrosion resistance. As expected, in all the low-copper amalgams, an extreme increase in current density was recorded immediately at 0 V, due to the release of tin from gamma 2. Cyclic voltammetry is useful for the rapid examination (less than an hour) of the electrochemical behavior of amalgams, specifically to obtain information on the formation of compounds and the sequences of electrochemical reactions.

  20. On numerically pluricanonical cyclic coverings

    International Nuclear Information System (INIS)

    Kulikov, V S; Kharlamov, V M

    2014-01-01

    We investigate some properties of cyclic coverings f:Y→X (where X is a complex surface of general type) branched along smooth curves B⊂X that are numerically equivalent to a multiple of the canonical class of X. Our main results concern coverings of surfaces of general type with p g =0 and Miyaoka-Yau surfaces. In particular, such coverings provide new examples of multi-component moduli spaces of surfaces with given Chern numbers and new examples of surfaces that are not deformation equivalent to their complex conjugates

  1. On charge-3 cyclic monopoles

    International Nuclear Information System (INIS)

    Braden, H W; D'Avanzo, Antonella; Enolski, V Z

    2011-01-01

    We determine the spectral curve of charge-3 BPS su(2) monopoles with C 3 cyclic symmetry. The symmetry means that the genus 4 spectral curve covers a (Toda) spectral curve of genus 2. A well adapted homology basis is presented enabling the theta functions and monopole data of the genus 4 curve to be given in terms of genus 2 data. The Richelot correspondence, a generalization of the arithmetic mean, is used to solve for this genus 2 curve. Results of other approaches are compared

  2. A system for cyclical voltametry

    International Nuclear Information System (INIS)

    Silva, R.P. da; Chierice, G.O.

    1974-01-01

    The constrution of a system composed by two instruments, voltametric circuit and potenciostate is depicted. Both instruments junction joined so that the voltametric circuit works as a triangular pulse generator, capable of operating with independent ascendant and descendant slope change, with unique pulse of continuous regime. The circuit of the potenciostate is composed of an amplifier with high entrance impedance and capable of supplying relatively high currents at the exit. The equipment was tested to study the aqueous Pb 2+ system in mercury electrode. this system depicted for the cyclical-voltometry technique set in use at I.E.A., Sao Paulo (Brazil), has very good linearity

  3. Universal low-temperature MWCNT-COOH-based counter electrode and a new thiolate/disulfide electrolyte system for dye-sensitized solar cells.

    Science.gov (United States)

    Hilmi, Abdulla; Shoker, Tharallah A; Ghaddar, Tarek H

    2014-06-11

    A new thiolate/disulfide organic-based electrolyte system composed of the tetrabutylammonium salt of 2-methyl-5-trifluoromethyl-2H-[1,2,4]triazole-3-thiol (S(-)) and its oxidized form 3,3'-dithiobis(2-methyl-5-trifluoromethyl-2H-[1,2,4]triazole) (DS) has been formulated and used in dye-sensitized solar cells (DSSCs). The electrocatalytic activity of different counter electrodes (CEs) has been evaluated by means of measuring J-V curves, cyclic voltammetry, Tafel plots, and electrochemical impedance spectroscopy. A stable and low-temperature CE based on acid-functionalized multiwalled carbon nanotubes (MWCNT-COOH) was investigated with our S(-)/DS, I(-)/I3(-), T(-)/T2, and Co(II/III)-based electrolyte systems. The proposed CE showed superb electrocatalytic activity toward the regeneration of the different electrolytes. In addition, good stability of solar cell devices based on the reported electrolyte and CE was shown.

  4. Cyclic AMP in rat pancreatic islets

    International Nuclear Information System (INIS)

    Grill, V.; Borglund, E.; Cerasi, E.; Uppsala Univ.

    1977-01-01

    The incorporation of [ 3 H]adenine into cyclic AMP was studied in rat pancreatic islets under varying conditions of labeling. Prolonging the exposure to [ 3 H]adenine progressively augmented the islet cyclic [ 3 H]AMP level. Islets labeled for different periods of time and subsequently incubated (without adenine) in the presence of D-glucose or cholera toxin showed stimulations of intra-islet cyclic [ 3 H]AMP that were proportionate to the levels of radioactive nucleotide present under non-stimulatory conditions. Labeling the islets in a high glucose concentration (27.7 mM) did not modify the nucleotide responses to glucose or cholera toxin. The specific activity of cyclic [ 3 H]AMP, determined by simultaneous assay of cyclic [ 3 H]AMP and total cyclic AMP, was not influenced by glucose or cholera toxin. Glucose had no effect on the specific activity of labeled ATP

  5. Simple Formation of Nanostructured Molybdenum Disulfide Thin Films by Electrodeposition

    Directory of Open Access Journals (Sweden)

    S. K. Ghosh

    2013-01-01

    Full Text Available Nanostructured molybdenum disulfide thin films were deposited on various substrates by direct current (DC electrolysis form aqueous electrolyte containing molybdate and sulfide ions. Post deposition annealing at higher temperatures in the range 450–700°C transformed the as-deposited amorphous films to nanocrystalline structure. High temperature X-ray diffraction studies clearly recorded the crystal structure transformations associated with grain growth with increase in annealing temperature. Surface morphology investigations revealed featureless structure in case of as-deposited surface; upon annealing it converts into a surface with protruding nanotubes, nanorods, or dumbbell shape nanofeatures. UV-visible and FTIR spectra confirmed about the presence of Mo-S bonding in the deposited films. Transmission electron microscopic examination showed that the annealed MoS2 films consist of nanoballs, nanoribbons, and multiple wall nanotubes.

  6. Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

    Science.gov (United States)

    Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G.

    2016-01-01

    Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials. PMID:27767030

  7. Contact-induced doping in aluminum-contacted molybdenum disulfide

    Science.gov (United States)

    Shimazu, Yoshihiro; Arai, Kensuke; Iwabuchi, Tatsuya

    2018-01-01

    The interface between two-dimensional semiconductors and metal contacts is an important topic of research of nanoelectronic devices based on two-dimensional semiconducting materials such as molybdenum disulfide (MoS2). We report transport properties of thin MoS2 flakes in a field-effect transistor geometry with Ti/Au and Al contacts. In contrast to widely used Ti/Au contacts, the conductance of flakes with Al contacts exhibits a smaller gate-voltage dependence, which is consistent with a substantial electron doping effect of the Al contacts. The temperature dependence of two-terminal conductance for the Al contacts is also considerably smaller than for the Ti/Au contacts, in which thermionic emission and thermally assisted tunneling play a dominant role. This result is explained in terms of the assumption that the carrier injection mechanism at an Al contact is dominated by tunneling that is not thermally activated.

  8. Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation.

    Science.gov (United States)

    Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G

    2016-10-21

    Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials.

  9. The Cyclical Characteristics of Universal Social Insurance

    OpenAIRE

    Richard Hemming

    2013-01-01

    This paper examines how a universal social insurance program proposed for Mexico can respond to cyclical variations in revenue while remaining selffinancing. More specifically, it discusses the issues involved in setting up a stabilization fund that can accumulate surpluses when revenue is cyclically high, which can be drawn down when revenue is cyclically low. Attention is also paid to the options available to create a fund with sufficient resources to respond to revenue shocks early it its ...

  10. Cyclic plasticity and fatigue of metals

    International Nuclear Information System (INIS)

    Mughrabi, H.

    1993-01-01

    This report is a survey of the cyclic deformation and fatigue behaviour of selected engineering steels and alloys. Emphasis is placed on the important roles of the cyclic slip mode and the stability of the microstructure during cyclic stressing and on the conditions of fatigue testing with respect to the failure mechanisms and fatigue life. The examples presented include low-temperature fatigue, high-temperature fatigue in the presence of dynamic strain ageing and thermomechanical fatigue. (orig.)

  11. Cyclic Vomiting Syndrome in Children

    Directory of Open Access Journals (Sweden)

    T.V. Sorokman

    2016-08-01

    Full Text Available Introduction. Cyclic vomiting syndrome (CVS — is a fairly common disease of unknown etiology that affects children of all age groups and sometimes adult population and refers to the functional disorders of the gastrointestinal tract. Objective: to evaluate the effectiveness of the usage of Rehydron Optim for oral rehydration therapy in children. Materials and methods. The treatment of 40 children aged 3 to 11 years with CVS (15 persons and primary acetonemic syndrome (25 persons in the period of acetonemic crisis, including 15 boys and 25 girls, was analyzed. All children were observed in the outpatient department of the Regional children’s hospital of Chernivtsi. Diagnosis was established based on anamnesis, clinical and laboratory data. Patients underwent required clinico-biological tests and instrumental examinations. The dynamics of the following syndromes was investigated: pain, vomiting, dehydration and intoxication. Rehydration therapy in all cases was oral with the usage of Rehydron Optim. Results of the study and their discussion. A cyclical vomiting was observed in children with primary acetonemic syndrome with satisfactory condition in attack-free period. Migraine-like headaches prevailed in 36 patients (80 %, and the age of these patients was older than 7 years. Same children had episodes of paroxysmal autonomic failure. Almost all surveyed children had in their family history the risk factors for CVS development. All children had positive dynamics of the main basic clinical manifestations on the background of oral rehydration therapy using Rehydron Optim. Within the 1st day of oral rehydration therapy with Rehydron Optim in children, we have noted a significant decrease in the incidence of lethargy, vomiting, spastic abdominal pain, smell of acetone in the exhaled air (p < 0.05. In children with the I degree of dehydration, clinical signs of dehydration were not seen before the treatment, and children with the II degree had an

  12. The multisubunit structure of synaptophysin. Relationship between disulfide bonding and homo-oligomerization.

    Science.gov (United States)

    Johnston, P A; Südhof, T C

    1990-05-25

    Synaptophysin, a major membrane protein of synaptic vesicles, contains four transmembrane regions and two intravesicular loops. Synaptophysin monomers associate into homopolymers that have the potential to form channels in the synaptic vesicle membrane. Here we show that in native synaptophysin, homopolymers are linked by noncovalent forces. The molecule contains unstable intramolecular disulfide bonds that undergo disulfide exchange during solubilization, thereby covalently cross-linking neighboring synaptophysin molecules. The locations of the intramolecular disulfide bonds in synaptophysin were determined, revealing that each of the two intravesicular loops of synaptophysin is circularized by a single disulfide bond. Cross-linking of synaptophysin by disulfide bonds can be triggered in synaptic vesicles and in intact cells by a cycle of reduction and oxidation, suggesting that native synaptophysin is a homomultimer in situ. In addition, chemical cross-linking of native synaptophysin demonstrates that a low molecular weight protein is specifically associated with synaptophysin complexes and is lost upon reduction of the intramolecular disulfide bonds. These data suggest that native synaptophysin forms a noncovalent homomultimeric complex whose structure and interaction with other proteins are dependent on the integrity of its intramolecular disulfide bonds and phospholipid environment.

  13. Modeling Cyclic Variation of Intracranial Pressure

    National Research Council Canada - National Science Library

    Daley, M

    2001-01-01

    ...) recording during mechanical ventilation are due to cyclic extravascular compressional modulation primarily of the cerebral venous bed, an established isovolumetric model of cerebrospinal fluid...

  14. Behaviour of Cohesionless Soils During Cyclic Loading

    DEFF Research Database (Denmark)

    Shajarati, Amir; Sørensen, Kris Wessel; Nielsen, Søren Kjær

    Offshore wind turbine foundations are typically subjected to cyclic loading from both wind and waves, which can lead to unacceptable deformations in the soil. However, no generally accepted standardised method is currently available, when accounting for cyclic loading during the design of offshore...... wind turbine foundations. Therefore a literature study is performed in order to investigate existing research treating the behaviour of cohesionless soils, when subjected to cyclic loading. The behaviour of a soil subjected to cyclic loading is found to be dependent on; the relative density, mean...

  15. 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.

  16. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    OpenAIRE

    Hoskins, J.T.; Zhou, Z.; Harding, P.A.

    2008-01-01

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser108/121, HB-EGF-Cys/Ser116/132, and HB-EGF-Cys/Ser134/143) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with Mr of 6.5, 21 and 24kDa were observed from lys...

  17. Native Conformation and Canonical Disulfide Bond Formation Are Interlinked Properties of HIV-1 Env Glycoproteins.

    Science.gov (United States)

    Go, Eden P; Cupo, Albert; Ringe, Rajesh; Pugach, Pavel; Moore, John P; Desaire, Heather

    2015-12-30

    We investigated whether there is any association between a native-like conformation and the presence of only the canonical (i.e., native) disulfide bonds in the gp120 subunits of a soluble recombinant human immunodeficiency virus type 1 (HIV-1) envelope (Env) glycoprotein. We used a mass spectrometry (MS)-based method to map the disulfide bonds present in nonnative uncleaved gp140 proteins and native-like SOSIP.664 trimers based on the BG505 env gene. Our results show that uncleaved gp140 proteins were not homogeneous, in that substantial subpopulations (20 to 80%) contained aberrant disulfide bonds. In contrast, the gp120 subunits of the native-like SOSIP.664 trimer almost exclusively retained the canonical disulfide bond pattern. We also observed that the purification method could influence the proportion of an Env protein population that contained aberrant disulfide bonds. We infer that gp140 proteins may always contain a variable but substantial proportion of aberrant disulfide bonds but that the impact of this problem can be minimized via design and/or purification strategies that yield native-like trimers. The same factors may also be relevant to the production and purification of monomeric gp120 proteins that are free of aberrant disulfide bonds. It is widely thought that a successful HIV-1 vaccine will include a recombinant form of the Env protein, a trimer located on the virion surface. To increase yield and simplify purification, Env proteins are often made in truncated, soluble forms. A consequence, however, can be the loss of the native conformation concomitant with the virion-associated trimer. Moreover, some soluble recombinant Env proteins contain aberrant disulfide bonds that are not expected to be present in the native trimer. To assess whether these observations are linked, to determine the extent of disulfide bond scrambling, and to understand why scrambling occurs, we determined the disulfide bond profiles of two soluble Env proteins with

  18. Investigating cyclic nucleotide and cyclic dinucleotide binding to HCN channels by surface plasmon resonance.

    Directory of Open Access Journals (Sweden)

    Sebastien Hayoz

    Full Text Available Hyperpolarization-activated cyclic nucleotide-modulated (HCN channels control cardiac and neuronal rhythmicity. HCN channels contain cyclic nucleotide-binding domain (CNBD in their C-terminal region linked to the pore-forming transmembrane segment with a C-linker. The C-linker couples the conformational changes caused by the direct binding of cyclic nucleotides to the HCN pore opening. Recently, cyclic dinucleotides were shown to antagonize the effect of cyclic nucleotides in HCN4 but not in HCN2 channels. Based on the structural analysis and mutational studies it has been proposed that cyclic dinucleotides affect HCN4 channels by binding to the C-linker pocket (CLP. Here, we first show that surface plasmon resonance (SPR can be used to accurately measure cyclic nucleotide binding affinity to the C-linker/CNBD of HCN2 and HCN4 channels. We then used SPR to investigate cyclic dinucleotide binding in HCN channels. To our surprise, we detected no binding of cyclic dinucleotides to the isolated monomeric C-linker/CNBDs of HCN4 channels with SPR. The binding of cyclic dinucleotides was further examined with isothermal calorimetry (ITC, which indicated no binding of cyclic dinucleotides to both monomeric and tetrameric C-linker/CNBDs of HCN4 channels. Taken together, our results suggest that interaction of the C-linker/CNBD with other parts of the channel is necessary for cyclic-dinucleotide binding in HCN4 channels.

  19. Cyclic nucleotide content of tobacco BY-2 cells.

    Science.gov (United States)

    Richards, Helen; Das, Swadipa; Smith, Christopher J; Pereira, Louisa; Geisbrecht, Alan; Devitt, Nicola J; Games, David E; van Geyschem, Jan; Gareth Brenton, A; Newton, Russell P

    2002-11-01

    The cyclic nucleotide content of cultured tobacco bright yellow-2 (BY-2) cells was determined, after freeze-killing, perchlorate extraction and sequential chromatography, by radioimmunoassay. The identities of the putative cyclic nucleotides, adenosine 3',5'-cyclic monophosphate (cyclic AMP), guanosine 3',5'-cyclic monophosphate (cyclic GMP) and cytidine 3',5'-cyclic monophosphate (cyclic CMP) were unambiguously confirmed by tandem mass spectrometry. The potential of BY-2 cell cultures as a model system for future investigations of cyclic nucleotide function in higher plants is discussed.

  20. CYCLICAL SUBNORMAL SEPARATION IN A-GROUPS

    African Journals Online (AJOL)

    :-at are split extensions of certain abelian p-groups by a metabelian pi-group, to satisfy the cyclic a1 subnormal separation condition. There is also a result which shows that A-groups with elementary abelian Sylow subgroups are. :icl~cally separated. KEYWORD: A-groups, Cyclical~Subnormal Separation, CS,-groups.

  1. Interactions of Cyclic Hydrocarbons with Biological Membranes

    NARCIS (Netherlands)

    SIKKEMA, J; DEBONT, JAM; POOLMAN, B

    1994-01-01

    Many cyclic hydrocarbons, e.g. aromatics, cycloalkanes, and terpenes, are toxic to microorganisms. The primary site of the toxic action is probably the cytoplasmic membrane, but the mechanism of the toxicity is still poorly understood. The effects of cyclic hydrocarbons were studied in liposomes

  2. Fractional behaviour at cyclic stretch-bending

    NARCIS (Netherlands)

    Emmens, W.C.; van den Boogaard, Antonius H.; Kazantzis, A.V.; de Hosson, J.Th.M.; Kolleck, R

    2010-01-01

    The fractional behaviour at cyclic stretch-bending has been studied by performing tensile tests at long specimens that are cyclically bent at the same time, on mild steel, dual-phase steel, stainless steel, aluminium and brass. Several types of fracture are observed, these are discussed, as are the

  3. Synthesis of cyclic alpha-MSH peptides

    NARCIS (Netherlands)

    Schaaper, W.M.M.; Adan, R.A.H.; Posthuma, T.A.; Oosterom, J.; Gispen, W.H.; Meloen, R.H.

    1998-01-01

    Cyclic lactam analogs of α-melanocyte stimulating hormone (α-MSH) have been shown to be potent agonists in the frog skin bioassay [Al-Obeidi, F. et al., J. Med. Chem., 32 (1989) 2555], demonstrating melanocortin-1 (MC1) receptor activity. We synthesized cyclic α-MSH(1-13) and α-MSH(4-10) lactam

  4. Synthesis of cyclic α-MSH peptides

    NARCIS (Netherlands)

    Gispen, W.H.; Schaaper, W.M.M..; Adan, R.A.H.; Posthuma, T.A.; Oosterom, J.; Meloen, R.H.

    1998-01-01

    Cyclic lactam analogs of -melanocyte stimulating hormone (-MSH) have been shown to be potent agonists in the frog skin bioassay [Al-Obeidi, F. et al., J. Med. Chem., 32 (1989) 2555], demonstrating melanocortin-1 (MC1) receptor activity. We synthesized cyclic -MSH(1-13) and -MSH(4-10) lactam analogs.

  5. Cyclic completion of the anamorphic universe

    Science.gov (United States)

    Ijjas, Anna

    2018-04-01

    Cyclic models of the universe have the advantage of avoiding initial conditions problems related to postulating any sort of beginning in time. To date, the best known viable examples of cyclic models have been ekpyrotic. In this paper, we show that the recently proposed anamorphic scenario can also be made cyclic. The key to the cyclic completion is a classically stable, non-singular bounce. Remarkably, even though the bounce construction was originally developed to connect a period of contraction with a period of expansion both described by Einstein gravity, we show here that it can naturally be modified to connect an ordinary contracting phase described by Einstein gravity with a phase of anamorphic smoothing. The paper will present the basic principles and steps in constructing cyclic anamorphic models.

  6. Protein disulfide bond generation in Escherichia coli DsbB–DsbA

    Energy Technology Data Exchange (ETDEWEB)

    Inaba, Kenji, E-mail: inaba-k@bioreg.kyushu-u.ac.jp [Medical Institute of Bioregulation, Kyushu University, Fukuoka 812-8582 (Japan)

    2008-05-01

    The crystal structure of the DsbB–DsbA–ubiquinone ternary complex has revealed a mechanism of protein disulfide bond generation in Escherichia coli. Protein disulfide bond formation is catalyzed by a series of Dsb enzymes present in the periplasm of Escherichia coli. The crystal structure of the DsbB–DsbA–ubiquinone ternary complex provided important insights into mechanisms of the de novo disulfide bond generation cooperated by DsbB and ubiquinone and of the disulfide bond shuttle from DsbB to DsbA. The structural basis for prevention of the crosstalk between the DsbA–DsbB oxidative and the DsbC–DsbD reductive pathways has also been proposed.

  7. Protein disulfide bond generation in Escherichia coli DsbB–DsbA

    International Nuclear Information System (INIS)

    Inaba, Kenji

    2008-01-01

    The crystal structure of the DsbB–DsbA–ubiquinone ternary complex has revealed a mechanism of protein disulfide bond generation in Escherichia coli. Protein disulfide bond formation is catalyzed by a series of Dsb enzymes present in the periplasm of Escherichia coli. The crystal structure of the DsbB–DsbA–ubiquinone ternary complex provided important insights into mechanisms of the de novo disulfide bond generation cooperated by DsbB and ubiquinone and of the disulfide bond shuttle from DsbB to DsbA. The structural basis for prevention of the crosstalk between the DsbA–DsbB oxidative and the DsbC–DsbD reductive pathways has also been proposed

  8. The Mitochondrial Disulfide Relay System: Roles in Oxidative Protein Folding and Beyond

    Directory of Open Access Journals (Sweden)

    Manuel Fischer

    2013-01-01

    Full Text Available Disulfide bond formation drives protein import of most proteins of the mitochondrial intermembrane space (IMS. The main components of this disulfide relay machinery are the oxidoreductase Mia40 and the sulfhydryl oxidase Erv1/ALR. Their precise functions have been elucidated in molecular detail for the yeast and human enzymes in vitro and in intact cells. However, we still lack knowledge on how Mia40 and Erv1/ALR impact cellular and organism physiology and whether they have functions beyond their role in disulfide bond formation. Here we summarize the principles of oxidation-dependent protein import mediated by the mitochondrial disulfide relay. We proceed by discussing recently described functions of Mia40 in the hypoxia response and of ALR in influencing mitochondrial morphology and its importance for tissue development and embryogenesis. We also include a discussion of the still mysterious function of Erv1/ALR in liver regeneration.

  9. Edge eigen-stress and eigen-displacement of armchair molybdenum disulfide nanoribbons

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Quan; Li, Xi [Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing 100083 (China); Volinsky, Alex A., E-mail: volinsky@usf.edu [Department of Mechanical Engineering, University of South Florida, Tampa, FL 33620 (United States); Su, Yanjing, E-mail: yjsu@ustb.edu.cn [Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE), University of Science and Technology Beijing, Beijing 100083 (China)

    2017-05-10

    Edge effects on mechanical properties of armchair molybdenum disulfide nanoribbons were investigated using first principles calculations. The edge eigen-stress model was applied to explain the relaxation process of forming molybdenum disulfide nanoribbon. Edge effects on surface atoms fluctuation degree were obtained from each fully relaxed nanoribbon with different width. Changes of the relaxed armchair molybdenum disulfide nanoribbons structure can be expressed using hexagonal perimeters pattern. Based on the thickness change, relaxed armchair molybdenum disulfide nanoribbons tensile/compression tests were simulated, providing intrinsic edge elastic parameters, such as eigen-stress, Young's modulus and Poisson's ratio. - Highlights: • Edge effects on mechanical properties of armchair MoS{sub 2} nanoribbons were investigated. • Structure changes of different width armchair MoS{sub 2} nanoribbons were obtained. • Tensile/compressive tests were conducted to determine elastic constants. • Mechanical properties are compared for two and three dimensional conditions.

  10. 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.

  11. 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

  12. 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...

  13. 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

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

    DEFF Research Database (Denmark)

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

    2015-01-01

    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...

  15. 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.

  16. Characterization of Disulfide-Linked Peptides Using Tandem Mass Spectrometry Coupled with Automated Data Analysis Software

    Science.gov (United States)

    Liang, Zhidan; McGuinness, Kenneth N.; Crespo, Alejandro; Zhong, Wendy

    2018-01-01

    Disulfide bond formation is critical for maintaining structure stability and function of many peptides and proteins. Mass spectrometry has become an important tool for the elucidation of molecular connectivity. However, the interpretation of the tandem mass spectral data of disulfide-linked peptides has been a major challenge due to the lack of appropriate tools. Developing proper data analysis software is essential to quickly characterize disulfide-linked peptides. A thorough and in-depth understanding of how disulfide-linked peptides fragment in mass spectrometer is a key in developing software to interpret the tandem mass spectra of these peptides. Two model peptides with inter- and intra-chain disulfide linkages were used to study fragmentation behavior in both collisional-activated dissociation (CAD) and electron-based dissociation (ExD) experiments. Fragments generated from CAD and ExD can be categorized into three major types, which result from different S-S and C-S bond cleavage patterns. DiSulFinder is a computer algorithm that was newly developed based on the fragmentation observed in these peptides. The software is vendor neutral and capable of quickly and accurately identifying a variety of fragments generated from disulfide-linked peptides. DiSulFinder identifies peptide backbone fragments with S-S and C-S bond cleavages and, more importantly, can also identify fragments with the S-S bond still intact to aid disulfide linkage determination. With the assistance of this software, more comprehensive disulfide connectivity characterization can be achieved. [Figure not available: see fulltext.

  17. Site‐Selective Disulfide Modification of Proteins: Expanding Diversity beyond the Proteome

    OpenAIRE

    Kuan, Seah Ling; Wang, Tao; Weil, Tanja

    2016-01-01

    Abstract The synthetic transformation of polypeptides with molecular accuracy holds great promise for providing functional and structural diversity beyond the proteome. Consequently, the last decade has seen an exponential growth of site‐directed chemistry to install additional features into peptides and proteins even inside living cells. The disulfide rebridging strategy has emerged as a powerful tool for site‐selective modifications since most proteins contain disulfide bonds. In this Revie...

  18. Disulfide-bond scrambling promotes amorphous aggregates in lysozyme and bovine serum albumin.

    Science.gov (United States)

    Yang, Mu; Dutta, Colina; Tiwari, Ashutosh

    2015-03-12

    Disulfide bonds are naturally formed in more than 50% of amyloidogenic proteins, but the exact role of disulfide bonds in protein aggregation is still not well-understood. The intracellular reducing agents and/or improper use of antioxidants in extracellular environment can break proteins disulfide bonds, making them unstable and prone to misfolding and aggregation. In this study, we report the effect of disulfide-reducing agent dithiothreitol (DTT) on hen egg white lysozyme (lysozyme) and bovine serum albumin (BSA) aggregation at pH 7.2 and 37 °C. BSA and lysozyme proteins treated with disulfide-reducing agents form very distinct amorphous aggregates as observed by scanning electron microscope. However, proteins with intact disulfide bonds were stable and did not aggregate over time. BSA and lysozyme aggregates show unique but measurable differences in 8-anilino-1-naphthalenesulfonic acid (ANS) and 4,4'-dianilino-1,1'-binaphthyl-5,5'-disulfonic acid (bis-ANS) fluorescence, suggesting a loose and flexible aggregate structure for lysozyme but a more compact aggregate structure for BSA. Scrambled disulfide-bonded protein aggregates were observed by nonreducing sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) for both proteins. Similar amorphous aggregates were also generated using a nonthiol-based reducing agent, tris(2-carboxyethyl)phosphine (TCEP), at pH 7.2 and 37 °C. In summary, formation of distinct amorphous aggregates by disulfide-reduced BSA and lysozyme suggests an alternate pathway for protein aggregation that may be relevant to several proteins.

  19. 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)

  20. 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...

  1. 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....

  2. 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.

  3. Bovicin HJ50-like lantibiotics, a novel subgroup of lantibiotics featured by an indispensable disulfide bridge.

    Directory of Open Access Journals (Sweden)

    Jian Wang

    Full Text Available Lantibiotics are ribosomally-synthesized and posttranslationally modified peptides with potent antimicrobial activities. Discovery of novel lantibiotics has been greatly accelerated with the soaring release of genomic information of microorganisms. As a unique class II lantibiotic, bovicin HJ50 is produced by Streptococcus bovis HJ50 and contains one rare disulfide bridge. By using its precursor BovA as a drive sequence, 16 BovA-like peptides were revealed in a wide variety of species. From them, three representative novel lan loci from Clostridium perfringens D str. JGS1721, Bacillus cereus As 1.348 and B. thuringiensis As 1.013 were identified by PCR screening. The corresponding mature lantibiotics designated perecin, cerecin and thuricin were obtained and structurally elucidated to be bovicin HJ50-like lantibiotics especially by containing a conserved disulfide bridge. The disulfide bridge was substantiated to be essential for the function of bovicin HJ50-like lantibiotics as its disruption eliminated their antimicrobial activities. Further analysis indicated that the disulfide bridge played a crucial role in maintaining the hydrophobicity of bovicin HJ50, which might facilitate it to exert antimicrobial function. This study unveiled a novel subgroup of disulfide-containing lantibiotics from bacteria of different niches and further demonstrated the indispensable role of disulfide bridge in these novel bovicin HJ50-like lantibiotics.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. Guanylin peptides: cyclic GMP signaling mechanisms

    Directory of Open Access Journals (Sweden)

    Forte L.R.

    1999-01-01

    Full Text Available Guanylate cyclases (GC serve in two different signaling pathways involving cytosolic and membrane enzymes. Membrane GCs are receptors for guanylin and atriopeptin peptides, two families of cGMP-regulating peptides. Three subclasses of guanylin peptides contain one intramolecular disulfide (lymphoguanylin, two disulfides (guanylin and uroguanylin and three disulfides (E. coli stable toxin, ST. The peptides activate membrane receptor-GCs and regulate intestinal Cl- and HCO3- secretion via cGMP in target enterocytes. Uroguanylin and ST also elicit diuretic and natriuretic responses in the kidney. GC-C is an intestinal receptor-GC for guanylin and uroguanylin, but GC-C may not be involved in renal cGMP pathways. A novel receptor-GC expressed in the opossum kidney (OK-GC has been identified by molecular cloning. OK-GC cDNAs encode receptor-GCs in renal tubules that are activated by guanylins. Lymphoguanylin is highly expressed in the kidney and heart where it may influence cGMP pathways. Guanylin and uroguanylin are highly expressed in intestinal mucosa to regulate intestinal salt and water transport via paracrine actions on GC-C. Uroguanylin and guanylin are also secreted from intestinal mucosa into plasma where uroguanylin serves as an intestinal natriuretic hormone to influence body Na+ homeostasis by endocrine mechanisms. Thus, guanylin peptides control salt and water transport in the kidney and intestine mediated by cGMP via membrane receptors with intrinsic guanylate cyclase activity.

  10. Cytotoxic and Antibiotic Cyclic Pentapeptide from an Endophytic Aspergillus tamarii of Ficus carica.

    Science.gov (United States)

    Ma, Yang-Min; Liang, Xi-Ai; Zhang, Hong-Chi; Liu, Rui

    2016-05-18

    A new cyclic pentapeptide, disulfide cyclo-(Leu-Val-Ile-Cys-Cys) (1), named malformin E, together with 13 known cyclic dipeptides, was isolated from the culture broth of endophytic fungus FR02 from the roots of Ficus carica. The strain FR02 was identified as Aspergillus tamarii on the basis of morphological characteristics and molecular analyses of internal transcribed spacer (ITS). Their structures were determined by the combination of 1D and 2D NMR spectroscopy, HRMS (ESI), UV, and Marfey's analysis. Compound 1 exhibited strong cytotoxic activities against human cancer cell strains MCF-7 and A549 with IC50 values of 0.65 and 2.42 μM, respectively. It also displayed remarkable antimicrobial activities against Bacillus subtilis, Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Penicillium chrysogenum, Candida albicans, and Fusarium solani with MIC values of 0.91, 0.45, 1.82, 0.91, 3.62, 7.24, and 7.24 μM, respectively.

  11. Optical Controlled Terahertz Modulator Based on Tungsten Disulfide Nanosheet.

    Science.gov (United States)

    Fan, Zhiyuan; Geng, Zhaoxin; Lv, Xiaoqin; Su, Yue; Yang, Yuping; Liu, Jian; Chen, Hongda

    2017-11-01

    The terahertz (THz) modulator, which will be applied in next-generation wireless communication, is a key device in a THz communication system. Current THz modulators based on traditional semiconductors and metamaterials have limited modulation depth or modulation range. Therefore, a THz modulator based on annealed tungsten disulfide (WS 2 , p-type) and high-resistivity silicon (n-type) is demonstrated. Pumped by a laser, the modulator presents a laser power-dependent modulation effect. Ranging from 0.25 to 2 THz, the modulation depth reaches 99% when the pumping laser is 2.59 W/cm 2 . The modulator works because the p-n heterojunction can separate and limit carriers to change the conductivity of the device, which results in a modulation of the THz wave. The wide band gap of WS 2 can promote the separation and limitation of carriers to obtain a larger modulation depth, which provides a new direction for choosing new materials and new structures to fabricate a better THz modulator.

  12. Oxidation Effect in Octahedral Hafnium Disulfide Thin Film.

    Science.gov (United States)

    Chae, Sang Hoon; Jin, Youngjo; Kim, Tae Soo; Chung, Dong Seob; Na, Hyunyeong; Nam, Honggi; Kim, Hyun; Perello, David J; Jeong, Hye Yun; Ly, Thuc Hue; Lee, Young Hee

    2016-01-26

    Atomically smooth van der Waals materials are structurally stable in a monolayer and a few layers but are susceptible to oxygen-rich environments. In particular, recently emerging materials such as black phosphorus and perovskite have revealed stronger environmental sensitivity than other two-dimensional layered materials, often obscuring the interesting intrinsic electronic and optical properties. Unleashing the true potential of these materials requires oxidation-free sample preparation that protects thin flakes from air exposure. Here, we fabricated few-layer hafnium disulfide (HfS2) field effect transistors (FETs) using an integrated vacuum cluster system and study their electronic properties and stability under ambient conditions. By performing all the device fabrication and characterization procedure under an oxygen- and moisture-free environment, we found that few-layer AA-stacking HfS2-FETs display excellent field effect responses (Ion/Ioff ≈ 10(7)) with reduced hysteresis compared to the FETs prepared under ambient conditions. Oxidation of HfS2 occurs uniformly over the entire area, increasing the film thickness by 250% at a prolonged oxidation time of >120 h, while defects on the surface are the preferential initial oxidation sites. We further demonstrated that the stability of the device in air is significantly improved by passivating FETs with BN in a vacuum cluster.

  13. Ferroelectric memory based on molybdenum disulfide and ferroelectric hafnium oxide

    Science.gov (United States)

    Yap, Wui Chung; Jiang, Hao; Xia, Qiangfei; Zhu, Wenjuan

    Recently, ferroelectric hafnium oxide (HfO2) was discovered as a new type of ferroelectric material with the advantages of high coercive field, excellent scalability (down to 2.5 nm), and good compatibility with CMOS processing. In this work, we demonstrate, for the first time, 2D ferroelectric memories with molybdenum disulfide (MoS2) as the channel material and aluminum doped HfO2 as the ferroelectric gate dielectric. A 16 nm thick layer of HfO2, doped with 5.26% aluminum, was deposited via atomic layer deposition (ALD), then subjected to rapid thermal annealing (RTA) at 1000 °C, and the polarization-voltage characteristics of the resulting metal-ferroelectric-metal (MFM) capacitors were measured, showing a remnant polarization of 0.6 μC/cm2. Ferroelectric memories with embedded ferroelectric hafnium oxide stacks and monolayer MoS2 were fabricated. The transfer characteristics after program and erase pulses revealed a clear ferroelectric memory window. In addition, endurance (up to 10,000 cycles) of the devices were tested and effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, were observed. This research can potentially lead to advances of 2D materials in low-power logic and memory applications.

  14. Protein Disulfide Isomerase and Host-Pathogen Interaction

    Directory of Open Access Journals (Sweden)

    Beatriz S. Stolf

    2011-01-01

    Full Text Available Reactive oxygen species (ROS production by immunological cells is known to cause damage to pathogens. Increasing evidence accumulated in the last decade has shown, however, that ROS (and redox signals functionally regulate different cellular pathways in the host-pathogen interaction. These especially affect (i pathogen entry through protein redox switches and redox modification (i.e., intra- and interdisulfide and cysteine oxidation and (ii phagocytic ROS production via Nox family NADPH oxidase enzyme and the control of phagolysosome function with key implications for antigen processing. The protein disulfide isomerase (PDI family of redox chaperones is closely involved in both processes and is also implicated in protein unfolding and trafficking across the endoplasmic reticulum (ER and towards the cytosol, a thiol-based redox locus for antigen processing. Here, we summarise examples of the cellular association of host PDI with different pathogens and explore the possible roles of pathogen PDIs in infection. A better understanding of these complex regulatory steps will provide insightful information on the redox role and coevolutional biological process, and assist the development of more specific therapeutic strategies in pathogen-mediated infections.

  15. Bright monolayer tungsten disulfide via exciton and trion chemical modulations.

    Science.gov (United States)

    Tao, Ye; Yu, Xuechao; Li, Jiewei; Liang, Houkun; Zhang, Ying; Huang, Wei; Wang, Qi Jie

    2018-04-05

    Atomically thin transition metal dichalcogenides (TMDCs) with exceptional electrical and optical properties have drawn tremendous attention for use in novel optoelectronic applications as photodetectors, transistors, light emitters, etc. However, electron bound trions formed through the combination of neutral excitons and electrons significantly decrease the photoluminescence (PL) efficiency of TMDCs. In this study, we report a simple yet efficient chemical doping strategy to modulate the optical properties of monolayer tungsten disulfide (WS2). As a demonstrative example, a chemically doped monolayer of WS2 exhibits remarkable PL enhancement of about one order of magnitude higher than that of pristine WS2. This outstanding PL enhancement is attributed to the fact that excess electrons, which promote the formation of electron-bound trions, are reduced in number through charge transfer from WS2 to the chemical dopant. Furthermore, an improved degree of circular polarization from ∼9.0% to ∼41.5% was also observed in the chemically doped WS2 monolayer. This work describes a feasible strategy to manipulate the optical properties of TMDCs via exciton modulation, making TMDCs promising candidates for versatile semiconductor-based photonic devices.

  16. Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer.

    Science.gov (United States)

    Pan, Hui

    2016-12-01

    Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

  17. Impairment of thiol-disulfide homeostasis in preeclampsia.

    Science.gov (United States)

    Korkmaz, Vakkas; Kurdoglu, Zehra; Alisik, Murat; Cetin, Orkun; Korkmaz, Hilal; Surer, Hatice; Erel, Ozcan

    2016-12-01

    To investigate the effects of severity of preeclampsia on thiol-disulfide homeostasis (TDH). A total of 108 participants were divided into three groups: Group 1 was composed of pregnant women with no obstetric complications, Group 2 included pregnant women with mild preeclampsia, and Group 3 consisted of pregnant women with severe preeclampsia. TDH parameters were determined, and comparisons of clinical and routine laboratory test findings were made in all groups. The serum native thiol level was 347.9 ± 27.4 in the control group, 237.2 ± 44.2 in the mild preeclampsia group, and 227.9 ± 53.1 in the severe preeclampsia group (p preeclampsia group, and 248.3 ± 57.4 in the severe preeclampsia group (p preeclampsia group, and 10.2 ± 4.8 in the severe preeclampsia group (p = 0.001). A significant correlation between impairment in degree of TDH and severity of preeclampsia was observed. TDH was impaired in women with preeclampsia, and this impairment increased with disease severity. Therefore, impaired TDH may have a role in the etiopathogenesis of the disease.

  18. Toward barrier free contact to molybdenum disulfide using graphene electrodes.

    Science.gov (United States)

    Liu, Yuan; Wu, Hao; Cheng, Hung-Chieh; Yang, Sen; Zhu, Enbo; He, Qiyuan; Ding, Mengning; Li, Dehui; Guo, Jian; Weiss, Nathan O; Huang, Yu; Duan, Xiangfeng

    2015-05-13

    Two-dimensional layered semiconductors such as molybdenum disulfide (MoS2) have attracted tremendous interest as a new class of electronic materials. However, there are considerable challenges in making reliable contacts to these atomically thin materials. Here we present a new strategy by using graphene as the back electrodes to achieve ohmic contact to MoS2. With a finite density of states, the Fermi level of graphene can be readily tuned by a gate potential to enable a nearly perfect band alignment with MoS2. We demonstrate for the first time a transparent contact to MoS2 with zero contact barrier and linear output behavior at cryogenic temperatures (down to 1.9 K) for both monolayer and multilayer MoS2. Benefiting from the barrier-free transparent contacts, we show that a metal-insulator transition can be observed in a two-terminal MoS2 device, a phenomenon that could be easily masked by Schottky barriers found in conventional metal-contacted MoS2 devices. With further passivation by boron nitride (BN) encapsulation, we demonstrate a record-high extrinsic (two-terminal) field effect mobility up to 1300 cm(2)/(V s) in MoS2 at low temperature.

  19. 9-Fluorenylmethyl (Fm) Disulfides: Biomimetic Precursors for Persulfides

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chung-Min; Johnson, Brett A.; Duan, Jicheng; Park, Jeong-Jin; Day, Jacob J.; Gang, David; Qian, Wei-Jun; Xian, Ming

    2016-03-04

    Protein S-sulfhydration has been recognized as an important post-translational modification that regulates H2S signals. However, the reactivity and biological implications of the products of S-sulfhydration, i.e. persulfides, are still unclear. This is mainly due to the instability of persulfides and difficulty to access these molecules. Under physiological conditions persulfides mainly exist in anionic forms because of their low pKa values. However, current methods do not allow for the direct generation of persulfide anions under biomimetic and non-H2S conditions. Herein we report the development of a functional disulfide, FmSSPy-A (Fm =9-fluorenylmethyl; Py = pyridinyl). This reagent can effectively convert both small molecule and protein thiols (-SH) to form –S-SFm adducts under mild conditions. It allows for a H2S-free and biomimetic protocol to generate highly reactive persulfides (in their anionic forms). We also demonstrated the high nucleophilicity of persulfides toward a number of thiol-blocking reagents. This method holds promise for further understanding the chemical biology of persulfides and S-sulfhydration.

  20. Graphene oxide – molybdenum disulfide hybrid membranes for hydrogen separation

    KAUST Repository

    Ostwal, Mayur

    2017-12-24

    Graphene oxide – molybdenum disulfide hybrid membranes were prepared using vacuum filtration technique. The thickness and the MoS2 content in the membranes were varied and their H2 permeance and H2/CO2 selectivity are reported. A 60nm hybrid membrane containing ~75% by weight of MoS2 exhibited the highest H2 permeance of 804×10−9mol/m2·s·Pa with corresponding H2/CO2 selectivity of 26.7; while a 150nm hybrid membrane with ~29% MoS2 showed the highest H2/CO2 selectivity of 44.2 with corresponding H2 permeance of 287×10−9mol/m2·s·Pa. The hybrid membranes exhibited much higher H2 permeance compared to graphene oxide membranes and higher selectivity compared to MoS2 membranes, which fully demonstrated the synergistic effect of both nanomaterials. The membranes also displayed excellent operational long-term stability.

  1. Biotechnology for removal of carbon disulfide emissions. Final report

    Energy Technology Data Exchange (ETDEWEB)

    McIntosh, M.J.

    1995-07-01

    Biological removal in a ``biofilter`` plant of carbon disulfide and hydrogen sulfide from the air effluent of a viscose plant at Teepak, Inc., is analyzed from process and economic standpoints by use of the Aspen Plus simulation program. The metabolic product from the biofilter, 3% sulfuric acid, must be transformed at the source into either a marketable or recyclable commodity (such as 95% sulfuric acid, high-quality sulfur, or high-quality gypsum) or a material with reasonable landfill costs (such as sulfur or gypsum). The simulations indicate that the total capital requirement for production of concentrated sulfuric acid is $48.9 million; for high-quality gypsum, $40.4 million; and for high-quality sulfur, $29.4 million. Production of concentrated sulfur for landfill is not economically practical. The process to neutralize the 3% acid effluent with limestone and landfill the resulting low-quality gypsum requires the lowest total investment of the processes simulated, $8.7 million, including the biofilter plant.

  2. DNA origami deposition on native and passivated molybdenum disulfide substrates

    Directory of Open Access Journals (Sweden)

    Xiaoning Zhang

    2014-04-01

    Full Text Available Maintaining the structural fidelity of DNA origami structures on substrates is a prerequisite for the successful fabrication of hybrid DNA origami/semiconductor-based biomedical sensor devices. Molybdenum disulfide (MoS2 is an ideal substrate for such future sensors due to its exceptional electrical, mechanical and structural properties. In this work, we performed the first investigations into the interaction of DNA origami with the MoS2 surface. In contrast to the structure-preserving interaction of DNA origami with mica, another atomically flat surface, it was observed that DNA origami structures rapidly lose their structural integrity upon interaction with MoS2. In a further series of studies, pyrene and 1-pyrenemethylamine, were evaluated as surface modifications which might mitigate this effect. While both species were found to form adsorption layers on MoS2 via physisorption, 1-pyrenemethylamine serves as a better protective agent and preserves the structures for significantly longer times. These findings will be beneficial for the fabrication of future DNA origami/MoS2 hybrid electronic structures.

  3. Undrained Cyclic Behaviour of Dense Frederikshavn Sand

    DEFF Research Database (Denmark)

    Nielsen, Søren Kjær; Ibsen, Lars Bo; Sørensen, Kris Wessel

    2013-01-01

    of undrained cyclic triaxial tests, which have been performed at the Geotechnical Laboratory at Aalborg University. In order to ensure offshore conditions, the tests were fully saturated and performed with a relative density of 80 %. During cyclic loading, special attention was given to the development of pore......A modified contour diagram is created for the Frederikshavn Sand in the undrained case for a relative density of ID = 80 %. It can be used to estimate the number of cycles to failure for a given combination of pore pressure, average and cyclic load ratio. The diagram is based on a series...

  4. Driving Force Based Design of Cyclic Distillation

    DEFF Research Database (Denmark)

    Nielsen, Rasmus Fjordbak; Huusom, Jakob Kjøbsted; Abildskov, Jens

    2017-01-01

    Driving force based design is adopted from conventional continuous distillation to cyclic distillation. This leads to a definition of the operating line representation for the cyclic distillation process. A possible realization of the driving force design is presented, which implies operation...... with mixed phase feeds. A range of binary test cases, benzene toluene, methanol water, and ethanol water, are evaluated. The advantage of the design approach in cyclic distillation is shown to be analogous to the advantages obtained in conventional continuous distillation, including a minimal utility...

  5. Novel Methods for the Chemical Synthesis of Insulin Superfamily Peptides and of Analogues Containing Disulfide Isosteres.

    Science.gov (United States)

    Hossain, Mohammed Akhter; Wade, John D

    2017-09-19

    The insulin superfamily of peptides is ubiquitous within vertebrates and invertebrates and is characterized by the presence of a set of three disulfide bonds in a unique disposition. With the exception of insulin-like growth factors I and II, which are single chain peptides, the remaining 8 members of the human insulin superfamily are two-chain peptides containing one intramolecular and two intermolecular disulfide bridges. These structural features have long made the chemical synthesis of the peptides a considerable challenge, in particular, including their correct disulfide bond pairing and formation. However, they have also afforded the opportunity to develop modern solid phase synthesis methods for the preparation of such peptides that incorporate novel or improved chemical methods for the controlled introduction of both disulfide bonds and their surrogates, both during and after peptide chain assembly. In turn, this has enabled a detailed probing of the structure and function relationship of this small but complex superfamily of peptides. After initially using and subsequently identifying significant limitations of the approach of simultaneous random chain combination and oxidative folding, our laboratory undertook to develop robust chemical synthesis strategies in concert with orthogonal cysteine S-protecting groups and corresponding regioselective disulfide bond formation. These have included the separate synthesis of each of the two chains or of the two chains linked by an artificial C-peptide that is removed following postoxidative folding. These, in turn, have enabled an increased ease of acquisition in a good yield of not only members of human insulin superfamily but other insulin-like peptides. Importantly, these successful methods have enabled, for the first time, a detailed analysis of the role that the disulfide bonds play in the structure and function of such peptides. This was achieved by selective removal of the disulfide bonds or by the judicious

  6. Identification of cyclic peptides for facilitation of transcellular transport of phages across intestinal epithelium in vitro and in vivo.

    Science.gov (United States)

    Yamaguchi, Shunsuke; Ito, Shingo; Kurogi-Hirayama, Mio; Ohtsuki, Sumio

    2017-09-28

    Methodology to enhance intestinal absorption of macromolecular drugs is an important challenge for developing next-generation biomedicines. So far, various cationic cell-penetrating peptides have been reported to facilitate uptake of certain bioactive proteins. However, cyclic peptides might be better candidates, as they are more metabolically stable than linear peptides. Accordingly, we hypothesized that suitable cyclic peptides would promote the absorption of macromolecules across intestinal epithelium. To test this idea, we adopted Caco-2 cell permeability assay as an in vitro human intestinal absorption model, and M13 phage as a model of macromolecules. Successive screenings of a phage library displaying cyclic heptapeptides via a short GGGS linker yielded 3 hits. Among them, phage displaying cyclic heptapeptide DNPGNET (DNP-phage) showed the greatest permeability across a Caco-2 cell monolayer and mouse intestinal epithelium. Interestingly, DNPGNET (DNP) does not contain any basic amino acids. Its isoelectric point (pI) was estimated to be 2.72. It did not reduce the viability or tight-junction integrity of Caco-2 cells at concentrations up to 100μM for 24h. Uptake of either DNP-phage or a fluorescence-labeled DNP derivative (AC-DNPGNET-CGGGS modified with 5/6-FAM at the C-terminal; the cysteines serve to generate the cyclic peptide via disulfide bond formation, and GGGS is the phage linker) by Caco-2 cells was inhibited by low temperature, unlabeled AC-DNPGNET-CGGGS and EIPA, a macropinocytosis inhibitor. Thus, DNP appears to facilitate transcellular permeability of phages via macropinocytosis, but not paracellular diffusion. These findings indicate that DNP is a promising candidate as a carrier to promote intestinal absorption of macromolecular drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. 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.

  8. Genetics Home Reference: cyclic vomiting syndrome

    Science.gov (United States)

    ... infections. Other triggers can include periods without eating (fasting), temperature extremes, lack of sleep, overexertion, allergies, ingesting ... include changes in brain function, hormonal abnormalities, and gastrointestinal problems. Many researchers believe that cyclic vomiting syndrome ...

  9. Cyclic hardening in bundled actin networks.

    Science.gov (United States)

    Schmoller, K M; Fernández, P; Arevalo, R C; Blair, D L; Bausch, A R

    2010-01-01

    Nonlinear deformations can irreversibly alter the mechanical properties of materials. Most soft materials, such as rubber and living tissues, display pronounced softening when cyclically deformed. Here we show that, in contrast, reconstituted networks of crosslinked, bundled actin filaments harden when subject to cyclical shear. As a consequence, they exhibit a mechano-memory where a significant stress barrier is generated at the maximum of the cyclic shear strain. This unique response is crucially determined by the network architecture: at lower crosslinker concentrations networks do not harden, but soften showing the classic Mullins effect known from rubber-like materials. By simultaneously performing macrorheology and confocal microscopy, we show that cyclic shearing results in structural reorganization of the network constituents such that the maximum applied strain is encoded into the network architecture.

  10. Anodic selective functionalization of cyclic amine derivatives

    OpenAIRE

    Onomura, Osamu

    2012-01-01

    Anodic reactions are desirable methods from the viewpoint of Green Chemistry, since no toxic oxidants are necessary for the oxidation of organic molecules. This review introduces usefulness of anodic oxidation and successive reaction for selective functionalization of cyclic amine derivatives.

  11. Cyclic voltammetry and reduction mechanistic studies of ...

    African Journals Online (AJOL)

    styrylpyrylium perchlorates have been evaluated using cyclic voltammetry, in comparison to their non-methylated derivatives values. The reduction peak of all studied compounds remained chemically irreversible. The presence of the ...

  12. Mortar constituent of concrete under cyclic compression

    Science.gov (United States)

    Maher, A.; Darwin, D.

    1980-10-01

    The behavior of the mortar constituent of concrete under cyclic compression was studied and a simple analytic model was developed to represent its cyclic behavior. Experimental work consisted of monotonic and cyclic compressive loading of mortar. Two mixes were used, with proportions corresponding to concretes having water cement ratios of 0.5 and 0.6. Forty-four groups of specimens were tested at ages ranging from 5 to 70 days. complete monotonic and cyclic stress strain envelopes were obtained. A number of loading regimes were investigated, including cycles to a constant maximum strain. Major emphasis was placed on tests using relatively high stress cycles. Degradation was shown to be a continuous process and a function of both total strain and load history. No stability or fatigue limit was apparent.

  13. cyclic -perimeter hydrocarbon ruthenium complexes bearing ...

    Indian Academy of Sciences (India)

    - cyclic -perimeter hydrocarbon ruthenium complexes bearing functionalized pyridyl diketones: Isolation of complexes with 2-N∩O and 4-N∩O bonding modes of ligands. Saphidabha L Nongbri Babulal Das Mohan Rao Kollipara.

  14. Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions.

    Science.gov (United States)

    Chen, Yaju; Luo, Rongchang; Xu, Qihang; Jiang, Jun; Zhou, Xiantai; Ji, Hongbing

    2017-06-09

    A facile and one-pot synthesis of metalloporphyrin-based ionic porous organic polymers (M-iPOPs) was performed through a typical Yamamoto-Ullmann coupling reaction for the first time. We used various characterization techniques to demonstrate that these strongly polar Al-based materials (Al-iPOP) possessed a relatively uniform microporosity, good swellable features, and a good CO 2 capture capacity. If we consider the particular physicochemical properties, heterogeneous Al-iPOP, which bears both a metal active center and halogen anion, acted as a bifunctional catalyst for the solvent- and additive-free synthesis of cyclic carbonates from various epoxides and CO 2 with an excellent activity and good recyclability under mild conditions. Interestingly, these CO 2 -philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO 2 in N 2 , v/v) as a raw material, which indicates that a stable local microenvironment and polymer swellability might promote the transformation. Thus, the introduction of polar ionic liquid units into metalloporphyrin-based porous materials is regarded as a promising new strategy for the chemical conversion of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. 3' : 5'-Cyclic AMP-dependent 3'

    NARCIS (Netherlands)

    Mato, José M.; Krens, Frans A.; Haastert, Peter J.M. van; Konijn, Theo M.

    1977-01-01

    Suspensions of 3':5'-cyclic AMP (cAMP)-sensitive cells of Dictyostelium discoideum responded to a cAMP pulse with increased 3':5'-cyclic GMP (cGMP) levels. Under the assay conditions used (2 × 10^8 cells per ml in 10 mM phosphate buffer, pH 6.0) cAMP (5 × 10-8 M final concentration) increased cGMP

  16. Empty Container Management in Cyclic Shipping Routes

    OpenAIRE

    Dong-Ping Song; Jing-Xin Dong

    2008-01-01

    This paper considers the empty container management problem in a cyclic shipping route. The objective is to seek the optimal empty container repositioning policy in a dynamic and stochastic situation by minimising the expected total costs consisting of inventory holding costs, demand lost-sale costs, lifting-on and lifting-off charges, and container transportation costs. A three-phase threshold control policy is developed to reposition empty containers in cyclic routes. The threshold values a...

  17. 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.

  18. Carbon disulfide mediates socially-acquired nicotine self-administration.

    Directory of Open Access Journals (Sweden)

    Tengfei Wang

    Full Text Available The social environment plays a critical role in smoking initiation as well as relapse. We previously reported that rats acquired nicotine self-administration with an olfactogustatory cue only when another rat consuming the same cue was present during self-administration. Because carbon disulfide (CS2 mediates social learning of food preference in rodents, we hypothesized that socially acquired nicotine self-administration is also mediated by CS2. We tested this hypothesis by placing female adolescent Sprague-Dawley rats in operant chambers equipped with two lickometers. Licking on the active spout meeting a fixed-ratio 10 schedule triggered the concurrent delivery of an i.v. infusion (saline, or 30 µg/kg nicotine, free base and an appetitive olfactogustatory cue containing CS2 (0-500 ppm. Rats that self-administered nicotine with the olfactogustatory cue alone licked less on the active spout than on the inactive spout. Adding CS2 to the olfactogustatory cue reversed the preference for the spouts. The group that received 500 ppm CS2 and the olfactogustatory cue obtained a significantly greater number of nicotine infusions than other groups. After extinction training, the original self-administration context reinstated nicotine-seeking behavior in all nicotine groups. In addition, in rats that received the olfactogustatory cue and 500 ppm CS2 during SA, a social environment where the nicotine-associated olfactory cue is present, induced much stronger drug-seeking behavior compared to a social environment lacking the olfactogustatory cue. These data established that CS2 is a critical signal that mediates social learning of nicotine self-administration with olfactogustatory cues in rodents. Additionally, these data showed that the social context can further enhance the drug-seeking behavior induced by the drug-taking environment.

  19. Consecutive exotropia following surgically corrected cyclic esotropia.

    Science.gov (United States)

    Post, Joel; Eidsness, Ryan B; Romanchuk, Kenneth G

    2007-01-01

    Cyclic esotropia is a rare form of strabismus consisting of regular intervals of esotropia alternating with periods of orthophoria in a rhythmic/cyclic manner. In the vast majority of cases, surgery appears to permanently correct the esotropia, with no sequelae after years of follow-up. We report a case of consecutive exotropia in a patient five years after bilateral medial rectus recessions for cyclic esotropia. A case report involving review of a clinical chart. A two-year-old male presented with right esotropia and mild amblyopia. He was treated with patching and following resolution of the amblyopia he developed a cyclic esotropia. Surgical correction was performed for the full amount measured on a "manifest" day. Following the surgery, he was orthophoric and demonstrated binocular vision. He remained stable for five years, and then returned with occasional diplopia and an intermittent exotropia. Cyclic esotropia is a rare disorder of ocular motility that spontaneously appears and disappears at regular intervals. After surgical correction, the deviation disappears and recurrence of esotropia is very infrequent. We present the first reported case of consecutive exotropia following surgical correction of a cyclic esotropia.

  20. Dynamic Chemistry of Disulfide Terminated Oligonucleotides in Duplexes and Double-Crossover Tiles.

    Science.gov (United States)

    De Stefano, Mattia; Vesterager Gothelf, Kurt

    2016-06-16

    Designed nanostructures formed by self-assembly of multiple DNA strands suffer from low stability at elevated temperature and under other denaturing conditions. Here, we propose a method for covalent coupling of DNA strands in such structures by the formation of disulfide bonds; this allows disassembly of the structure under reducing conditions. The dynamic chemistry of disulfides and thiols was applied to crosslink DNA strands with terminal disulfide modifications. The formation of disulfide-linked DNA duplexes consisting of three strands is demonstrated, as well as a more-complex DNA double-crossover tile. All the strands in the fully disulfide-linked structures are covalently and geometrically interlocked, and it is demonstrated that the structures are stable under heating and in the presence of denaturants. Such a reversible system can be exploited in applications where higher DNA stability is needed only temporarily, such as delivery of cargoes to cells by DNA nanostructures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Disulfide bond within mu-calpain active site inhibits activity and autolysis.

    Science.gov (United States)

    Lametsch, René; Lonergan, Steven; Huff-Lonergan, Elisabeth

    2008-09-01

    Oxidative processes have the ability to influence mu-calpain activity. In the present study the influence of oxidation on activity and autolysis of mu-calpain was examined. Furthermore, LC-MS/MS analysis was employed to identify and characterize protein modifications caused by oxidation. The results revealed that the activity of mu-calpain is diminished by oxidation with H2O2 in a reversible manner involving cysteine and that the rate of autolysis of mu-calpain concomitantly slowed. The LC-MS/MS analysis of the oxidized mu-calpain revealed that the amino acid residues 105-133 contained a disulfide bond between Cys(108) and Cys(115). The finding that the active site cysteine in mu-calpain is able to form a disulfide bond has, to our knowledge, not been reported before. This could be part of a unique oxidation mechanism for mu-calpain. The results also showed that the formation of the disulfide bond is limited in the control (no oxidant added), and further limited in a concentration-dependent manner when beta-mercaptoethanol is added. However, the disulfide bond is still present to some extent in all conditions indicating that the active site cysteine is potentially highly susceptible to the formation of this intramolecular disulfide bond.

  2. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    International Nuclear Information System (INIS)

    Hoskins, J.T.; Zhou, Z.; Harding, P.A.

    2008-01-01

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser 108/121 , HB-EGF-Cys/Ser 116/132 , and HB-EGF-Cys/Ser 134/143 ) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with M r of 6.5, 21 and 24 kDa were observed from lysates of HB-EGF and each HB-EGF disulfide analogue. HB-EGF immunohistochemical analyses of each HB-EGF stable cell line demonstrated ubiquitous protein expression except HB-EGF-Cys/Ser 108/121 and HB-EGF-Cys/Ser 116/132 stable cell lines which exhibited accumulated expression immediately outside the nucleus. rHB-EGF, HB-EGF, and HB-EGF 134/143 proteins competed with 125 I-EGF in an A431 competitive binding assay, whereas HB-EGF-Cys/Ser 108/121 and HB-EGF-Cys/Ser 116/132 failed to compete. Each HB-EGF disulfide analogue lacked the ability to stimulate tyrosine phosphorylation of the 170 kDa EGFR. These results suggest that HB-EGF-Cys/Ser 134/143 antagonizes EGFRs

  3. Delicate balance of electrostatic interactions and disulfide bridges in thermostability of firefly luciferase.

    Science.gov (United States)

    Karimzadeh, Somayeh; Moradi, Maryam; Hosseinkhani, Saman

    2012-12-01

    The wild type Photinus pyralis luciferase does not have any disulfide bridge. Disulfide bridges are determinant in inherent stability of protein at moderate temperatures. Meanwhile, arginin is responsible for thermostability at higher temperatures. In this study, by concomitant introduction of disulfide bridge and a surface arginin in a mutant (A296C-A326C/I232R), the contribution of disulfide bridge introduction and surface hydrophilic residue on activity and global stability of P. pyralis luciferase is investigated. In addition to the mentioned mutant; I232R, A296C-A326C and wild type luciferases are characterized. Though addition of Arg caused stability against proteolysis but in combination with disulfide bridge resulted in decreased thermal stability compared to A296C-A326C mutant. In spite of long distance of two different mutations (A296C-A326C and I232R) from each other in the three-dimensional structure, combination of their effects on the stability of luciferase was not cumulative. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Immediate stabilization of human blood for delayed quantification of endogenous thiols and disulfides

    Science.gov (United States)

    Giustarini, Daniela; Galvagni, Federico; Orlandini, Maurizio; Fanti, Paolo; Rossi, Ranieri

    2016-01-01

    Endogenous thiols undergo rapid and reversible oxidation to disulfides when exposed to oxidants and are, therefore, suitable biomarkers of oxidative stress. However, accurate analysis of thiols in blood is frequently compromised by their artifactual oxidation during sample manipulation, which spuriously elevates the disulfide levels. Here, we describe a validated pre-analytical procedure that prevents both artifactual oxidation of thiols during sample manipulation and their oxidative decay for months in biosamples that are stored at −80°C. Addition of N-ethylmaleimide to blood samples from healthy donors was used to stabilize whole blood, red blood cells, platelets and plasma disulfides, whereas addition of citrate buffer followed by dilution of plasma with H2O was used to stabilize plasma thiols. The concentrations of thiols and disulfides were stable in all biosamples for at least 6 months when analyzed by UV/Vis HPLC at regular intervals. Only 3 ml of blood were needed to perform the analyses of thiols and disulfides in the different blood fractions. This pre-analytical procedure is reliable for use in both animal and human prospective studies. Its ease of implementation makes the method suitable for application to multicenter studies where blood samples are collected by different sites and personnel and are shipped to specific specialized laboratories. PMID:26896310

  5. 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.

  6. Polyethylenedioxythiophene and molybdenum disulfide nanocomposite electrodes for supercapacitor applications

    International Nuclear Information System (INIS)

    Alamro, Turki; Ram, Manoj K.

    2017-01-01

    Highlights: • MoS 2 -PEDOT nanocomposite electrode material was synthesized using polyanion ‘PSS’ and surfactant CTAB in an aqueous media. • The supercapacitor based on composite MoS 2 -PEDOT electrode revealed higher energy density than graphene composite electrodes. • The specific capacitance of 361 Farad/gram (F/g) was obtained for 1:2 weight ratio of MoS2 to the EDOT monomer in MoS 2 -PEDOT nanocomposite based electrodes. - Abstract: An innovative nanocomposite electrode was chemically synthesized using molybdenum disulphide (MoS 2 )- polyethylenedioxythiophene (PEDOT) to understand the charge mechanism in a symmetric supercapacitor. The MoS 2 -PEDOT nanocomposite was produced at various ratios of MoS 2 to ethylenedioxythiophene (EDOT) in an aqueous medium of polyanions polystyrene sulfonate (PSS) and cetyltrimethylammonium bromide (CTAB) at controlled conditions. The morphology, crystallinity, and optical properties of MoS 2 -PEDOT nanocomposite materials were characterized using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, particle size analyzer, Raman spectroscopy, X-ray-diffraction, and transmission electron microscopy (TEM) techniques, respectively. The electrochemical properties of the supercapacitor were investigated using cyclic voltammetry, charging–discharging at constant current and electrochemical impedance spectroscopy (EIS) techniques. The specific capacitance, power and energy densities of the supercapacitor were estimated using cyclic voltammetry (CV), charging–discharging, Nyquist and Bode plots. The specific capacitance was estimated to be 361 Farad/gram (F/g) for the 1:2 weight ratio of MoS 2 to the EDOT monomer in the MoS 2 -PEDOT nanocomposite based electrodes. Nevertheless, this study provides a fundamental aspect of synthesis of nanocomposite material for optimum attainment supercapacitive properties based on the MoS 2 -PEDOT nanocomposite electrode for practical energy storage

  7. 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.

  8. Cyclic versus Noncyclic Chelating Scaffold for 89Zr-Labeled ZEGFR:2377 Affibody Bioconjugates Targeting Epidermal Growth Factor Receptor Overexpression.

    Science.gov (United States)

    Summer, Dominik; Garousi, Javad; Oroujeni, Maryam; Mitran, Bogdan; Andersson, Ken G; Vorobyeva, Anzhelika; Löfblom, John; Orlova, Anna; Tolmachev, Vladimir; Decristoforo, Clemens

    2018-01-02

    Zirconium-89 is an emerging radionuclide for positron emission tomography (PET) especially for biomolecules with slow pharmacokinetics as due to its longer half-life, in comparison to fluorine-18 and gallium-68, imaging at late time points is feasible. Desferrioxamine B (DFO), a linear bifunctional chelator (BFC) is mostly used for this radionuclide so far but shows limitations regarding stability. Our group recently reported on fusarinine C (FSC) with similar zirconium-89 complexing properties but potentially higher stability related to its cyclic structure. This study was designed to compare FSC and DFO head-to-head as bifunctional chelators for 89 Zr-radiolabeled EGFR-targeting ZEGFR:2377 affibody bioconjugates. 2377 and DFO-ZEGFR:2377 were evaluated regarding radiolabeling, in vitro stability, specificity, cell uptake, receptor affinity, biodistribution, and microPET-CT imaging. Both conjugates were efficiently labeled with zirconium-89 at room temperature but radiochemical yields increased substantially at elevated temperature, 85 °C. Both 89 Zr-FSC-ZEGFR:2377 and 89 Zr-DFO-ZEGFR:2377 revealed remarkable specificity, affinity and slow cell-line dependent internalization. Radiolabeling at 85 °C showed comparable results in A431 tumor xenografted mice with minor differences regarding blood clearance, tumor and liver uptake. In comparison 89 Zr-DFO-ZEGFR:2377, radiolabeled at room temperature, showed a significant difference regarding tumor-to-organ ratios. MicroPET-CT imaging studies of 89 Zr-FSC-ZEGFR:2377 as well as 89 Zr-DFO-ZEGFR:2377 confirmed these findings. In summary we were able to show that FSC is a suitable alternative to DFO for radiolabeling of biomolecules with zirconium-89. Furthermore, our findings indicate that 89 Zr-radiolabeling of DFO conjugates at higher temperature reduces off-chelate binding leading to significantly improved tumor-to-organ ratios and therefore enhancing image contrast.

  9. 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.

  10. 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.

  11. Development of novel hybrid materials based on poly(2-aminophenyl disulfide)/silica gel: Preparation, characterization and electrochemical studies

    Science.gov (United States)

    Benyakhou, S.; Belmokhtar, A.; Zehhaf, A.; Benyoucef, A.

    2017-12-01

    Hydrochloric acid functionalized silica gel (SiO2) has been successfully used for the grafting of poly(2-Aminophenyl disulfide) (poly(2APhS)) moieties through in-situ polymerization in the presence of ammonium peroxodisulfate (APS) as oxidant. The organic-inorganic hybrid (poly(2APhS)/SiO2 with different amounts of SiO2: 0.5 g, 1.5 g and 2 g) were thoroughly characterized through powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and ultraviolet spectroscopy (UV) measurements. The results confirm the successful formation of the poly(2APhS)/SiO2 composite. The surface morphology of the samples was characterized by transmission electron microscopy (TEM). The obtained images show the formation of poly(2APhS) on surface of silica gel. Although the incorporation of SiO2 nanoparticles reduces the electric conductivity of the poly(2APhS), the resulting samples still keep high conductivities, ranging between 8.2 × 10-4 to 1.1 × 10-6 S cm-1. The electrochemical properties of the composite were characterized by the cyclic voltammetry. The comparison between the different samples shows that the electrochemical activity is significantly depending on the amount of added SiO2. There is a clear and good electroactivity for poly(2APhS)/SiO2 with amounts of SiO2: 0.5 g and 1.5 g, respectively, compared to that observed in materials nanocomposite with amounts of SiO2: 2.0 g. However, that effect may be explained by a decrease of polymer in surface area with increase amount of SiO2 nanoparticle.

  12. Structure-Based Design and Synthesis of Potent Cyclic Peptides Inhibiting the YAP-TEAD Protein-Protein Interaction.

    Science.gov (United States)

    Zhang, Zhisen; Lin, Zhaohu; Zhou, Zheng; Shen, Hong C; Yan, S Frank; Mayweg, Alexander V; Xu, Zhiheng; Qin, Ning; Wong, Jason C; Zhang, Zhenshan; Rong, Yiping; Fry, David C; Hu, Taishan

    2014-09-11

    The YAP-TEAD protein-protein interaction (PPI) mediates the oncogenic function of YAP, and inhibitors of this PPI have potential usage in treatment of YAP-involved cancers. Here we report the design and synthesis of potent cyclic peptide inhibitors of the YAP-TEAD interaction. A truncation study of YAP interface 3 peptide identified YAP(84-100) as a weak peptide inhibitor (IC50 = 37 μM), and an alanine scan revealed a beneficial mutation, D94A. Subsequent replacement of a native cation-π interaction with an optimized disulfide bridge for conformational constraint and synergistic effect between macrocyclization and modification at positions 91 and 93 greatly boosted inhibitory activity. Peptide 17 was identified with an IC50 of 25 nM, and the binding affinity (K d = 15 nM) of this 17mer peptide to TEAD1 proved to be stronger than YAP(50-171) (K d = 40 nM).

  13. 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.)

  14. 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)

  15. 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

  16. 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.

  17. 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)

  18. 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.

  19. pH-dependent sustained release characteristics of disulfide polymers prepared by simple thermal polymerization.

    Science.gov (United States)

    Park, Chul Ho; Lee, Jonghwi

    2013-01-01

    Biocompatible polymers have played an integral role in the advancement of drug delivery systems. The discovery of a novel polymer with innovative properties can provide great opportunities to enhance drug efficacy as well as reduce side effects. In this study, a novel disulfide polymer was synthesized and characterized. Its monomer is alpha-lipoic acid (ALA), which is synthesized in all cells in the human body. The disulfide polymer was obtained by the simple thermal polymerization of crystalline particles at a temperature higher than its melting point, followed by precipitation purification. It had rubbery and sticky characteristics. In vitro release tests demonstrated that the disulfide polymer had both pH-dependent degradation and related sustained release profiles, with a degraded form of ALA. Therefore, this novel class of responsive polymers that can be prepared by simple thermal polymerization has pronounced potential to contribute to future drug delivery systems.

  20. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... in the intrinsic fluorescence. Inter conversion between the two redox states could thus be followed in vitro as well as in vivoby non- invasive fluorimetric measurements. The 1.5 Angstrom crystal structure of the oxidized protein revealed a disulfide bond- induced distortion of the beta -barrel, as well...... as a structural reorganization of residues in the immediate chromophore environment. By combining this information with spectroscopic data, we propose a detailed mechanism accounting for the observed redox state-dependent fluorescence. The redox potential of the cysteine couple was found to be within...

  1. Shedding light on disulfide bond formation: engineering a redox switch in green fluorescent protein

    DEFF Research Database (Denmark)

    Østergaard, H.; Henriksen, A.; Hansen, Flemming G.

    2001-01-01

    To visualize the formation of disulfide bonds in living cells, a pair of redox-active cysteines was introduced into the yellow fluorescent variant of green fluorescent protein. Formation of a disulfide bond between the two cysteines was fully reversible and resulted in a >2-fold decrease...... the physiological range for redox-active cysteines. In the cytoplasm of Escherichia coli, the protein was a sensitive probe for the redox changes that occur upon disruption of the thioredoxin reductive pathway....... in the intrinsic fluorescence. Inter conversion between the two redox states could thus be followed in vitro as well as in vivoby non- invasive fluorimetric measurements. The 1.5 Angstrom crystal structure of the oxidized protein revealed a disulfide bond- induced distortion of the beta -barrel, as well...

  2. Allicin-inspired pyridyl disulfides as antimicrobial agents for multidrug-resistant Staphylococcus aureus.

    Science.gov (United States)

    Sheppard, Jordan G; McAleer, Jeremy P; Saralkar, Pushkar; Geldenhuys, Werner J; Long, Timothy E

    2018-01-01

    A chemical library comprised of nineteen synthesized pyridyl disulfides that emulate the chemical reactivity of allicin (garlic) was evaluated for antimicrobial activity against a panel of pathogenic bacteria. Gram-positive species including vancomycin-intermediate and vancomycin-resistant Staphylococcus aureus (VISA, VRSA) demonstrated the highest level of susceptibility toward analogs with S-alkyl chains of 7-9 carbons in length. Further biological studies revealed that the disulfides display synergy with vancomycin against VRSA, cause dispersal of S. aureus biofilms, exhibit low cytotoxicity, and decelerate S. aureus metabolism. In final analysis, pyridyl disulfides represent a novel class of mechanism-based antibacterial agents that have a potential application as antibiotic adjuvants in combination therapy of S. aureus infections with reduced vancomycin susceptibility. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  3. Multi-terminal memtransistors from polycrystalline monolayer molybdenum disulfide

    Science.gov (United States)

    Sangwan, Vinod K.; Lee, Hong-Sub; Bergeron, Hadallia; Balla, Itamar; Beck, Megan E.; Chen, Kan-Sheng; Hersam, Mark C.

    2018-02-01

    Memristors are two-terminal passive circuit elements that have been developed for use in non-volatile resistive random-access memory and may also be useful in neuromorphic computing. Memristors have higher endurance and faster read/write times than flash memory and can provide multi-bit data storage. However, although two-terminal memristors have demonstrated capacity for basic neural functions, synapses in the human brain outnumber neurons by more than a thousandfold, which implies that multi-terminal memristors are needed to perform complex functions such as heterosynaptic plasticity. Previous attempts to move beyond two-terminal memristors, such as the three-terminal Widrow-Hoff memristor and field-effect transistors with nanoionic gates or floating gates, did not achieve memristive switching in the transistor. Here we report the experimental realization of a multi-terminal hybrid memristor and transistor (that is, a memtransistor) using polycrystalline monolayer molybdenum disulfide (MoS2) in a scalable fabrication process. The two-dimensional MoS2 memtransistors show gate tunability in individual resistance states by four orders of magnitude, as well as large switching ratios, high cycling endurance and long-term retention of states. In addition to conventional neural learning behaviour of long-term potentiation/depression, six-terminal MoS2 memtransistors have gate-tunable heterosynaptic functionality, which is not achievable using two-terminal memristors. For example, the conductance between a pair of floating electrodes (pre- and post-synaptic neurons) is varied by a factor of about ten by applying voltage pulses to modulatory terminals. In situ scanning probe microscopy, cryogenic charge transport measurements and device modelling reveal that the bias-induced motion of MoS2 defects drives resistive switching by dynamically varying Schottky barrier heights. Overall, the seamless integration of a memristor and transistor into one multi-terminal device could

  4. On the relevance of sophisticated structural annotations for disulfide connectivity pattern prediction.

    Directory of Open Access Journals (Sweden)

    Julien Becker

    Full Text Available Disulfide bridges strongly constrain the native structure of many proteins and predicting their formation is therefore a key sub-problem of protein structure and function inference. Most recently proposed approaches for this prediction problem adopt the following pipeline: first they enrich the primary sequence with structural annotations, second they apply a binary classifier to each candidate pair of cysteines to predict disulfide bonding probabilities and finally, they use a maximum weight graph matching algorithm to derive the predicted disulfide connectivity pattern of a protein. In this paper, we adopt this three step pipeline and propose an extensive study of the relevance of various structural annotations and feature encodings. In particular, we consider five kinds of structural annotations, among which three are novel in the context of disulfide bridge prediction. So as to be usable by machine learning algorithms, these annotations must be encoded into features. For this purpose, we propose four different feature encodings based on local windows and on different kinds of histograms. The combination of structural annotations with these possible encodings leads to a large number of possible feature functions. In order to identify a minimal subset of relevant feature functions among those, we propose an efficient and interpretable feature function selection scheme, designed so as to avoid any form of overfitting. We apply this scheme on top of three supervised learning algorithms: k-nearest neighbors, support vector machines and extremely randomized trees. Our results indicate that the use of only the PSSM (position-specific scoring matrix together with the CSP (cysteine separation profile are sufficient to construct a high performance disulfide pattern predictor and that extremely randomized trees reach a disulfide pattern prediction accuracy of [Formula: see text] on the benchmark dataset SPX[Formula: see text], which corresponds to

  5. New analogs of the CART peptide with anorexigenic potency: the importance of individual disulfide bridges.

    Science.gov (United States)

    Blechová, Miroslava; Nagelová, Veronika; Záková, Lenka; Demianová, Zuzana; Zelezná, Blanka; Maletínská, Lenka

    2013-01-01

    The CART (cocaine- and amphetamine-regulated transcript) peptide is an anorexigenic neuropeptide that acts in the hypothalamus. The receptor and the mechanism of action of this peptide are still unknown. In our previous study, we showed that the CART peptide binds specifically to PC12 rat pheochromocytoma cells in both the native and differentiated into neuronal phenotype. Two biologically active forms, CART(55-102) and CART(61-102), with equal biological activity, contain three disulfide bridges. To clarify the importance of each of these disulfide bridges in maintaining the biological activity of CART(61-102), an Ala scan at particular S-S bridges forming cysteines was performed, and analogs with only one or two disulfide bridges were synthesized. In this study, a stabilized CART(61-102) analog with norleucine instead of methionine at position 67 was also prepared and was found to bind to PC12 cells with an anorexigenic potency similar to that of CART(61-102). The binding study revealed that out of all analogs tested, [Ala(68,86)]CART(61-102), which contains two disulfide bridges (positions 74-94 and 88-101), preserved a high affinity to both native PC12 cells and those that had been differentiated into neurons. In food intake and behavioral tests with mice after intracerebroventricular administration, this analog showed strong and long-lasting anorexigenic potency. Therefore, the disulfide bridge between cysteines 68 and 86 in CART(61-102) can be omitted without a loss of biological activity, but the preservation of two other disulfide bridges and the full-length peptide are essential for biological activity. Copyright © 2012 Elsevier Inc. All rights reserved.

  6. Enzymatic synthesis and characterizations of cyclic GDP-ribose. A procedure for distinguishing enzymes with ADP-ribosyl cyclase activity.

    Science.gov (United States)

    Graeff, R M; Walseth, T F; Fryxell, K; Branton, W D; Lee, H C

    1994-12-02

    Cyclic nucleotides such as cAMP and cGMP are second messengers subserving various signaling pathways. Cyclic ADP-ribose (cADPR), a recently discovered member of the family, is derived from NAD+ and is a mediator of Ca2+ mobilization in various cellular systems. The synthesis and degradation of cADPR are, respectively, catalyzed by ADP-ribosyl cyclase and cADPR hydrolase. CD38, a differentiation antigen of B lymphocytes, has recently been shown to be a bifunctional enzyme catalyzing both the formation and hydrolysis of cADPR. The overall reaction catalyzed by CD38 is the formation of ADP-ribose and nicotinamide from NAD+, identical to that catalyzed by NADase. The difficulties in detecting the formation of cADPR have led to frequent identification of CD38 as a classical NADase. In this study, we show that both ADP-ribosyl cyclase and CD38, but not NADase, can cyclize nicotinamide guanine dinucleotide (NGD+) producing a new nucleotide. Analyses by high performance liquid chromatography and mass spectroscopy indicate the product is cyclic GDP-ribose (cGDPR) with a structure similar to cADPR except with guanine replacing adenine. Compared to cADPR, cGDPR is a more stable compound showing 2.8 times more resistance to heat-induced hydrolysis. These results are consistent with a catalytic scheme for CD38 where the cyclization of the substrate precedes the hydrolytic reaction. Spectroscopic analyses show that cGDPR is fluorescent and has an absorption spectrum different from both NGD+ and GDPR, providing a very convenient way for monitoring its enzymatic formation. The use of NGD+ as substrate for assaying the cyclization reaction was found to be applicable to pure enzymes as well as crude tissue extracts making it a useful diagnostic tool for distinguishing CD38-like enzymes from degradative NADases.

  7. On the equivalence of cyclic and quasi-cyclic codes over finite fields

    Directory of Open Access Journals (Sweden)

    Kenza Guenda

    2017-07-01

    Full Text Available This paper studies the equivalence problem for cyclic codes of length $p^r$ and quasi-cyclic codes of length $p^rl$. In particular, we generalize the results of Huffman, Job, and Pless (J. Combin. Theory. A, 62, 183--215, 1993, who considered the special case $p^2$. This is achieved by explicitly giving the permutations by which two cyclic codes of prime power length are equivalent. This allows us to obtain an algorithm which solves the problem of equivalency for cyclic codes of length $p^r$ in polynomial time. Further, we characterize the set by which two quasi-cyclic codes of length $p^rl$ can be equivalent, and prove that the affine group is one of its subsets.

  8. Chain dimension of cyclic polymers in solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ohta, Yutaka [Department of Applied Chemistry, Nagoya University Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Masuoka, Keisuke [Department of Applied Chemistry, Nagoya University Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Takano, Atsushi [Department of Applied Chemistry, Nagoya University Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Matsushita, Yushu [Department of Applied Chemistry, Nagoya University Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)]. E-mail: yushu@apchem.nagoya-u.ac.jp

    2006-11-15

    Telechelic polystyrenes (PSs) were synthesized and cyclized by end-to-end ring closure reaction under extremely diluted condition. Cyclic PSs were isolated from coupling products by GPC fractionation and precipitational fractionation, and 4 cyclic polymers, whose molecular weights M{sub w} are covering the range 20k=cyclic polymers have high purity (over 95%) by HPLC. Their radii of gyration R{sub g} were determined in benzene-d{sub 6} (good solvent) and cyclohexane-d{sub 12} (theta solvent) by small-angle neutron scattering and light scattering. It was found that R{sub g} of cyclic polymer can be scaled with M{sub w} as R{sub g}{proportional_to}M{sub w}{sup 0.6} in benzene-d{sub 6} and as R{sub g}{proportional_to}M{sub w}{sup 0.5} in cyclohexane-d{sub 12}, both exponents being the same as for linear counterparts. However, experimentally determined contraction ratio, R{sub g(cyclic)}/R{sub g(linear)}, is smaller than the theoretical predictions.

  9. Further studies on cyclic erythropoiesis in mice

    International Nuclear Information System (INIS)

    Gibson, C.M.; Gurney, C.W.; Simmons, E.L.; Gaston, E.O.

    1985-01-01

    When young adult female W/Wv mice are given 0.5 micro+Ci 89 Sr/g body weight intravenously, their hematocrit values oscillate from nadirs of 26% to zeniths of 42% with a periodicity of 16 days. The response of the W/Wv mouse to an assortment of radioactive and hematologic stresses have been examined in an effort to understand better the pathophysiology of cyclic erythropoiesis. When the dose of 89 Sr is increased, the amplitude of cycling increases as nadirs are lowered, but periodicity is unchanged. When the dose of 89 Sr is lowered to 0.3 microCi or less, cyclic erythropoiesis of substantial amplitude is observed only after five or six microoscillations. A single hematopoietic insult of 80 rad x-irradiation coupled with phlebotomy produces a transient form of cyclic erythropoiesis, namely, a series of dampened oscillations prior to recovery. Finally, we report that Wv/Wv mice exhibit a form of cyclic erythropoiesis in response to 0.5 microCi 89 Sr/g body weight, in which the hematocrit values of successive nadirs gradually increase, and stabilize at about 100 days. 89 Sr does not induce cyclic erythropoiesis in the +/+, W/+, or W/v/+ mice, the Hertwig strain of anemic mice, or in normal BDF1 mice

  10. Identification of Reduction-Susceptible Disulfide Bonds in Transferrin by Differential Alkylation Using O16/O18 Labeled Iodoacetic Acid

    Science.gov (United States)

    Wang, Shunhai; Kaltashov, Igor A.

    2015-05-01

    Stabilization of native three-dimensional structure has been considered for decades to be the main function of disulfide bonds in proteins. More recently, it was becoming increasingly clear that in addition to this static role, disulfide bonds are also important for many other aspects of protein behavior, such as regulating protein function in a redox-sensitive fashion. Dynamic disulfide bonds can be taken advantage of as candidate anchor sites for site-specific modification (such as PEGylation of conjugation to a drug molecule), but are also frequently implicated in protein aggregation (through disulfide bond scrambling leading to formation of intermolecular covalent linkages). A common feature of all these labile disulfide bonds is their high susceptibility to reduction, as they need to be selectively regulated by either specific local redox conditions in vivo or well-controlled experimental conditions in vitro. The ability to identify labile disulfide bonds in a cysteine-rich protein can be extremely beneficial for a variety of tasks ranging from understanding the mechanistic aspects of protein function to identification of troublesome "hot spots" in biopharmaceutical products. Herein, we describe a mass spectrometry (MS)-based method for reliable identification of labile disulfide bonds, which consists of limited reduction, differential alkylation with an O18-labeled reagent, and LC-MS/MS analysis. Application of this method to a cysteine-rich protein transferrin allows the majority of its native disulfide bonds to be measured for their reduction susceptibility, which appears to reflect both solvent accessibility and bond strain energy.

  11. Rapid expansion of the protein disulfide isomerase gene family facilitates the folding of venom peptides

    DEFF Research Database (Denmark)

    Safavi-Hemami, Helena; Li, Qing; Jackson, Ronneshia L.

    2016-01-01

    Formation of correct disulfide bonds in the endoplasmic reticulum is a crucial step for folding proteins destined for secretion. Protein disulfide isomerases (PDIs) play a central role in this process. We report a previously unidentified, hypervariable family of PDIs that represents the most...... diverse gene family of oxidoreductases described in a single genus to date. These enzymes are highly expressed specifically in the venom glands of predatory cone snails, animals that synthesize a remarkably diverse set of cysteine-rich peptide toxins (conotoxins). Enzymes in this PDI family, termed...

  12. Minor element distribution in iron disulfides in coal: a geochemical review

    Science.gov (United States)

    Kolker, Allan

    2012-01-01

    Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe3S4), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to

  13. Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Salbo, Rune; Ploug, Michael

    2014-01-01

    requires a high concentration (>200 mM) of the chemical reducing agent Tris(2-carboxyethyl)phosphine (TCEP) as the reduction rate constant is decreased at low pH and temperature. Serious adverse effects on chromatographic and mass spectrometric performances have been reported when using high concentrations......Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0°C). The reduction typically...

  14. 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.

  15. The nature of solar cyclicity. I

    Science.gov (United States)

    Romanchuk, P. R.

    1981-02-01

    The report contains a critical survey of work devoted to the study of the nature of solar cyclicity. The inconsistency of the representation of cyclic curves using a frequency spectrum is indicated. The useful contribution of the ideas of Wolf, Newcomb, and Waldmeier to the solution of the problem is noted. Data are cited in favor of the theory of the tidal nature of solar cyclicity developed by the author, which also takes into account the ideas of the above-mentioned authors: the continuous paired and single tidal actions of the planets and the resonance character of this action, thanks to which the approximately 10-year period of action of Jupiter and Saturn is transformed into the 11-year activity cycle.

  16. HOST liner cyclic facilities: Facility description

    Science.gov (United States)

    Schultz, D.

    1982-01-01

    A quartz lamp box, a quartz lamp annular rig, and a low pressure liner cyclic can rig planned for liner cyclic tests are described. Special test instrumentation includes an IR-TV camera system for measuring liner cold side temperatures, thin film thermocouples for measuring liner hot side temperatures, and laser and high temperature strain gages for obtaining local strain measurements. A plate temperature of 2,000 F was obtained in an initial test of an apparatus with three quartz lamps. Lamp life, however, appeared to be limited for the standard commercial quartz lamps available. The design of vitiated and nonvitiated preheaters required for the quartz lamp annular rig and the cyclic can test rigs is underway.

  17. Cyclic distillation technology - A mini-review

    DEFF Research Database (Denmark)

    Bîldea, Costin Sorin; Pătruţ, Cătălin; Jørgensen, Sten Bay

    2016-01-01

    Process intensification in distillation systems has received much attention during the pastdecades, with the aim of increasing both energy and separation efficiency. Varioustechniques, such as internal heat-integrated distillation, membrane distillation, rotating packedbed, dividing-wall columns...... and reactive distillation were studied and reported in literature. All these techniques employ the conventional continuous counter-current contact of vapor andliquid phases. Cyclic distillation technology is based on an alternative operating mode usingseparate phase movement which leads to key practical...... advantages in both chemical andbiochemical processes. This article provides a mini-review of cyclic distillation technology.The topics covered include the working principle, design and control methods, main benefitsand limitations as well as current industrial applications. Cyclic distillation can...

  18. Cyclic cellular automata in 3D

    International Nuclear Information System (INIS)

    Reiter, Clifford A.

    2011-01-01

    Highlights: → We explore the self-organization of cyclic cellular automata in 3D. → Von Neumann, Moore and two types of intermediate neighborhoods are investigated. → Random neighborhoods self organize through phases into complex nested structures. → Demons are seen to have many alternatives in 3D. - Abstract: Cyclic cellular automata in two dimensions have long been intriguing because they self organize into spirals and that behavior can be analyzed. The form for the patterns that develop is highly dependent upon the form of the neighborhood. We extend this work to three dimensional cyclic cellular automata and observe self organization dependent upon the neighborhood type. This includes neighborhood types intermediate between Von Neumann and Moore neighborhoods. We also observe that the patterns include nested shells with the appropriate forms but that the nesting is far more complex than the spirals that occur in two dimensions.

  19. Role of disulfide linkage in action of bis(dialkylaminethiocarbonyl)disulfides as potent double-Edged microbicidal spermicide: Design, synthesis and biology.

    Science.gov (United States)

    Lal, Nand; Jangir, Santosh; Bala, Veenu; Mandalapu, Dhanaraju; Sarswat, Amit; Kumar, Lalit; Jain, Ashish; Kumar, Lokesh; Kushwaha, Bhavana; Pandey, Atindra K; Krishna, Shagun; Rawat, Tara; Shukla, Praveen K; Maikhuri, Jagdamba P; Siddiqi, Mohammad I; Gupta, Gopal; Sharma, Vishnu L

    2016-06-10

    Trichomoniasis and candidiasis are amongst the most common morbidity-causing reproductive tract infections, generally treated by Metronidazole and Fluconazole respectively. Poor vaginal efficacy, drug-resistance and non-spermicidal nature limit their use as topical microbicidal contraceptives. Bis(dialkylaminethiocarbonyl)disulfides (4-38) were designed as dually active, non-surfactant molecules capable of eliminating Trichomonas vaginalis and Candida strains as well as irreversibly immobilizing 100% human sperm instantly, at doses non-cytotoxic to human cervical epithelial cells and vaginal microflora in vitro. Compounds 12, 16, 17 were fifty times more active than nonoxynol-9, OTC vaginal spermicide, and compounds 12 and 17 have shown remarkable in vivo activity in rabbit model. Most promising compound 17 has shown promise for further development as a double-edged vaginal microbicide due to their improved activity and safety along with notable in vivo trichomonicidal activity. Role of disulfide group was established by loss of spermicidal activity on chemical modifications (39-56). These disulfides might be targeting thiol groups present over cell membrane of human sperm and Trichomonas as shown by fluorescence labeling of free thiols. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  20. Cyclic microplasticity factors of some metals

    Energy Technology Data Exchange (ETDEWEB)

    Puskar, A. (University of Transport and Telecommunications, Zilina (Czechoslovakia))

    1983-11-01

    The measurement of the internal friction and the elasticity modulus defect together with a new approximation for evaluating the plastic deformation amplitude from the total deformation amplitude enable the cyclic deformation curves, the changes in hysteresis loop area on increasing the deformation amplitude and many other important characteristics of cyclic microplasticity to be determined during a push-pull type of loading at a frequency of 23kHz on dumb-bell shaped specimens of titanium, molybdenum, niobium and low carbon unalloyed steel.

  1. SICLOPPS cyclic peptide libraries in drug discovery.

    Science.gov (United States)

    Tavassoli, Ali

    2017-06-01

    Cyclic peptide libraries have demonstrated significant potential when employed against challenging targets such as protein-protein interactions. While a variety of methods for library generation exist, genetically encoded libraries hold several advantages over their chemically synthesized counterparts; they are more readily accessible and allow straightforward hit deconvolution. One method for the intracellular generation of such libraries is split-intein circular ligation of peptides and proteins (SICLOPPS). Here we detail and discuss the deployment of SICLOPPS libraries for the identification of cyclic peptide inhibitors of a variety of targets. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Towards Optimization of Cyclic Production Systems

    OpenAIRE

    Chauvet, Fabrice; Herrmann, Jeffrey W.; Proth, Jean-Marie

    1999-01-01

    In this paper, the expression "production systems" refers to flow-shops, job-shops, assembly systems, Kanban systems and, in general, to any Discrete Event System (DES) which transforms raw material and/or components into products and/or components. Such a system is said to be cyclic if it provides indefinitely the same sequence of products. A schedule of a cyclic production system is defined as soon as the starting time of each operation on the related resource is known. It has been showed t...

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. Opportunities and challenges in the electrocatalysis of CO2 and CO reduction using bifunctional surfaces

    DEFF Research Database (Denmark)

    Jovanov, Zarko; Hansen, Heine A.; Varela Gasque, Ana Sofia

    2016-01-01

    "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...

  17. 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

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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.

  4. Selective removal of heavy metal ions by disulfide linked polymer networks

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Dongah [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark); Lee, Joo Sung [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Patel, Hasmukh A. [Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States); Jakobsen, Mogens H. [Department of Micro and Nano technology, Technical University of Denmark, Ørsteds Plads, 345B, 2800 Kgs. Lyngby (Denmark); Hwang, Yuhoon [Department of Environmental Engineering, Seoul National University of Science and Technology, 232 Gongreung-ro, Nowon-gu, Seoul 01811 (Korea, Republic of); Yavuz, Cafer T. [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Hansen, Hans Chr. Bruun [Department of Plant and Environmental Sciences, University of Copenhagen, Frederiksberg, Thorvaldsensvej 40, 1871 Frederiksberg C (Denmark); Andersen, Henrik R., E-mail: henrik@ndersen.net [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark)

    2017-06-15

    Highlights: • Disulfide/thiol polymer networks are promising as sorbent for heavy metals. • Rapid sorption and high Langmuir affinity constant (a{sub L}) for stormwater treatment. • Selective sorption for copper, cadmium, and zinc in the presence of calcium. • Reusability likely due to structure stability of disulfide linked polymer networks. - Abstract: Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions–copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

  5. Per-2,3-O-alkylated beta-cyclodextrin duplexes connected with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Tatar, Ameneh; Grishina, Anastasia; Buděšínský, Miloš; Kraus, Tomáš

    2017-01-01

    Roč. 29, č. 1 (2017), s. 40-48 ISSN 1061-0278 R&D Projects: GA MŠk LD12019 Grant - others:COST(XE) CM1005 Institutional support: RVO:61388963 Keywords : cyclodextrins * inclusion complexes * disulfide bonds Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 1.264, year: 2016

  6. Disulfide-bridging PEGylation during refolding for the more efficient production of modified proteins.

    Science.gov (United States)

    Ginn, Claire; Choi, Ji-Won; Brocchini, Steve

    2016-08-01

    Proteins that are modified by chemical conjugation require at least two separate purification processes. First the bulk protein is purified, and then after chemical conjugation, a second purification process is required to obtain the modified protein. In an effort to develop new enabling technologies to integrate bioprocessing and protein modification, we describe the use of disulfide-bridging conjugation to conduct PEGylation during protein refolding. Preliminary experiments using a PEG-mono-sulfone reagent with partially unfolded leptin and unfolded RNAse T1 indicated that the cysteine thiols underwent disulfide-bridging conjugation to give the PEGylated proteins. Interferon-β1b (IFN-β1b) was then expressed in E.coli as inclusion bodies and found to undergo disulfide bridging-conjugation during refolding. The PEG-IFN-β1b was isolated by ion-exchange chromatography and displayed in vitro biological activity. In the absence of the PEGylation reagent, IFN-β1b refolding was less efficient and yielded protein aggregates. No PEGylation was observed if the cysteines on IFN-β1b were first modified with iodoacetamide prior to refolding. Our results demonstrate that the simultaneous refolding and disulfide bridging PEGylation of proteins could be a useful strategy in the development of affordable modified protein therapeutics. Copyright © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Structural basis for target protein recognition by the protein disulfide reductase thioredoxin

    DEFF Research Database (Denmark)

    Maeda, Kenji; Hägglund, Per; Finnie, Christine

    2006-01-01

    Thioredoxin is ubiquitous and regulates various target proteins through disulfide bond reduction. We report the structure of thioredoxin (HvTrxh2 from barley) in a reaction intermediate complex with a protein substrate, barley alpha-amylase/subtilisin inhibitor (BASI). The crystal structure...

  8. Sulfur-Switch Ugi Reaction for Macrocyclic Disulfide-Bridged Peptidomimetics

    NARCIS (Netherlands)

    Vishwanatha, Thimmalapura M; Bergamaschi, Enrico; Dömling, Alexander

    2017-01-01

    A general strategy is introduced for the efficient synthetic access of disulfide linked artificial macrocycles via a Ugi four-component reaction (U4CR) followed by oxidative cyclization. The double-mercapto input is proposed for use in the Ugi reaction, thereby yielding all six topologically

  9. Impact of SCILL catalysts for the S-S coupling of thiols to disulfides.

    Science.gov (United States)

    Pavel, Octavian D; Podolean, Iunia; Parvulescu, Vasile I; Taylor, S F Rebecca; Manyar, Haresh G; Ralphs, Kathryn; Goodrich, Peter; Hardacre, Christopher

    2018-01-01

    This study reports the behaviour of SCILL based catalysts in the oxidative S-S coupling of aliphatic and aromatic thiols, namely 1-butanethiol and thiophenol, to dibutyl disulfide and diphenyl disulfide. A range of ionic liquids (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide) and metal supported catalysts (5% Pt/SiO 2 ; 5% Ru/SiO 2 ; 5% Ru/C; 5% Pt/OMS-2) were used to prepare the SCILL catalysts and all were found to be active for the reaction following the trend 5% Pt-OMS-2 > 5% Pt/SiO 2 > 5% Ru/C > 5% Ru/SiO 2 . The presence of SCILL catalysts afforded high selectivity to the disulfide, and the activity of the SCILL catalyst was dependent on the ionic liquid used. A significant increase in the stability of all the supported metal catalysts was found in the presence of the ionic liquid, and there was no change in the selectivity towards disulfides. This demonstrated that the ionic liquids protect the active sites of the catalyst against sulfation, thus providing more stable and active catalysts.

  10. Increasing the reactivity of an artificial dithiol-disulfide pair through modification of the electrostatic milieu

    DEFF Research Database (Denmark)

    Hansen, Rosa E; Østergaard, Henrik; Winther, Jakob R

    2005-01-01

    . Introduction of positively charged amino acids in the proximity of the two cysteines resulted in an up to 13-fold increase in reactivity toward glutathione disulfide. Determination of the individual pK(a) values of the cysteines showed that the observed increase in reactivity was caused by a decrease in the pK(a...

  11. Decontamination of Oils Contaminated with Polychlorinated Biphenyls and Dibenzyl Disulfide Using Polar Aprotic Solvents

    Czech Academy of Sciences Publication Activity Database

    Kaštánek, František; Matějková, Martina; Spáčilová, Lucie; Maléterová, Ywetta; Kaštánek, P.; Šolcová, Olga

    2015-01-01

    Roč. 4, č. 2 (2015), s. 41-48 ISSN 2319-5967 R&D Projects: GA TA ČR(CZ) TA04020151 Institutional support: RVO:67985858 Keywords : corrosive sulfur * dibenzyl disulfide * polar aprotic solvents Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www.ijesit.com/Volume%204/Issue%202/IJESIT201502_06.pdf

  12. Identification of Thioredoxin Target Disulfides Using Isotope-Coded Affinity Tags

    DEFF Research Database (Denmark)

    Hägglund, Per; Bunkenborg, Jakob; Maeda, Kenji

    2014-01-01

    extracts is described. The procedure utilizes the isotope-coded affinity tag (ICAT) reagents containing a thiol reactive iodoacetamide group and a biotin affinity tag to target peptides containing reduced cysteine residues. The identification of substrates for Trx and the extent of target disulfide...

  13. Inactivation of barley limit dextrinase inhibitor by thioredoxin-catalysed disulfide reduction

    DEFF Research Database (Denmark)

    Jensen, Johanne Mørch; Hägglund, Per; Christensen, Hans Erik Mølager

    2012-01-01

    Barley limit dextrinase (LD) that catalyses hydrolysis of α-1,6 glucosidic linkages in starch-derived dextrins is inhibited by limit dextrinase inhibitor (LDI) found in mature seeds. LDI belongs to the chloroform/methanol soluble protein family (CM-protein family) and has four disulfide bridges...

  14. Production of asymmetric disulfides based metiltiol - example of nano-structure of elemental sulfur

    Directory of Open Access Journals (Sweden)

    К. Dyusengaliev

    2012-09-01

    Full Text Available The methods of obtaining of asymmetric organic disulfides on the basis of metylthiol and nanostructures of element sulfur are discussed. The way of preparation of metyletyldisulfide with the release of 99 % was protected by the innovative patent of RK.

  15. Functional Groups and Sulfur K-Edge XANES Spectra : Divalent Sulfur and Disulfides

    NARCIS (Netherlands)

    Mijovilovich, A.E.; Pettersson, Lars G. M.; de Groot, Frank M. F.; Weckhuysen, Bert M.

    2010-01-01

    Sulfur K-edge XANES was measured for two divalent sulfurs (dibenzyl and benzyl phenyl) and two disulfides (dibenzyl and diphenyl). The absorption spectra could be assigned using density functional theory with the "half core hole" approximation for the core hole including relaxation of selected

  16. Accurate disulfide-bonding network predictions improve ab initio structure prediction of cysteine-rich proteins.

    Science.gov (United States)

    Yang, Jing; He, Bao-Ji; Jang, Richard; Zhang, Yang; Shen, Hong-Bin

    2015-12-01

    Cysteine-rich proteins cover many important families in nature but there are currently no methods specifically designed for modeling the structure of these proteins. The accuracy of disulfide connectivity pattern prediction, particularly for the proteins of higher-order connections, e.g., >3 bonds, is too low to effectively assist structure assembly simulations. We propose a new hierarchical order reduction protocol called Cyscon for disulfide-bonding prediction. The most confident disulfide bonds are first identified and bonding prediction is then focused on the remaining cysteine residues based on SVR training. Compared with purely machine learning-based approaches, Cyscon improved the average accuracy of connectivity pattern prediction by 21.9%. For proteins with more than 5 disulfide bonds, Cyscon improved the accuracy by 585% on the benchmark set of PDBCYS. When applied to 158 non-redundant cysteine-rich proteins, Cyscon predictions helped increase (or decrease) the TM-score (or RMSD) of the ab initio QUARK modeling by 12.1% (or 14.4%). This result demonstrates a new avenue to improve the ab initio structure modeling for cysteine-rich proteins. http://www.csbio.sjtu.edu.cn/bioinf/Cyscon/ zhng@umich.edu or hbshen@sjtu.edu.cn. Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  17. Protein disulfide isomerase of Toxoplasma gondii is targeted by mucosal IgA antibodies in humans

    NARCIS (Netherlands)

    Meek, Bob; Back, Jaap Willem; Klaren, Vincent N. A.; Speijer, Dave; Peek, Ron

    2002-01-01

    Mass spectrometric analysis identified a 49 kDa antigen from Toxoplasma gondii as protein disulfide isomerase (PDI). This antigen is generally recognized by IgA in tears of healthy humans. We determined the complete open reading frame and expressed PDI recombinantly. Recombinant PDI was recognized

  18. Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide

    NARCIS (Netherlands)

    Verkruijsse, H.D.; Brandsma, L.

    1987-01-01

    Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide. Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in high yields. Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained

  19. Breaking antidunes: Cyclic behavior due to hysteresis

    DEFF Research Database (Denmark)

    Deigaard, Rolf

    2006-01-01

    The cyclic behavior of breaking antidunes (growth, breaking of surface wave, obliteration) is investigated by use of a numerical model. The model includes the transition between supercritical and transcritical flow. As the antidune grows the flow becomes transcritical and a hydraulic jump is form...

  20. Cyclic Plastic Deformation and Welding Simulation

    NARCIS (Netherlands)

    Ten Horn, C.H.L.J.

    2003-01-01

    One of the concerns of a fitness for purpose analysis is the quantification of the relevant material properties. It is known from experiments that the mechanical properties of a material can change due to a monotonic plastic deformation or a cyclic plastic deformation. For a fitness for purpose

  1. Cyclical Variability of Prominences, CMEs and Flares

    Indian Academy of Sciences (India)

    tribpo

    tions of solar activity. For many years, qualitative studies were made about the cyclical behaviour of such phenomena. Nowadays, more quantitative ... phenomenon has been observed in every cycle and is independent of the intensity of the cycle. The characteristic pattern of the polar zone is a "rush to the poles" and the.

  2. Cyclical Variability of Prominences, CMEs and Flares

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Journal of Astrophysics and Astronomy; Volume 21; Issue 3-4. Cyclical Variability of Prominences, CMEs and Flares. J. L. Ballester. Session V – Vector Magnetic Fields, Prominences, CMEs & Flares Volume 21 Issue 3-4 September-December 2000 pp ...

  3. Steady state oxygen reduction and cyclic voltammetry

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Karlberg, Gustav; Jaramillo, Thomas

    2008-01-01

    The catalytic activity of Pt and Pt3Ni for the oxygen reduction reaction is investigated by applying a Sabatier model based on density functional calculations. We investigate the role of adsorbed OH on the activity, by comparing cyclic voltammetry obtained from theory with previously published...

  4. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    Science.gov (United States)

    Wilkinson, Bruce H.

    1982-01-01

    Discusses causes of cyclicity in cratonic carbonate sequences and evidence for and potential significance of postulated primary calcite sediment components in past Paleozoic seas, outlining problems, focusing on models explaining existing data, and identifying background. Future sedimentary geologists will need to address these and related areas…

  5. Cyclic olefin copolymer-silica nanocomposites foams

    Czech Academy of Sciences Publication Activity Database

    Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

    2016-01-01

    Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

  6. Dissecting the role of disulfide bonds on the amyloid formation of insulin

    International Nuclear Information System (INIS)

    Li, Yang; Gong, Hao; Sun, Yue; Yan, Juan; Cheng, Biao; Zhang, Xin; Huang, Jing; Yu, Mengying; Guo, Yu; Zheng, Ling; Huang, Kun

    2012-01-01

    Highlights: ► We dissect how individual disulfide bond affects the amyloidogenicity of insulin. ► A controlled reduction system for insulin is established in this study. ► Disulfide breakage is associated with unfolding and increased amyloidogenicity. ► Breakage of A6-A11 is associated with significantly increased cytotoxicity. ► Analogs without A6-A11 have a higher potency to form high order toxic oligomers. -- Abstract: Disulfide bonds play a critical role in the stability and folding of proteins. Here, we used insulin as a model system, to investigate the role of its individual disulfide bond during the amyloid formation of insulin. Tris(2-carboxyethyl)phosphine (TCEP) was applied to reduce two of the three disulfide bonds in porcine insulin and the reduced disulfide bonds were then alkylated by iodoacetamide. Three disulfide bond-modified insulin analogs, INS-2 (lack of A6-A11), INS-3 (lack of A7-B7) and INS-6 (lack of both A6-A11 and A7-B7), were obtained. Far-UV circular dichroism (CD) spectroscopy results indicated that the secondary structure of INS-2 was the closest to insulin under neutral conditions, followed by INS-3 and INS-6, whereas in an acidic solution all analogs were essentially unfolded. To test how these modifications affect the amyloidogenicity of insulin, thioflavin-T (ThT) fluorescence and transmission electronic microscopy (TEM) were performed. Our results showed that all analogs were more prone to aggregation than insulin, with the order of aggregation rates being INS-6 > INS-3 > INS-2. Cross-linking of unmodified proteins (PICUP) assay results showed that analogs without A6-A11 (INS-2 and INS-6) have a higher potential for oligomerization than insulin and INS-3, which is accompanied with a higher cytotoxicity as the hemolytic assays of human erythrocytes suggested. The results indicated that breakage of A7-B7 induced more unfolding of the insulin structure and a higher amyloidogenicity than breakage of A6-A11, but breakage of A6

  7. Stabilisation of the Fc fragment of human IgG1 by engineered intradomain disulfide bonds.

    Directory of Open Access Journals (Sweden)

    Gordana Wozniak-Knopp

    Full Text Available We report the stabilization of the human IgG1 Fc fragment by engineered intradomain disulfide bonds. One of these bonds, which connects the N-terminus of the CH3 domain with the F-strand, led to an increase of the melting temperature of this domain by 10°C as compared to the CH3 domain in the context of the wild-type Fc region. Another engineered disulfide bond, which connects the BC loop of the CH3 domain with the D-strand, resulted in an increase of T(m of 5°C. Combined in one molecule, both intradomain disulfide bonds led to an increase of the T(m of about 15°C. All of these mutations had no impact on the thermal stability of the CH2 domain. Importantly, the binding of neonatal Fc receptor was also not influenced by the mutations. Overall, the stabilized CH3 domains described in this report provide an excellent basic scaffold for the engineering of Fc fragments for antigen-binding or other desired additional or improved properties. Additionally, we have introduced the intradomain disulfide bonds into an IgG Fc fragment engineered in C-terminal loops of the CH3 domain for binding to Her2/neu, and observed an increase of the T(m of the CH3 domain for 7.5°C for CysP4, 15.5°C for CysP2 and 19°C for the CysP2 and CysP4 disulfide bonds combined in one molecule.

  8. Identification of a disulfide bridge important for transport function of SNAT4 neutral amino acid transporter.

    Directory of Open Access Journals (Sweden)

    Rugmani Padmanabhan Iyer

    Full Text Available SNAT4 is a member of system N/A amino acid transport family that primarily expresses in liver and muscles and mediates the transport of L-alanine. However, little is known about the structure and function of the SNAT family of transporters. In this study, we showed a dose-dependent inhibition in transporter activity of SNAT4 with the treatment of reducing agents, dithiothreitol (DTT and Tris(2-carboxyethylphosphine (TCEP, indicating the possible involvement of disulfide bridge(s. Mutation of residue Cys-232, and the two highly conserved residues Cys-249 and Cys-321, compromised the transport function of SNAT4. However, this reduction was not caused by the decrease of SNAT4 on the cell surface since the cysteine-null mutant generated by replacing all five cysteines with alanine was equally capable of being expressed on the cell surface as wild-type SNAT4. Interestingly, by retaining two cysteine residues, 249 and 321, a significant level of L-alanine uptake was restored, indicating the possible formation of disulfide bond between these two conserved residues. Biotinylation crosslinking of free thiol groups with MTSEA-biotin provided direct evidence for the existence of a disulfide bridge between Cys-249 and Cys-321. Moreover, in the presence of DTT or TCEP, transport activity of the mutant retaining Cys-249 and Cys-321 was reduced in a dose-dependent manner and this reduction is gradually recovered with increased concentration of H2O2. Disruption of the disulfide bridge also decreased the transport of L-arginine, but to a lesser degree than that of L-alanine. Together, these results suggest that cysteine residues 249 and 321 form a disulfide bridge, which plays an important role in substrate transport but has no effect on trafficking of SNAT4 to the cell surface.

  9. Interaction of tachykinins with their receptors studied with cyclic analogues of substance P and neurokinin B

    Energy Technology Data Exchange (ETDEWEB)

    Ploux, O.; Lavielle, S.; Chassaing, G.; Julien, S.; Marquet, A.; D' Orleans-Juste, P.; Dion, S.; Regoli, D.; Beaujouan, J.C.; Bergstroem, L.

    1987-11-01

    The activities of two groups of cyclic agonists of substance P (SP) have been studied. The disulfide bridge constraints have been designed on the basis of conformational studies on SP and physalaemin indicating an ..cap alpha..-helical structure for the core of these two tachykinins (group I) and a folding of the C-terminal carboxamide towards the side chains of the glutamines 5 and 6 (group II). Only peptides simulating the ..cap alpha..-helix present substantial potencies. (Cys/sup 3,6/)SP is as active as SP in inhibiting /sup 125/I-labeled Bolton and Hunter SP-specific binding on rat brain synaptosomes and on dog carotid bioassay, two assays specific for the neurokinin 1 receptor. Moreover, (Cys/sup 3,6/)SP is a potent as neurokinin B in inhibiting /sup 125/I-labeled Bolton and Hunter eledoisin-specific binding on rat cortical synaptosomes as well as in stimulating rat portal vein, two tests specific for the neurokinin 3 receptor. Interestingly, in contrast to neurokinin B, (Cys/sup 3,6/)SP is a weak agonist of the neurokinin 2 receptor subtype, as evidenced by its binding potency in inhibiting /sup 3/H-labeled neurokinin A-specific binding on rat duodenum and in inducing the contractions of the rabbit pulmonary artery, a neurokinin 2-type bioassay. To increase the specificity of the cyclic analogue (Cys/sup 3,6/)SP positions 8 and 9 were modified. Collectively, these results suggest that the neurokinin 1 and neurokinin 3 tachykinin receptors may recognize a similar three-dimensional structure of the core of the tachykinins. Different orientations of the common C-terminal tripeptide may be related to the selectivity for the different receptor subtypes.

  10. Effects of hypokinesia on cyclic nucleotides and hormonal regulation ...

    African Journals Online (AJOL)

    PTH), calcitonin (CT), cyclic nucleotides (cAMP, cGMP) and calcium in the blood of rats, while in urine - phosphate, calcium and cyclic nucleotides. Design: Laboratory based experiment. Setting: Laboratory in the Department of Biochemistry, ...

  11. Augmentation Quotients for Real Representation Rings of Cyclic ...

    Indian Academy of Sciences (India)

    29

    Augmentation Quotients for Real Representation Rings of Cyclic Groups. Article Type: Reseach Article. Keywords: cyclic group; real representation; augmentation ideal; augmentation quotient. Corresponding Author: Hang Liu, Ph.D. Shaanxi Normal University. Xi'an, Shaanxi CHINA. Corresponding Author Secondary.

  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. Compressed sensing with cyclic-S Hadamard matrix for terahertz imaging applications

    Science.gov (United States)

    Ermeydan, Esra Şengün; ćankaya, Ilyas

    2018-01-01

    Compressed Sensing (CS) with Cyclic-S Hadamard matrix is proposed for single pixel imaging applications in this study. In single pixel imaging scheme, N = r . c samples should be taken for r×c pixel image where . denotes multiplication. CS is a popular technique claiming that the sparse signals can be reconstructed with samples under Nyquist rate. Therefore to solve the slow data acquisition problem in Terahertz (THz) single pixel imaging, CS is a good candidate. However, changing mask for each measurement is a challenging problem since there is no commercial Spatial Light Modulators (SLM) for THz band yet, therefore circular masks are suggested so that for each measurement one or two column shifting will be enough to change the mask. The CS masks are designed using cyclic-S matrices based on Hadamard transform for 9 × 7 and 15 × 17 pixel images within the framework of this study. The %50 compressed images are reconstructed using total variation based TVAL3 algorithm. Matlab simulations demonstrates that cyclic-S matrices can be used for single pixel imaging based on CS. The circular masks have the advantage to reduce the mechanical SLMs to a single sliding strip, whereas the CS helps to reduce acquisition time and energy since it allows to reconstruct the image from fewer samples.

  15. 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.

  16. Cyclic Soft Groups and Their Applications on Groups

    Directory of Open Access Journals (Sweden)

    Hacı Aktaş

    2014-01-01

    Full Text Available In crisp environment the notions of order of group and cyclic group are well known due to many applications. In this paper, we introduce order of the soft groups, power of the soft sets, power of the soft groups, and cyclic soft group on a group. We also investigate the relationship between cyclic soft groups and classical groups.

  17. 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.

  18. 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

  19. 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).

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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

  12. 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

  13. Cosmic evolution in a cyclic universe

    International Nuclear Information System (INIS)

    Steinhardt, Paul J.; Turok, Neil

    2002-01-01

    Based on concepts drawn from the ekpyrotic scenario and M theory, we elaborate our recent proposal of a cyclic model of the universe. In this model, the universe undergoes an endless sequence of cosmic epochs which begin with the universe expanding from a 'big bang' and end with the universe contracting to a 'big crunch'. Matching from 'big crunch' to 'big bang' is performed according to the prescription recently proposed with Khoury, Ovrut and Seiberg. The expansion part of the cycle includes a period of radiation and matter domination followed by an extended period of cosmic acceleration at low energies. The cosmic acceleration is crucial in establishing the flat and vacuous initial conditions required for ekpyrosis and for removing the entropy, black holes, and other debris produced in the preceding cycle. By restoring the universe to the same vacuum state before each big crunch, the acceleration ensures that the cycle can repeat and that the cyclic solution is an attractor

  14. Strain gradient effects on cyclic plasticity

    DEFF Research Database (Denmark)

    Niordson, Christian Frithiof; Legarth, Brian Nyvang

    2010-01-01

    Size effects on the cyclic shear response are studied numerically using a recent higher order strain gradient visco-plasticity theory accounting for both dissipative and energetic gradient hardening. Numerical investigations of the response under cyclic pure shear and shear of a finite slab between...... rigid platens have been carried out, using the finite element method. It is shown for elastic–perfectly plastic solids how dissipative gradient effects lead to increased yield strength, whereas energetic gradient contributions lead to increased hardening as well as a Bauschinger effect. For linearly...... hardening materials it is quantified how dissipative and energetic gradient effects promote hardening above that of conventional predictions. Usually, increased hardening is attributed to energetic gradient effects, but here it is found that also dissipative gradient effects lead to additional hardening...

  15. A cyclic symmetry principle in physics

    International Nuclear Information System (INIS)

    Green, H.S.; Adelaide Univ., SA

    1994-01-01

    Many areas of modern physics are illuminated by the application of a symmetry principle, requiring the invariance of the relevant laws of physics under a group of transformations. This paper examines the implications and some of the applications of the principle of cyclic symmetry, especially in the areas of statistical mechanics and quantum mechanics, including quantized field theory. This principle requires invariance under the transformations of a finite group, which may be a Sylow π-group, a group of Lie type, or a symmetric group. The utility of the principle of cyclic invariance is demonstrated in finding solutions of the Yang-Baxter equation that include and generalize known solutions. It is shown that the Sylow π-groups have other uses, in providing a basis for a type of generalized quantum statistics, and in parametrising a new generalization of Lie groups, with associated algebras that include quantized algebras. 31 refs

  16. Analysis of cyclic creep and rupture. Part 1: bounding theorems and cyclic reference stresses

    Energy Technology Data Exchange (ETDEWEB)

    Carter, P. [Stress Engineering Services, Inc., Mason, OH 45040 (United States)]. E-mail: peter.carter@ses-oh.com

    2005-01-01

    Cyclic loading on structures can produce failures not readily predicted by conventional static analysis. Ratcheting or incremental distortion leads to structural failure, and complicates the problems of creep and fatigue prediction. Predicting shakedown, ratcheting, accelerated creep and rupture, for cyclic loading, are the objectives of cyclic stress analysis.Limit load, shakedown and ratcheting analyses provide a comprehensive basis to understand static structural behaviour for ductile inelastic materials, subject to variable loading but excluding inertial dynamic effects. From them we can predict the following failure modes:-Plastic collapse.-Failure to shakedown.-Ratcheting.-Accelerated creep and rupture.This is achieved with a generalisation of the reference stress concept. Conventionally, and for steady loading, the limit load reference stress is the lowest yield stress for which the structure does not collapse. For cyclic loading two definitions are available. The more conservative is the lowest yield stress for which the structure shakes down (behaves elastically). The less conservative is the lowest yield stress for which the structure does not ratchet. They have different meanings and uses.Explaining and justifying the use of cyclic reference stresses to bound creep and rupture is the objective of Part 1. Part 2 gives examples illustrating a range of structural behaviours. The methodology of these papers involves so-called approximate methods at one level, that of inferring limiting or conservative time-dependent behaviour from time-independent elastic-plastic cyclic analyses. The elastic-plastic cyclic analyses themselves are straightforward if tedious. Some ideas and a new analysis technique are available to reduce the trial-and-error.

  17. Numerically investigating the emergent cyclic inflation scenario

    International Nuclear Information System (INIS)

    Duhe, William; Biswas, Tirthabir

    2014-01-01

    We provide a comprehensive numerical study of the emergent cyclic inflation scenario. This is a scenario where instead of traditional monotonic slow roll inflation, the universe expands over numerous short asymmetric cycles due to the production of entropy via interactions among different species. This is one of the very few scenarios of inflation that provides a non-singular geodesically complete space-time and does not require any ‘reheating’ mechanism. (paper)

  18. Scale factor duality for conformal cyclic cosmologies

    International Nuclear Information System (INIS)

    Silva, University Camara da; Lima, A.L. Alves; Sotkov, G.M.

    2016-01-01

    The scale factor duality is a symmetry of dilaton gravity which is known to lead to pre-big-bang cosmologies. A conformal time version of the scale factor duality (SFD) was recently implemented as a UV/IR symmetry between decelerated and accelerated phases of the post-big-bang evolution within Einstein gravity coupled to a scalar field. The problem investigated in the present paper concerns the employment of the conformal time SFD methods to the construction of pre-big-bang and cyclic extensions of these models. We demonstrate that each big-bang model gives rise to two qualitatively different pre-big-bang evolutions: a contraction/expansion SFD model and Penrose’s Conformal Cyclic Cosmology (CCC). A few examples of SFD symmetric cyclic universes involving certain gauged Kähler sigma models minimally coupled to Einstein gravity are studied. We also describe the specific SFD features of the thermodynamics and the conditions for validity of the generalized second law in the case of Gauss-Bonnet (GB) extension of these selected CCC models.

  19. Visualization of cyclic nucleotide dynamics in neurons

    Directory of Open Access Journals (Sweden)

    Kirill eGorshkov

    2014-12-01

    Full Text Available The second messengers cAMP and cGMP transduce many neuromodulatory signals from hormones and neurotransmitters into specific functional outputs. Their production, degradation and signaling are spatiotemporally regulated to achieve high specificity in signal transduction. The development of genetically encodable fluorescent biosensors has provided researchers with useful tools to study these versatile second messengers and their downstream effectors with unparalleled spatial and temporal resolution in cultured cells and living animals. In this review, we introduce the general design of these fluorescent biosensors and describe several of them in more detail. Then we discuss a few examples of using cyclic nucleotide fluorescent biosensors to study regulation of neuronal function and finish with a discussion of advances in the field. Although there has been significant progress made in understanding how the specific signaling of cyclic nucleotide second messengers is achieved, the mechanistic details in complex cell types like neurons are only just beginning to surface. Current and future fluorescent protein reporters will be essential to elucidate the role of cyclic nucleotide signaling dynamics in the functions of individual neurons and their networks.

  20. A second disulfide bridge from the N-terminal domain to extracellular loop 2 dampens receptor activity in GPR39

    DEFF Research Database (Denmark)

    Storjohann, Laura; Holst, Birgitte; Schwartz, Thue W

    2008-01-01

    A highly conserved feature across all families of 7TM receptors is a disulfide bridge between a Cys residue located at the extracellular end of transmembrane segment III (TM-III) and one in extracellular loop 2 (ECL-2). The zinc sensor GPR39 contains four Cys residues in the extracellular domains...... on the receptor already lacking the second disulfide bridge and already displaying a high Zn (2+) potency. We conclude that the second disulfide bridge, which according to the beta2-adrenergic structure will form a covalent link across the entrance to the main ligand binding pocket, serves to dampen GPR39...... activation. We suggest that formation of extra disulfide bridges may be an important general mechanism for regulating the activity of 7TM receptors....

  1. Multiaxial elastoplastic cyclic loading of austenitic 316L steel

    Directory of Open Access Journals (Sweden)

    V. Mazánová

    2017-04-01

    Full Text Available Cyclic stress-strain response and fatigue damage character has been investigated in austenitic stainless steel 316L. Hollow cylindrical specimens have been cyclically deformed in combined tension-compression and torsion under constant strain rate condition and different constant strain and shear strain amplitudes. In-phase and 90° out-of-phase cyclic straining was applied and the stress response has been monitored. Cyclic hardening/softening curves were assessed in both channels. Cyclic softening followed for higher strain amplitudes by long-term cyclic hardening was observed. Cyclic stress-strain curves were determined. Study of the surface damage in fractured specimens revealed the types and directions of principal cracks and the sources of fatigue crack initiation in slip bands.

  2. Disruption of reducing pathways is not essential for efficient disulfide bond formation in the cytoplasm of E. coli

    Directory of Open Access Journals (Sweden)

    Hatahet Feras

    2010-09-01

    Full Text Available Abstract Background The formation of native disulfide bonds is a complex and essential post-translational modification for many proteins. The large scale production of these proteins can be difficult and depends on targeting the protein to a compartment in which disulfide bond formation naturally occurs, usually the endoplasmic reticulum of eukaryotes or the periplasm of prokaryotes. It is currently thought to be impossible to produce large amounts of disulfide bond containing protein in the cytoplasm of wild-type bacteria such as E. coli due to the presence of multiple pathways for their reduction. Results Here we show that the introduction of Erv1p, a sulfhydryl oxidase and FAD-dependent catalyst of disulfide bond formation found in the inter membrane space of mitochondria, allows the efficient formation of native disulfide bonds in heterologously expressed proteins in the cytoplasm of E. coli even without the disruption of genes involved in disulfide bond reduction, for example trxB and/or gor. Indeed yields of active disulfide bonded proteins were higher in BL21 (DE3 pLysSRARE, an E. coli strain with the reducing pathways intact, than in the commercial Δgor ΔtrxB strain rosetta-gami upon co-expression of Erv1p. Conclusions Our results refute the current paradigm in the field that disruption of at least one of the reducing pathways is essential for the efficient production of disulfide bond containing proteins in the cytoplasm of E. coli and open up new possibilities for the use of E. coli as a microbial cell factory.

  3. Disulfide bridges in tomato pectinesterase: variations from pectinesterases of other species; conservation of possible active site segments.

    OpenAIRE

    Markovic, O.; Jörnvall, H.

    1992-01-01

    Analysis of tomato pectinesterase by carboxymethylation, with and without reduction, shows that the enzyme has two intrachain disulfide bridges. Analysis of fragments obtained from the native enzyme after digestion with pepsin identified bridges connecting Cys-98 with Cys-125, and Cys-166 with Cys-200. The locations of disulfide bridges in tomato pectinesterase are not identical to those in three distantly related pectinesterases (18-33% residue identities) from microorganisms. However, one h...

  4. The biologically active form of the sea urchin egg receptor for sperm is a disulfide-bonded homo-multimer

    OpenAIRE

    1994-01-01

    Since many cell surface receptors exist in their active form as oligomeric complexes, we have investigated the subunit composition of the biologically active sperm receptor in egg plasma membranes from Strongylocentrotus purpuratus. Electrophoretic analysis of the receptor without prior reduction of disulfide bonds revealed that the surface receptor exists in the form of a disulfide-bonded multimer, estimated to be a tetramer. These findings are in excellent agreement with the fact that the N...

  5. A Strategy for Production of Correctly Folded Disulfide-Rich Peptides in the Periplasm of E. coli.

    Science.gov (United States)

    Saez, Natalie J; Cristofori-Armstrong, Ben; Anangi, Raveendra; King, Glenn F

    2017-01-01

    Recombinant expression of disulfide-reticulated peptides and proteins is often challenging. We describe a method that exploits the periplasmic disulfide-bond forming machinery of Escherichia coli and combines this with a cleavable, solubility-enhancing fusion tag to obtain higher yields of correctly folded target protein than is achievable via cytoplasmic expression. The protocols provided herein cover all aspects of this approach, from vector construction and transformation to purification of the cleaved target protein and subsequent quality control.

  6. Nicotinamidase/pyrazinamidase of Mycobacterium tuberculosis forms homo-dimers stabilized by disulfide bonds.

    Science.gov (United States)

    Rueda, Daniel; Sheen, Patricia; Gilman, Robert H; Bueno, Carlos; Santos, Marco; Pando-Robles, Victoria; Batista, Cesar V; Zimic, Mirko

    2014-12-01

    Recombinant wild-pyrazinamidase from H37Rv Mycobacterium tuberculosis was analyzed by gel electrophoresis under differential reducing conditions to evaluate its quaternary structure. PZAse was fractionated by size exclusion chromatography under non-reducing conditions. PZAse activity was measured and mass spectrometry analysis was performed to determine the identity of proteins by de novo sequencing and to determine the presence of disulfide bonds. This study confirmed that M. tuberculosis wild type PZAse was able to form homo-dimers in vitro. Homo-dimers showed a slightly lower specific PZAse activity compared to monomeric PZAse. PZAse dimers were dissociated into monomers in response to reducing conditions. Mass spectrometry analysis confirmed the existence of disulfide bonds (C72-C138 and C138-C138) stabilizing the quaternary structure of the PZAse homo-dimer. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Selective removal of heavy metal ions by disulfide linked polymer networks.

    Science.gov (United States)

    Ko, Dongah; Lee, Joo Sung; Patel, Hasmukh A; Jakobsen, Mogens H; Hwang, Yuhoon; Yavuz, Cafer T; Hansen, Hans Chr Bruun; Andersen, Henrik R

    2017-06-15

    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions-copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Autonomic healable waterborne organic-inorganic polyurethane hybrids based on aromatic disulfide moieties

    Directory of Open Access Journals (Sweden)

    R. H. Aguirresarobe

    2017-04-01

    Full Text Available Aromatic disulfide dynamic structures were incorporated as chain extenders in waterborne organic-inorganic polyurethane hybrids in order to provide autonomic healable characteristics. The synthesis was carried out following the acetone process methodology and the influence of the introduction of the healing agents in the polymer dispersion stability was analyzed. After the crosslinking process at room temperature, organic-inorganic hybrid films, which presented autonomic healing characteristics, were obtained. These features were evaluated by means of stress-strain tests and the films showed repetitive healing abilities. Thus, the optimum healing time at room temperature (25 °C as well as the influence of different parameters in the healing efficiency, such the aromatic disulfide concentration or the physical properties of the polymer matrix were analyzed.

  9. Disulfide bond effects on protein stability: designed variants of Cucurbita maxima trypsin inhibitor-V.

    Science.gov (United States)

    Zavodszky, M; Chen, C W; Huang, J K; Zolkiewski, M; Wen, L; Krishnamoorthi, R

    2001-01-01

    Attempts to increase protein stability by insertion of novel disulfide bonds have not always been successful. According to the two current models, cross-links enhance stability mainly through denatured state effects. We have investigated the effects of removal and addition of disulfide cross-links, protein flexibility in the vicinity of a cross-link, and disulfide loop size on the stability of Cucurbita maxima trypsin inhibitor-V (CMTI-V; 7 kD) by differential scanning calorimetry. CMTI-V offers the advantage of a large, flexible, and solvent-exposed loop not involved in extensive intra-molecular interactions. We have uncovered a negative correlation between retention time in hydrophobic column chromatography, a measure of protein hydrophobicity, and melting temperature (T(m)), an indicator of native state stabilization, for CMTI-V and its variants. In conjunction with the complete set of thermodynamic parameters of denaturation, this has led to the following deductions: (1) In the less stable, disulfide-removed C3S/C48S (Delta Delta G(d)(50 degrees C) = -4 kcal/mole; Delta T(m) = -22 degrees C), the native state is destabilized more than the denatured state; this also applies to the less-stable CMTI-V* (Delta Delta G(d)(50 degrees C) = -3 kcal/mole; Delta T(m) = -11 degrees C), in which the disulfide-containing loop is opened by specific hydrolysis of the Lys(44)-Asp(45) peptide bond; (2) In the less stable, disulfide-inserted E38C/W54C (Delta Delta G(d)(50 degrees C) = -1 kcal/mole; Delta T(m) = +2 degrees C), the denatured state is more stabilized than the native state; and (3) In the more stable, disulfide-engineered V42C/R52C (Delta Delta G(d)(50 degrees C) = +1 kcal/mole; Delta T(m) = +17 degrees C), the native state is more stabilized than the denatured state. These results show that a cross-link stabilizes both native and denatured states, and differential stabilization of the two states causes either loss or gain in protein stability. Removal of hydrogen

  10. Conversion of a disulfide bond into a thioacetal group during echinomycin biosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hotta, Kinya; Keegan, Ronan M.; Ranganathan, Soumya; Fang, Minyi; Bibby, Jaclyn; Winn, Martyn D.; Sato, Michio; Lian, Mingzhu; Watanabe, Kenji; Rigden, Daniel J.; Kim, Chu-Young (Liverpool); (Daresbury); (NU Singapore); (Shizuoka); (RAL)

    2013-12-02

    Echinomycin is a nonribosomal depsipeptide natural product with a range of interesting bioactivities that make it an important target for drug discovery and development. It contains a thioacetal bridge, a unique chemical motif derived from the disulfide bond of its precursor antibiotic triostin A by the action of an S-adenosyl-L-methionine-dependent methyltransferase, Ecm18. The crystal structure of Ecm18 in complex with its reaction products S-adenosyl-L-homocysteine and echinomycin was determined at 1.50 Å resolution. Phasing was achieved using a new molecular replacement package called AMPLE, which automatically derives search models from structure predictions based on ab initio protein modelling. Structural analysis indicates that a combination of proximity effects, medium effects, and catalysis by strain drives the unique transformation of the disulfide bond into the thioacetal linkage.

  11. Disulfide bridges remain intact while native insulin converts into amyloid fibrils.

    Directory of Open Access Journals (Sweden)

    Dmitry Kurouski

    Full Text Available Amyloid fibrils are β-sheet-rich protein aggregates commonly found in the organs and tissues of patients with various amyloid-associated diseases. Understanding the structural organization of amyloid fibrils can be beneficial for the search of drugs to successfully treat diseases associated with protein misfolding. The structure of insulin fibrils was characterized by deep ultraviolet resonance Raman (DUVRR and Nuclear Magnetic Resonance (NMR spectroscopy combined with hydrogen-deuterium exchange. The compositions of the fibril core and unordered parts were determined at single amino acid residue resolution. All three disulfide bonds of native insulin remained intact during the aggregation process, withstanding scrambling. Three out of four tyrosine residues were packed into the fibril core, and another aromatic amino acid, phenylalanine, was located in the unordered parts of insulin fibrils. In addition, using all-atom MD simulations, the disulfide bonds were confirmed to remain intact in the insulin dimer, which mimics the fibrillar form of insulin.

  12. Insulin analog with additional disulfide bond has increased stability and preserved activity

    DEFF Research Database (Denmark)

    Vinther, Tine N.; Norrman, Mathias; Ribel, Ulla

    2013-01-01

    under high physical stress even though the C-terminus of the B-chain thought to be directly involved in fibril formation was not modified. Importantly, this analog was capable of forming hexamer upon Zn addition as typical for wild-type insulin and its crystal structure showed only minor deviations from...... (HI) structure. This insulin analog had increased affinity for the insulin receptor and apparently augmented glucodynamic potency in a normal rat model compared with HI. Addition of the disulfide bond also resulted in a 34.6°C increase in melting temperature and prevented insulin fibril formation...... bond may enhance insulin structural stability which would be highly desirable in a pharmaceutical use. To address this hypothesis, we designed insulin with an additional interchain disulfide bond in positions A10/B4 based on Cα-Cα distances, solvent exposure, and side-chain orientation in human insulin...

  13. Regional cerebral blood flow after long-term exposure to carbon disulfide

    International Nuclear Information System (INIS)

    Aaserud, O.; Russell, D.; Nyberg-Hansen, R.; Joergensen, E.B.; Gjerstad, L.; Rootwelt, K.; Nakstad, P.; Hommeren, O.J.; Tvedt, B.

    1992-01-01

    Sixteen former rayon viscose workers were investigated four years after the exposure to carbon disulfide was discontinued. Median age was 58 years (range 43-65 years), median exposure time was 17 years (range 10-35 years). Encephalopathy was diagnosed in altogether 14 workers. To further explore pathophysiological mechanisms, cerebrovascular investigations were employed. Doppler ultrasound examination of the precerebral vessels in 15 workers showed a slight stenosis of the left internal carotid artery in one. Regional cerebral blood flow investigation (rCBF) with single photon emission computerized tomography (SPECT) with Xenon-133 gas was performed in 14. There was no significant difference from a control group. Regional side-to-side asymmetries beyond reference limits were demonstrated in eight workers. The abnormalities were modest, but may indicate a tendency toward focal blood flow disturbances in workers with long-term exposure to carbon disulfide. (au)

  14. Determination of Disulfide Bond Connectivity of Cysteine-rich Peptide IpTx{sub a}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Chul Won; Kim, Jim Il [Chonnam National Univ., Gwangju (Korea, Republic of); Sato, Kazuki [Fukuoka Women' s Univ., Fukuoka (Japan)

    2013-06-15

    Cysteine-rich peptides stabilized by intramolecular disulfide bonds have often been isolated from venoms of microbes, animals and plants. These peptides typically have much higher stability and improved biopharmaceutical properties compared to their linear counterparts. Therefore the correct disulfide bond formation of small proteins and peptides has been extensively studied for a better understanding of their folding mechanism and achieving efficient generation of the naturally occurring biologically active product. Imperatoxin A (IpTx{sub a}), a peptide toxin containing 6 cysteine residues, was isolated from the venom of scorpion Pandinus imperator, selectively binds the ryanodine receptors and activates Ca{sup 2+} release from sarcoplasmic reticulum (SR). IpTx{sub a} increases the binding of ryanodine to ryanodine receptors (RyRs) and encourages reconstituted single channel to induce subconductance states.

  15. Plant antimicrobial peptides snakin-1 and snakin-2: chemical synthesis and insights into the disulfide connectivity.

    Science.gov (United States)

    Harris, Paul W R; Yang, Sung-Hyun; Molina, Antonio; López, Gemma; Middleditch, Martin; Brimble, Margaret A

    2014-04-22

    Antimicrobial peptides and proteins represent an important class of plant defensive compounds against pathogens and provide a rich source of lead compounds in the field of drug discovery. We describe the effective preparation of the cysteine-rich snakin-1 and -2 antimicrobial peptides by using a combination of solid-phase synthesis and native chemical ligation. A subsequent cysteine/cystine mediated oxidative folding to form the six internal disulfide bonds concurrently gave the folded proteins in 40-50 % yield. By comparative evaluation of mass spectrometry, HPLC, biological data and trypsin digest mapping of folded synthetic snakin-2 compared to natural snakin-2, we demonstrated that synthetic snakin-2 possesses full antifungal activity and displayed similar chromatographic behaviour to natural snakin-2. Trypsin digest analysis allowed tentative assignment of three of the purported six disulfide bonds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Selective removal of heavy metal ions by disulfide linked polymer networks

    DEFF Research Database (Denmark)

    Ko, Dongah; Sung Lee, Joo; Patel, Hasmukh A.

    2017-01-01

    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has...... a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal...... sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions―copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water....

  17. Electronic and Vibrational Optical Activity of Several Peptides Related to Neurohypophyseal Hormones: Disulfide Group Conformation

    Czech Academy of Sciences Publication Activity Database

    Pazderková, Markéta; Bednárová, Lucie; Dlouhá, Helena; Flegel, Martin; Lebl, M.; Hlaváček, Jan; Setnička, V.; Urbanová, M.; Hynie, S.; Klenerová, V.; Baumruk, V.; Maloň, Petr

    2012-01-01

    Roč. 97, č. 11 (2012), s. 923-932 ISSN 0006-3525 R&D Projects: GA ČR GAP205/10/1276 Grant - others:GA UK(CZ) 578212 Institutional research plan: CEZ:AV0Z40550506 Keywords : neurohypophyseal hormones * disulfide bridge * Raman optical activity * vibrational circular dichroism Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.879, year: 2012

  18. {sup 13}C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Mitsuhiro [Kumamoto University, Department of Structural BioImaging, Faculty of Life Sciences (Japan); Miyanoiri, Yohei [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan); Terauchi, Tsutomu [Tokyo Metropolitan University, Graduate School of Science and Engineering (Japan); Kainosho, Masatsune, E-mail: kainosho@tmu.ac.jp [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan)

    2016-09-15

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14–Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D {sup 13}C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically {sup 13}C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14–Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m{sub c14} and m{sub c38}). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for {sup 13}C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m{sub c38} isomerization, the {sup 1}H-{sup 13}C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  19. (13)C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI).

    Science.gov (United States)

    Takeda, Mitsuhiro; Miyanoiri, Yohei; Terauchi, Tsutomu; Kainosho, Masatsune

    2016-09-01

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14-Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D (13)C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically (13)C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14-Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m c14 and m c38). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for (13)C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m c38 isomerization, the (1)H-(13)C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  20. 13C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

    International Nuclear Information System (INIS)

    Takeda, Mitsuhiro; Miyanoiri, Yohei; Terauchi, Tsutomu; Kainosho, Masatsune

    2016-01-01

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14–Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D 13 C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically 13 C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14–Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m c14 and m c38 ). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for 13 C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m c38 isomerization, the 1 H- 13 C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  1. Neutron in-beam Moessbauer spectroscopic study of iron disulfide at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Kubo, M. K. [International Christian University, College of Liberal Arts (Japan); Kobayashi, Y., E-mail: kyoshio@riken.jp [RIKEN (Japan); Nonaka, H.; Yamada, Y. [Science University of Tokyo, Department of Chemistry (Japan); Sakai, Y. [Daido Institute of Technology (Japan); Shoji, H. [Tokyo Metropolitan University, Graduate School of Science (Japan); Matsue, H. [Japan Atomic Energy Research Institute (Japan)

    2005-11-15

    An in-beam emission Moessbauer spectrum of {sup 57}Fe arising from the {sup 56}Fe(n, {gamma}) {sup 57}Fe reaction in iron disulfide at room temperature was measured with a parallel plate avalanche counter. It was clearly observed that the nuclear reaction and the following process lead to the production of a new chemical species of iron different from the parent compound.

  2. Neutron in-beam Moessbauer spectroscopy of iron disulfide at 298 and 78 K

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Y., E-mail: kyoshio@riken.jp [RIKEN (Japan); Yamada, Y. [Tokyo University of Science, Department of Chemistry (Japan); Tsuruoka, Y.; Kubo, M. K. [International Christian University (Japan); Shoji, H. [Tokyo Metropolitan University, Graduate School of Science (Japan); Watanabe, Y. [Saint-Gobain K. K., Crystal Division (Japan); Takayama, T.; Sakai, Y. [Daido Institute of Technology (Japan); Sato, W.; Shinohara, A. [Osaka University, Graduate School of Science (Japan); Segawa, M.; Matsue, H. [Japan Atomic Energy Agency (Japan)

    2008-11-15

    Emission Moessbauer spectra of {sup 57}Fe arising from the {sup 56}Fe(n, {gamma}){sup 57}Fe reaction in two crystal forms of iron disulfide were measured at room temperature and liquid nitrogen temperature. Both forms exhibited two doublets assignable to the parent material and the new species produced by the nuclear reaction. At low temperature three doublets explained the spectra obtained. Production of thermally unstable species after the neutron capture reaction was suggested.

  3. Modified electrophoretic and digestion conditions allow a simplified mass spectrometric evaluation of disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Pompach, Petr; Man, Petr; Kavan, Daniel; Hofbauerová, Kateřina; Kumar, Vinay; Bezouška, Karel; Havlíček, Vladimír; Novák, Petr

    2009-01-01

    Roč. 44, č. 11 (2009), s. 1571-1578 ISSN 1076-5174 R&D Projects: GA AV ČR KJB400200501; GA AV ČR IAA5020403; GA AV ČR KJB500200612; GA MŠk LC545; GA MŠk LC07017 Institutional research plan: CEZ:AV0Z50200510 Keywords : disulfide bond * cystamine * gel electrophoresis Subject RIV: CE - Biochemistry Impact factor: 3.411, year: 2009

  4. Evaporation dynamics of microdroplets on self-assembled monolayers of dialkyl disulfides.

    Science.gov (United States)

    Li, Guangfen; Flores, Susana Moreno; Vavilala, Chandrasekhar; Schmittel, Michael; Graf, Karlheinz

    2009-12-01

    We present a study of the static wettability and evaporation dynamics of sessile microdroplets of water on self-assembled monolayers (SAMs) prepared with unsymmetric dialkyl disulfides CH(3)-(CH(2))(11+m)-S-S-(CH(2))(11)-OH (m = 0, +/- 2, +/- 4, +/- 6) on gold-covered mica. The advancing and receding contact angles decrease linearly with increasing hydrophilicity of the SAM. The latter was changed either via the molar ratio or via the chain length of the hydroxyl-terminated alkyl chains in the monolayer. In contrast to SAMs made of thiols, the contact angle hysteresis was 10 degrees for all disulfides, irrespective of their chain lengths. During evaporation of single droplets, a transition from pinning to constant contact angle mode was observed. The transition time between the modes increases with the surface hydrophilicity, leading to longer pinning. This way, the time for complete droplet evaporation decreases by approximately 30% owing to the fact that during pinning the overall droplet area stays large for a longer time. For single droplets the measured total evaporation times agree well with the calculated ones, showing the validity of the standard evaporation model for both evaporation modes. In contrast to the results for single droplets, many droplets with different initial volumes show a power-law dependence on the total evaporation time with an exponent different from 1.5 as expected from the standard model. For disulfides with m not equal 0, the exponent is in the range of 1.40-1.47 increasing with the surface hydrophilicity. For the SAMs with m = 0 the exponent increases up to 1.61 for the most hydrophilic surface. We explain this deviation from the standard evaporation model with the presence of a liquid precursor film around the droplet, which either enhances or decelerates evaporation. Our results suggest that SAMs of dialkyl disulfides offer the possibility to tune the wettability of gold surfaces in a more controlled way than thiols do.

  5. Photochemical synthesis of ultrafine organosilicon particles from trimethyl(2-propynyloxy)silane and carbon disulfide

    Czech Academy of Sciences Publication Activity Database

    Morita, H.; Nozawa, R.; Bastl, Zdeněk; Šubrt, Jan; Pola, Josef

    2006-01-01

    Roč. 179, 1-2 (2006), s. 142-148 ISSN 1010-6030 Grant - others:MEXT(JP) 767/15085203 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40320502; CEZ:AV0Z40720504 Keywords : ultrafine particles * photo-polymerization * trimethyl(2-propynyloxy)silane * carbon disulfide Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.098, year: 2006

  6. The Intramolecular Hydrogen Bond N-H···S in 2,2'-Diaminodiphenyl Disulfide: Experimental and Computational Thermochemistry.

    Science.gov (United States)

    Ramos, Fernando; Flores, Henoc; Hernández-Pérez, Julio M; Sandoval-Lira, Jacinto; Camarillo, E Adriana

    2018-01-11

    The intramolecular hydrogen bond of the N-H···S type has been investigated sparingly by thermochemical and computational methods. In order to study this interaction, the standard molar enthalpies of formation in gaseous phase of diphenyl disulfide, 2,2'-diaminodiphenyl disulfide and 4,4'-diaminodiphenyl disulfide at T = 298.15 K were determined by experimental thermochemical methods and computational calculations. The experimental enthalpies of formation in gas-phase were obtained from enthalpies of formation in crystalline phase and enthalpies of sublimation. Enthalpies of formation in crystalline phase were obtained using rotatory bomb combustion calorimetry. By thermogravimetry, enthalpies of vaporization were obtained, and by combining them with enthalpies of fusion, the enthalpies of sublimation were calculated. The Gaussian-4 procedure and the atomization method were applied to obtain enthalpies of formation in gas-phase of the compounds under study. Theoretical and experimental values are in good agreement. Through natural bond orbital (NBO) analysis and a topological analysis of the electronic density, the intramolecular hydrogen bridge (N-H···S) in the 2,2'-diaminodiphenyl disulfide was confirmed. Finally, an enthalpic difference of 11.8 kJ·mol -1 between the 2,2'-diaminodiphenyl disulfide and 4,4'-diaminodiphenyl disulfide was found, which is attributed to the intramolecular N-H···S interaction.

  7. Role of protein disulfide isomerase and other thiol-reactive proteins in HIV-1 envelope protein-mediated fusion

    International Nuclear Information System (INIS)

    Ou Wu; Silver, Jonathan

    2006-01-01

    Cell-surface protein disulfide isomerase (PDI) has been proposed to promote disulfide bond rearrangements in HIV-1 envelope protein (Env) that accompany Env-mediated fusion. We evaluated the role of PDI in ways that have not been previously tested by downregulating PDI with siRNA and by overexpressing wild-type or variant forms of PDI in transiently and stably transfected cells. These manipulations, as well as treatment with anti-PDI antibodies, had only small effects on infection or cell fusion mediated by NL4-3 or AD8 strains of HIV-1. However, the cell-surface thiol-reactive reagent 5, 5'-dithiobis(2-nitrobenzoic acid) (DTNB) had a much stronger inhibitory effect in our system, suggesting that cell-surface thiol-containing molecules other than PDI, acting alone or in concert, have a greater effect than PDI on HIV-1 Env-mediated fusion. We evaluated one such candidate, thioredoxin, a PDI family member reported to reduce a labile disulfide bond in CD4. We found that the ability of thioredoxin to reduce the disulfide bond in CD4 is enhanced in the presence of HIV-1 Env gp120 and that thioredoxin also reduces disulfide bonds in gp120 directly in the absence of CD4. We discuss the implications of these observations for identification of molecules involved in disulfide rearrangements in Env during fusion

  8. An analytic study of molybdenum disulfide nanofluids using the modern approach of Atangana-Baleanu fractional derivatives

    Science.gov (United States)

    Ali Abro, Kashif; Hussain, Mukkarum; Mahmood Baig, Mirza

    2017-10-01

    The significance of the different shapes of molybdenum disulfide nanoparticles contained in ethylene glycol has recently attracted researchers, because of the numerical or experimental analyses on the shapes of molybdenum disulfide and the lack of fractionalized analytic approaches. This work is dedicated to examining the shape impacts of molybdenum disulfide nanofluids in the mixed convection flow with magnetic field and a porous medium. Ethylene glycol is chosen as the base fluid in which molybdenum disulfide nanoparticles are suspended. Non-spherically shaped molybdenum disulfide nanoparticles, namely, platelet, blade, cylinder and brick, are utilized in this analysis. The modeling of the problem is characterized by employing the modern approach of Atangana-Baleanu fractional derivatives and the governing partial differential equations are solved via Laplace transforms with inversion. Solutions are obtained for temperature distribution and velocity field and expressed in terms of compact form of M-function, Mba(T) . In the end, a figures are drawn to compare the different non-spherically shaped molybdenum disulfide nanoparticles. Furthermore, the Atangana-Baleanu fractional derivatives model has been compared with ordinary derivatives models and discussed graphically by setting various rheological parameters.

  9. 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.

  10. 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%.

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Resolution of Disulfide Heterogeneity in Nogo Receptor 1 Fusion Proteins by Molecular Engineering

    Energy Technology Data Exchange (ETDEWEB)

    P Weinreb; D Wen; F Qian; C Wildes; E Garber; L Walus; M Jung; J Wang; J Relton; et al.

    2011-12-31

    NgRI (Nogo-66 receptor) is part of a signalling complex that inhibits axon regeneration in the central nervous system. Truncated soluble versions of NgRI have been used successfully to promote axon regeneration in animal models of spinal-cord injury, raising interest in this protein as a potential therapeutic target. The LRR (leucine-rich repeat) regions in NgRI are flanked by N- and C-terminal disulfide-containing 'cap' domains (LRRNT and LRRCT respectively). In the present work we show that, although functionally active, the NgRI(310)-Fc fusion protein contains mislinked and heterogeneous disulfide patterns in the LRRCT domain, and we report the generation of a series of variant molecules specifically designed to prevent this heterogeneity. Using these variants we explored the effects of modifying the NgRI truncation site or the spacing between the NgRI and Fc domains, or replacing cysteines within the NgRI or IgG hinge regions. One variant, which incorporates replacements of Cys{sup 266} and Cys{sup 309} with alanine residues, completely eliminated disulfide scrambling while maintaining functional in vitro and in vivo efficacy. This modified NgRI-Fc molecule represents a significantly improved candidate for further pharmaceutical development, and may serve as a useful model for the optimization of other IgG fusion proteins made from LRR proteins.

  17. Structure of the Noncatalytic Domains and Global Fold of the Protein Disulfide Isomerase ERp72

    Energy Technology Data Exchange (ETDEWEB)

    Kozlov, G.; Määttänen, P; Schrag, J; Hura, G; Gabrielli, L; Cygler, M; Thomas, D; Gehring, K

    2009-01-01

    Protein disulfide isomerases are a family of proteins that catalyze the oxidation and isomerization of disulfide bonds in newly synthesized proteins in the endoplasmic reticulum. The family includes general enzymes such as PDI that recognize unfolded proteins, and others that are selective for specific classes of proteins. Here, we report the X-ray crystal structure of central non-catalytic domains of a specific isomerase, ERp72 (also called CaBP2 and protein disulfide-isomerase A4) from Rattus norvegicus. The structure reveals strong similarity to ERp57, a PDI-family member that interacts with the lectin-like chaperones calnexin and calreticulin but, unexpectedly, ERp72 does not interact with calnexin as shown by isothermal titration calorimetry and nuclear magnetic resonance (NMR) spectroscopy. Small-angle X-ray scattering (SAXS) of ERp72 was used to develop models of the full-length protein using both rigid body refinement and ab initio simulated annealing of dummy atoms. The two methods show excellent agreement and define the relative positions of the five thioredoxin-like domains of ERp72 and potential substrate or chaperone binding sites.

  18. Protein disulfide-isomerase interacts with a substrate protein at all stages along its folding pathway.

    Directory of Open Access Journals (Sweden)

    Alistair G Irvine

    Full Text Available In contrast to molecular chaperones that couple protein folding to ATP hydrolysis, protein disulfide-isomerase (PDI catalyzes protein folding coupled to formation of disulfide bonds (oxidative folding. However, we do not know how PDI distinguishes folded, partly-folded and unfolded protein substrates. As a model intermediate in an oxidative folding pathway, we prepared a two-disulfide mutant of basic pancreatic trypsin inhibitor (BPTI and showed by NMR that it is partly-folded and highly dynamic. NMR studies show that it binds to PDI at the same site that binds peptide ligands, with rapid binding and dissociation kinetics; surface plasmon resonance shows its interaction with PDI has a Kd of ca. 10(-5 M. For comparison, we characterized the interactions of PDI with native BPTI and fully-unfolded BPTI. Interestingly, PDI does bind native BPTI, but binding is quantitatively weaker than with partly-folded and unfolded BPTI. Hence PDI recognizes and binds substrates via permanently or transiently unfolded regions. This is the first study of PDI's interaction with a partly-folded protein, and the first to analyze this folding catalyst's changing interactions with substrates along an oxidative folding pathway. We have identified key features that make PDI an effective catalyst of oxidative protein folding - differential affinity, rapid ligand exchange and conformational flexibility.

  19. Two-dimensional metallic tantalum disulfide as a hydrogen evolution catalyst.

    Science.gov (United States)

    Shi, Jianping; Wang, Xina; Zhang, Shuai; Xiao, Lingfeng; Huan, Yahuan; Gong, Yue; Zhang, Zhepeng; Li, Yuanchang; Zhou, Xiebo; Hong, Min; Fang, Qiyi; Zhang, Qing; Liu, Xinfeng; Gu, Lin; Liu, Zhongfan; Zhang, Yanfeng

    2017-10-16

    Two-dimensional metallic transition metal dichalcogenides are emerging as prototypes for uncovering fundamental physical phenomena, such as superconductivity and charge-density waves, as well as for engineering-related applications. However, the batch production of such envisioned transition metal dichalcogenides remains challenging, which has hindered the aforementioned explorations. Herein, we fabricate thickness-tunable tantalum disulfide flakes and centimetre-sized ultrathin films on an electrode material of gold foil via a facile chemical vapour deposition route. Through temperature-dependent Raman characterization, we observe the transition from nearly commensurate to commensurate charge-density wave phases with our ultrathin tantalum disulfide flakes. We have obtained high hydrogen evolution reaction efficiency with the as-grown tantalum disulfide flakes directly synthesized on gold foils comparable to traditional platinum catalysts. This work could promote further efforts for exploring new efficient catalysts in the large materials family of metallic transition metal dichalcogenides, as well as exploiting their applications towards more versatile applications.Metallic transition metal dichalcogenides are important materials for catalysis, but scalable and controllable preparation methods are scarce. Here, the authors synthesize 2H-TaS 2 as centimetre-scale films of tunable thickness and show they are an efficient catalyst for hydrogen evolution.

  20. 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....

  1. 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.

  2. 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,...

  3. 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...

  4. 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).

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Kinetic and thermodynamic studies on the disulfide-bond reducing potential of hydrogen sulfide.

    Science.gov (United States)

    Vasas, Anita; Dóka, Éva; Fábián, István; Nagy, Péter

    2015-04-30

    The significance of persulfide species in hydrogen sulfide biology is increasingly recognized. However, the molecular mechanisms of their formation remain largely elusive. The obvious pathway of the reduction of biologically abundant disulfide moieties by sulfide was challenged on both thermodynamic and kinetic grounds. Using DTNB (5,5'-dithiobis-(2-nitrobenzoic acid), also known as Ellman's reagent) as a model disulfide we conducted a comprehensive kinetic study for its reaction with sulfide. The bimolecular reaction is relatively fast with a second-order rate constant of 889 ± 12 M(-1)s(-1) at pH = 7.4. pH dependence of the rate law revealed that the reaction proceeds via the bisulfide anion species with an initial nucleophilic thiol-disulfide exchange reaction to give 5-thio-2-nitrobenzoic acid (TNB) and TNB-persulfide with a pH independent second-order rate constant of 1090 ± 12 M(-1)s(-1). However, kinetic studies and stoichiometric analyses in a wide range of reactant ratios together with kinetic simulations revealed that it is a multistep process that proceeds via kinetically driven, practically irreversible reactions along the disulfide → persulfide → inorganic polysulfides axis. The kinetic model postulated here, which is fully consistent with the experimental data, suggests that the TNB-persulfide is further reduced by sulfide with a second-order rate constant in the range of 5 × 10(3) - 5 × 10(4) M(-1)s(-1) at pH 7.4 and eventually yields inorganic polysulfides and TNB. The reactions of cystine and GSSG with sulfide were found to be significantly slower and to occur via more complicated reaction schemes. (1)H NMR studies suggest that these reactions also generate Cys-persulfide and inorganic polysulfide species, but in contrast with DTNB, in consecutive equilibrium processes that are sensitive to changes in the reactant and product ratios. Collectively, our results demonstrate that the reaction of disulfides with sulfide is a highly system

  12. Nitration Study of Cyclic Ladder Polyphenylsilsesquioxane

    Directory of Open Access Journals (Sweden)

    LIANG Jia-xiang

    2017-05-01

    Full Text Available Several nitration reagents including fuming nitric acid, HNO3-H2SO4, KNO3-H2SO4, HNO3-KNO3, CH3COOH-KNO3, (CH3CO2O-HNO3 were used to nitrate cyclic ladder polyphenylsilsesquioxane (CL-PPSQ in different conditions in order to enhance the compatibility of the CL-PPSQ in polymers, the NO2-PPSQ was obtained. FTIR, element analysis, GPC, TGA and 1H NMR were used to characterize the structures of the nitrated products. The results show that the nitrating abilities of the fuming nitric acid, HNO3-H2SO4 and KNO3-H2SO4 are very strong. Many nitro groups can be linked with phenyl groups in CL-PPSQ, but with low molecular mass, fracture occurs in siloxane segment. However, the Mn of the product NO2-PPSQ sharply drops by 50% compared with that of CL-PPSQ, so the nitration reagents can break the cyclic structure of CL-PPSQ. The nitrating reagents of HNO3-KNO3 and CH3COOH-KNO3 have no nitration effects on CL-PPSQ. At last, NO2-CL-PPSQ was prepared using (CH3CO2O-HNO3 because of the moderate nitration process and ability. The cyclic structure of PPSQ is remained, although the number of —NO2 group is not too much. At the same time, the nitration mechanism using different nitration reagents was analyzed. A certain amount of NO2+, which is a kind of activator owning strong nitration ability, can be found in the fuming nitric acid and H2SO4-HNO3(KNO3 systems. As to the (CH3CO2O-HNO3 system, the main activator is CH3COONO2.

  13. Cosmological D-instantons and cyclic universes

    International Nuclear Information System (INIS)

    Bergshoeff, E A; Collinucci, A; Roest, D; Russo, J G; Townsend, P K

    2005-01-01

    For models of gravity coupled to hyperbolic sigma models, such as the metric-scalar sector of IIB supergravity, we show how smooth trajectories in the 'augmented target space' connect FLRW cosmologies to non-extremal D-instantons through a cosmological singularity. In particular, we find closed cyclic universes that undergo an endless sequence of big-bang to big-crunch cycles separated by instanton 'phases'. We also find 'big-bounce' universes in which a collapsing closed universe bounces off its cosmological singularity to become an open expanding universe

  14. Numerical Simulation of Cyclic Thermodynamic Processes

    DEFF Research Database (Denmark)

    Andersen, Stig Kildegård

    2006-01-01

    This thesis is on numerical simulation of cyclic thermodynamic processes. A modelling approach and a method for finding periodic steady state solutions are described. Examples of applications are given in the form of four research papers. Stirling machines and pulse tube coolers are introduced......, compressible flow in one space dimension is presented. The implementation produces models where all the equations, which are on a form that should be understandable to someone with a background in engineering thermodynamics, can be accessed and modified individually. The implementation was designed to make...

  15. Improved production of single domain antibodies with two disulfide bonds by co-expression of chaperone proteins in the Escherichia coli periplasm.

    Science.gov (United States)

    Shriver-Lake, Lisa C; Goldman, Ellen R; Zabetakis, Daniel; Anderson, George P

    2017-04-01

    Single domain antibodies are recombinantly expressed variable domains derived from camelid heavy chain antibodies. Natural single domain antibodies can have noncanonical disulfide bonds between their complementarity-determining regions that help position the binding site. In addition, engineering a second disulfide bond serves to tie together β-sheets thereby inhibiting unfolding. Unfortunately, the additional disulfide bond often significantly decreases yield, presumably due to formation of incorrect disulfide bonds during the folding process. Here, we demonstrate that inclusion of the helper plasmid pTUM4, which results in the expression of four chaperones, DsbA, DsbC, FkpA, and SurA, increased yield on average 3.5-fold for the nine multi-disulfide bond single domain antibodies evaluated. No increase in production was observed for single domain antibodies containing only the canonical disulfide bond. Published by Elsevier B.V.

  16. 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

  17. Investigation of Cyclic Deformation and Fatigue of Polycrystalline Cu under Pure Compression Cyclic Loading Conditions

    Science.gov (United States)

    Hsu, Tzu-Yin Jean

    It is commonly accepted that fatigue crack is initiated under tensile fatigue stresses. However, practical examples demonstrate that cracks may also initiate under pure compressive fluctuating loads such as the failures observed in aircraft landing gear frames. However, the mechanism of such failures is rarely investigated. Furthermore, knowledge on cyclic deformation response under pure compressive fatigue condition is also very limited or non-existent. Our recent work already verified that fatigue cracks may nucleate from stress concentration sites under pure compression fatigue, but whether or not a form of stress concentration is always needed to initiate a crack under pure compression fatigue remains uncertain. In this study, compression fatigue tests under different peak stresses were carried out on smooth bars of fully annealed OFHC Copper. The purpose of these tests is to investigate not only the cyclic deformation response but also the possibility of crack nucleation without the stress concentrator. Results showed that overall the cyclic stress-strain response and microstructural evolution of OFHC Copper under pure compression fatigue exhibits rather dissimilar behaviour compared to those under symmetrical fatigue. The specimens hardened rapidly within 10 cycles under pure compression fatigue unlike the gradual cyclic hardening behaviour in symmetrical fatigue with the same peak stress amplitude. Compressive cyclic creep behaviour was also observed under the same testing conditions. Moreover, unlike conventional tension-compression fatigue, only moderate slip activity was detectable on the surface instead of typical PSB features detected from TEM observations. The surface observations has revealed that surface slip bands did not increase in number nor did they become more pronounced in height with increasing number of cycles. In addition, surface roughening by grain boundary extrusion was detected to become more severe as the cycling progressed. Therefore

  18. SHuffle, a novel Escherichia coli protein expression strain capable of correctly folding disulfide bonded proteins in its cytoplasm

    Directory of Open Access Journals (Sweden)

    Lobstein Julie

    2012-05-01

    Full Text Available Abstract Background Production of correctly disulfide bonded proteins to high yields remains a challenge. Recombinant protein expression in Escherichia coli is the popular choice, especially within the research community. While there is an ever growing demand for new expression strains, few strains are dedicated to post-translational modifications, such as disulfide bond formation. Thus, new protein expression strains must be engineered and the parameters involved in producing disulfide bonded proteins must be understood. Results We have engineered a new E. coli protein expression strain named SHuffle, dedicated to producing correctly disulfide bonded active proteins to high yields within its cytoplasm. This strain is based on the trxB gor suppressor strain SMG96 where its cytoplasmic reductive pathways have been diminished, allowing for the formation of disulfide bonds in the cytoplasm. We have further engineered a major improvement by integrating into its chromosome a signal sequenceless disulfide bond isomerase, DsbC. We probed the redox state of DsbC in the oxidizing cytoplasm and evaluated its role in assisting the formation of correctly folded multi-disulfide bonded proteins. We optimized protein expression conditions, varying temperature, induction conditions, strain background and the co-expression of various helper proteins. We found that temperature has the biggest impact on improving yields and that the E. coli B strain background of this strain was superior to the K12 version. We also discovered that auto-expression of substrate target proteins using this strain resulted in higher yields of active pure protein. Finally, we found that co-expression of mutant thioredoxins and PDI homologs improved yields of various substrate proteins. Conclusions This work is the first extensive characterization of the trxB gor suppressor strain. The results presented should help researchers design the appropriate protein expression conditions using

  19. Collision Induced Dissociation Products of Disulfide-Bonded Peptides: Ions Result from the Cleavage of More Than One Bond

    Science.gov (United States)

    Clark, Daniel F.; Go, Eden P.; Toumi, Melinda L.; Desaire, Heather

    2011-03-01

    Disulfide bonds are a post-translational modification (PTM) that can be scrambled or shuffled to non-native bonds during recombinant expression, sample handling, or sample purification. Currently, mapping of disulfide bonds is not easy because of various sample requirements and data analysis difficulties. One step towards facilitating this difficult work is developing a better understanding of how disulfide-bonded peptides fragment during collision induced dissociation (CID). Most automated analysis algorithms function based on the assumption that the preponderance of product ions observed during the dissociation of disulfide-bonded peptides result from the cleavage of just one peptide bond, and in this report we tested that assumption by extensively analyzing the product ions generated when several disulfide-bonded peptides are subjected to CID on a quadrupole time of flight (QTOF) instrument. We found that one of the most common types of product ions generated resulted from two peptide bond cleavages, or a double cleavage. We found that for several of the disulfide-bonded peptides analyzed, the number of double cleavage product ions outnumbered those of single cleavages. The influence of charge state and precursor ion size was investigated, to determine if those parameters dictated the amount of double cleavage product ions formed. It was found in this sample set that no strong correlation existed between the charge state or peptide size and the portion of product ions assigned as double cleavages. These data show that these ions could account for many of the product ions detected in CID data of disulfide bonded peptides. We also showed the utility of double cleavage product ions on a peptide with multiple cysteines present. Double cleavage products were able to fully characterize the bonding pattern of each cysteine where typical single b/ y cleavage products could not.

  20. A cyclically actuated electrolytic drug delivery device

    KAUST Repository

    Yi, Ying

    2015-01-01

    This work, focusing on an implantable drug delivery system, presents the first prototype electrolytic pump that combines a catalytic reformer and a cyclically actuated mode. These features improve the release performance and extend the lifetime of the device. Using our platinum (Pt)-coated carbon fiber mesh that acts as a catalytic reforming element, the cyclical mode is improved because the faster recombination rate allows for a shorter cycling time for drug delivery. Another feature of our device is that it uses a solid-drug-in-reservoir (SDR) approach, which allows small amounts of a solid drug to be dissolved in human fluid, forming a reproducible drug solution for long-term therapies. We have conducted proof-of-principle drug delivery studies using such an electrolytic pump and solvent blue 38 as the drug substitute. These tests demonstrate power-controlled and pulsatile release profiles of the chemical substance, as well as the feasibility of this device. A drug delivery rate of 11.44 ± 0.56 μg min-1 was achieved by using an input power of 4 mW for multiple pulses, which indicates the stability of our system. © The Royal Society of Chemistry 2015.

  1. Effects of Cyclic Loading on Gravel

    Science.gov (United States)

    Modoni, Giuseppe; Dan, Le Quang; Koseki, Junichi; Maqbool, Sajjad

    The effects of a large number of load repetitions on gravel are discussed based on experimental evidences. To this purpose the results of several triaxial tests carried out on a coarse grained soil, artificially reconstituted at different prescribed levels of density, are reported and compared. The tests reproduce a broad variety of possible field conditions, being performed at different mean effective stresses, by applying sequences of load-unload repetitions, different by number of repetitions and amplitudes of cycles. The analysis of the experimental results has been conducted by focusing the attention on the plastic components of strain, calculated by scaling the non negligible elastic components from the measured ones. A theory for the interpretation of monotonic test results is first briefly presented to form the basis of the analysis of the cyclic test results. This last is referred to the evolution of the stress-strain relationships along with load repetitions, and particularly to the accumulation of distortional and volumetric strains and to the effects of previous cyclic loading on subsequent soil response.

  2. Fault diagnosis of rolling bearing based on cyclic spectrum density

    International Nuclear Information System (INIS)

    Shi Qingfeng; Yan Junming; Zhang Yanhong

    2009-01-01

    The paper considered the vibration signals of rotating equipment as cyclo stationary signals through analyzing the features of this kind of signals. Based on the analytic method of cyclic spectrum density, the paper pointed out that the impact frequency could be extracted effectively with the help of scanning cyclic frequency domain. The validity of the method of cyclic spectrum density is proved by simulating signals and the method is applied to the diagnosis of rolling bearings. (authors)

  3. Synthesis of Cyclic Py-Im Polyamide Libraries

    OpenAIRE

    Li, Benjamin C.; Montgomery, David C.; Puckett, James W.; Dervan, Peter B.

    2013-01-01

    Cyclic Py-Im polyamides containing two GABA turn units exhibit enhanced DNA binding affinity, but extensive studies of their biological properties have been hindered due to synthetic inaccessibility. A facile modular approach toward cyclic polyamides has been developed via microwave-assisted solid-phase synthesis of hairpin amino acid oligomer intermediates followed by macrocyclization. A focused library of cyclic polyamides 1–7 targeted to the androgen response element (ARE) and the estrogen...

  4. Cyclical mastalgia: Prevalence and associated determinants in Hamadan City, Iran

    OpenAIRE

    Shobeiri, Fatemeh; Oshvandi, Khodayar; Nazari, Mansour

    2016-01-01

    Objective: To assess prevalence of cyclical mastalgia and its main determinants in women who attended in health centers of Hamadan City, Iran. Methods: This case–control study was conducted on 400 women (case: cyclical mastalgia, n = 240; control: without cyclical mastalgia, n = 160) who attended family planning clinic for routine follow-up in health centers. The cluster sampling was used. Information was collected by interviewing and using a standardized validated questionnaire. Severity ...

  5. 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.

  6. Real-time Monitoring of Intermediates Reveals the Reaction Pathway in the Thiol-Disulfide Exchange between Disulfide Bond Formation Protein A (DsbA) and B (DsbB) on a Membrane-immobilized Quartz Crystal Microbalance (QCM) System*

    Science.gov (United States)

    Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio

    2013-01-01

    Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

  7. Cyclic Team Teaching in Ninth-Grade Physical Science

    Science.gov (United States)

    Swainson, Ralph; And Others

    1971-01-01

    Presents the instructional procedures used in a team teaching situation. Identifies advantages and problems encountered in cyclic approach to demonstration, laboratory, programed, and large group activities. (DS)

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. "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.

  9. 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.

  10. 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

  11. Estrous Cyclicity in Mice During Simulated Weightlessness

    Science.gov (United States)

    Moyer, E. L.; Talyansky, Y.; Scott, R. T.; Tash, J. S.; Christenson, L. K.; Alwood, J. S.; Ronca, A. E.

    2017-01-01

    Hindlimb unloading (HU) is a rodent model system used to simulate weightlessness experienced in space. However, some effects of this approach on rodent physiology are under-studied, specifically the effects on ovarian estrogen production which drives the estrous cycle. To resolve this deficiency, we conducted a ground-based validation study using the HU model, while monitoring estrous cycles in 16-weeks-old female C57BL6 mice. Animals were exposed to HU for 12 days following a 3 day HU cage acclimation period, and estrous cycling was analyzed in HU animals (n=22), normally loaded HU Cage Pair-Fed controls (CPF; n=22), and Vivarium controls fed ad libitum (VIV; n=10). Pair feeding was used to control for potential nutritional deficits on ovarian function. Vaginal cells were sampled daily in all mice via saline lavage. Cells were dried and stained with crystal violet, and the smears evaluated using established vaginal cytology techniques by two individuals blinded to the animal treatment group. Estrous cyclicity was disrupted in nearly all HU and CPF mice, while those maintained in VIV had an average normal cycle length of 4.8+/- 0.5 days, with all stages in the cycle visibly observed. CPF and HU animals arrested in the diestrous phase, which precedes the pre-ovulatory estrogen surge. Additionally, infection-like symptoms characterized by vaginal discharge and swelling arose in several HU animals, which we suspect was due to an inability of these mice to properly groom themselves, and/or due to the change in the gravity vector relative to the vaginal opening, which prevented drainage of the lavage solution. Pair-feeding resulted in similar weight gains of HU and CPF (1.5% vs 3.0%, respectively). The current results indicate that pair-feeding controlled weight gain and that the HU cage alone influenced estrous cyclicity. Thus, longer acclimation needs to be tested to determine if and when normal estrous cycling resumes in non-loaded mice in HU cages prior to HU

  12. Estrous Cyclicity of Mice During Simulated Weightlessness

    Science.gov (United States)

    Moyer, Eric; Talyansky, Yuli; Scott, Ryan; Tash, Joseph; Christenson, Lane; Alwood, Joshua; Ronca, April

    2017-01-01

    Hindlimb unloading (HU) is a rodent model system used to simulate weightlessness experienced in space. However, some effects of this approach on rodent physiology are under-studied, specifically the effects on ovarian estrogen production which drives the estrous cycle. To resolve this deficiency, we conducted a ground-based validation study using the HU model, while monitoring estrous cycles in 16-weeks-old female C57BL6 mice. Animals were exposed to HU for 12 days following a 3 day HU cage acclimation period, and estrous cycling was analyzed in HU animals (n22), normally loaded HU Cage Pair-Fed controls (CPF; n22), and Vivarium controls fed ad libitum (VIV; n10). Pair feeding was used to control for potential nutritional deficits on ovarian function. Vaginal cells were sampled daily in all mice via saline lavage. Cells were dried and stained with crystal violet, and the smears evaluated using established vaginal cytology techniques by two individuals blinded to the animal treatment group. Estrous cyclicity was disrupted in nearly all HU and CPF mice, while those maintained in VIV had an average normal cycle length of 4.8 0.5 days, with all stages in the cycle visibly observed. CPF and HU animals arrested in the diestrous phase, which precedes the pre-ovulatory estrogen surge. Additionally, infection-like symptoms characterized by vaginal discharge and swelling arose in several HU animals, which we suspect was due to an inability of these mice to properly groom themselves, andor due to the change in the gravity vector relative to the vaginal opening, which prevented drainage of the lavage solution. Pair-feeding resulted in similar weight gains of HU and CPF (1.5 vs 3.0, respectively). The current results indicate that pair-feeding controlled weight gain and that the HU cage alone influenced estrous cyclicity. Thus, longer acclimation needs to be tested to determine if and when normal estrous cycling resumes in non-loaded mice in HU cages prior to HU testing. Future

  13. Study of the helium cross-section of unsymmetric disulfide self-assembled monolayers on Au(111)

    Energy Technology Data Exchange (ETDEWEB)

    Albayrak, Erol [Department of Materials and Metallurgical Engineering, Ahi Evran University, Kırşehir 40000 (Turkey); Karabuga, Semistan [Department of Chemistry, Kahramanmaraş Sütçü İmam University, Kahramanmaraş 46030 (Turkey); Bracco, Gianangelo [CNR-IMEM and Department of Physics, University of Genoa, Via Dodecaneso 33, Genoa 16146 (Italy); Danışman, M. Fatih, E-mail: danisman@metu.edu.tr [Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)

    2016-12-30

    Highlights: • Unsymmetrtic disulfide (HDD and HOD) self assembled monolayers were grown on Au(111) by supersonic molecular beam deposition. • Helium scattering cross sections for these two different unsymmetric disulfides were determined. • A common low temperature film phase was observed for the studied disulfides. - Abstract: We have investigated the formation of self-assembled monolayers (SAMs) of 11-hydroxyundecyl decyl disulfide (CH{sub 3}-(CH{sub 2}){sub 9}-S-S-(CH{sub 2}){sub 11}-OH, HDD) and 11-hydroxyundecyl octadecyl disulfide (CH{sub 3}-(CH{sub 2}){sub 17}-S-S-(CH{sub 2}){sub 11}-OH, HOD) produced by supersonic molecular beam deposition (SMBD). The study has been carried out by means of helium diffraction at very low film coverage. In this regime helium single molecule cross sections have been estimated in a temperature range between 100 K and 450 K. The results show a different behavior above 300 K that has been interpreted as the starting of mobility with the formation of two thiolate moieties either linked by a gold adatom or distant enough to prevent cross section overlapping. Finally, helium diffraction patterns measured at 80 K for the SAMs grown at 200 K are discussed and the results support the proposed hypothesis of molecular dissociation based on the cross section data.

  14. Antagonistic effect of disulfide-rich peptide aptamers selected by cDNA display on interleukin-6-dependent cell proliferation

    International Nuclear Information System (INIS)

    Nemoto, Naoto; Tsutsui, Chihiro; Yamaguchi, Junichi; Ueno, Shingo; Machida, Masayuki; Kobayashi, Toshikatsu; Sakai, Takafumi

    2012-01-01

    Highlights: ► Disulfide-rich peptide aptamer inhibits IL-6-dependent cell proliferation. ► Disulfide bond of peptide aptamer is essential for its affinity to IL-6R. ► Inhibitory effect of peptide depends on number and pattern of its disulfide bonds. -- Abstract: Several engineered protein scaffolds have been developed recently to circumvent particular disadvantages of antibodies such as their large size and complex composition, low stability, and high production costs. We previously identified peptide aptamers containing one or two disulfide-bonds as an alternative ligand to the interleukin-6 receptor (IL-6R). Peptide aptamers (32 amino acids in length) were screened from a random peptide library by in vitro peptide selection using the evolutionary molecular engineering method “cDNA display”. In this report, the antagonistic activity of the peptide aptamers were examined by an in vitro competition enzyme-linked immunosorbent assay (ELISA) and an IL-6-dependent cell proliferation assay. The results revealed that a disulfide-rich peptide aptamer inhibited IL-6-dependent cell proliferation with similar efficacy to an anti-IL-6R monoclonal antibody.

  15. Disulfide Bonds within the C2 Domain of RAGE Play Key Roles in Its Dimerization and Biogenesis

    Science.gov (United States)

    Wei, Wen; Lampe, Leonie; Park, Sungha; Vangara, Bhavana S.; Waldo, Geoffrey S.; Cabantous, Stephanie; Subaran, Sarah S.; Yang, Dongmei; Lakatta, Edward G.; Lin, Li

    2012-01-01

    Background The receptor for advanced glycation end products (RAGE) on the cell surface transmits inflammatory signals. A member of the immunoglobulin superfamily, RAGE possesses the V, C1, and C2 ectodomains that collectively constitute the receptor's extracellular structure. However, the molecular mechanism of RAGE biogenesis remains unclear, impeding efforts to control RAGE signaling through cellular regulation. Methodology and Result We used co-immunoprecipitation and crossing-linking to study RAGE oligomerization and found that RAGE forms dimer-based oligomers. Via non-reducing SDS-polyacrylamide gel electrophoresis and mutagenesis, we found that cysteines 259 and 301 within the C2 domain form intermolecular disulfide bonds. Using a modified tripartite split GFP complementation strategy and confocal microscopy, we also found that RAGE dimerization occurs in the endoplasmic reticulum (ER), and that RAGE mutant molecules without the double disulfide bridges are unstable, and are subjected to the ER-associated degradation. Conclusion Disulfide bond-mediated RAGE dimerization in the ER is the critical step of RAGE biogenesis. Without formation of intermolecular disulfide bonds in the C2 region, RAGE fails to reach cell surface. Significance This is the first report of RAGE intermolecular disulfide bond. PMID:23284645

  16. Determination and reoxidation of the disulfide bridges of a squash-type trypsin inhibitor from Sechium edule seeds.

    Science.gov (United States)

    Faça, Vitor M; Pereira, Sandra R; Laure, Hélen J; Greene, Lewis J

    2004-07-01

    The determination of the disulfide pairings of SETI-II, a trypsin inhibitor isolated from Sechium edule, is described herein. The inhibitor contains 31 amino acid residues per mol, 6 of which are cysteine. Forty-five nmol (160 microg) of SETI-II was hydrolyzed with 20 microg thermolysin for 48 hr at 45 degrees C, and peptides were separated by reverse phase high performance liquid chromatography (RP-HPLC). The major products were identified by amino acid composition, Edman degradation, and on the basis of the sequence of the inhibitor. The disulfide bridge pairings and (yields) are: Cys1-Cys4 (79%), Cys2-Cys5 (21%) and Cys3-Cys6 (43%). When the reduced inhibitor was reoxidized with glutathione reduced form (GSH)/glutathione oxidized form (GSSG) at pH 8.5 for 3 hr, full activity was recovered. These data show that disulfide bridge pairing and oxidation can be determined at nanomole levels and that sensitive and quantitative Edman degradation can eliminate the final time- and material-consuming step of disulfide determinations by eliminating the need to purify and cleave each peptide containing a disulfide bridge.

  17. Biologic activity of cyclic and caged phosphates: a review.

    Science.gov (United States)

    Lorke, Dietrich E; Stegmeier-Petroianu, Anka; Petroianu, Georg A

    2017-01-01

    The recognition in the early 1960s by Morifusa Eto that tri-o-cresyl phosphate (TOCP) is hydroxylated by the cytochrome P450 system to an intermediate that spontaneously cyclizes to a neurotoxic phosphate (saligenin phosphate ester) ignited the interest in this group of compounds. Only the ortho isomer can cyclize and clinically cause Organo Phosphate Induced Delayed Neurotoxicity (OPIDN); the meta and para isomers of tri-cresyl phosphate are not neuropathic because they are unable to form stable cyclic saligenin phosphate esters. This review identifies the diverse biological effects associated with various cyclic and caged phosphates and phosphonates and their possible use. Cyclic compounds that inhibit acetylcholine esterase (AChE), such as salithion, can be employed as pesticides. Others are neurotoxic, most probably because of inhibition of neuropathy target esterase (NTE). Cyclic phosphates that inhibit lipases, the cyclipostins, possibly represent promising therapeutic avenues for the treatment of type 2 diabetes mellitus and/or microbial infections; those compounds inhibiting β-lactamase may prevent bacterial resistance against β-lactam antibiotics. Naturally occurring cyclic phosphates, such as cyclic AMP, cyclic phosphatidic acid and the ryanodine receptor modulator cyclic adenosine diphosphate ribose, play an important physiological role in signal transduction. Moreover, some cyclic phosphates are GABA-antagonists, while others are an essential component of Molybdenum-containing enzymes. Some cyclic phosphates (cyclophosphamide, ifosfamide) are clinically used in tumor therapy, while the coupling of therapeutic agents with other cyclic phosphates (HepDirect® Technology) allows drugs to be targeted to specific organs. Possible clinical applications of these compounds are considered. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  18. Differential regulation of tissue thiol-disulfide redox status in a murine model of peritonitis

    Directory of Open Access Journals (Sweden)

    Benton Shana M

    2012-10-01

    Full Text Available Abstract Background Glutathione (GSH/glutathione disulfide (GSSG and cysteine (Cys/cystine (CySS are major redox pools with important roles in cytoprotection. We determined the impact of septic peritonitis on thiol-disulfide redox status in mice. Methods FVB/N mice (6–12 week old; 8/group underwent laparotomy with cecal ligation and puncture (CLP or laparotomy alone (control. Sections of ileum, colon, lung and liver were obtained and GSH, GSSG, Cys and CySS concentrations determined by HPLC 24 h after laparotomy. Redox potential [Eh in millivolts (mV] of the GSH/GSSG and Cys/CySS pools was calculated using the Nernst equation. Data were analyzed by ANOVA (mean ± SE. Results GSH/GSSG Eh in ileum, colon, and liver was significantly oxidized in septic mice versus control mice (ileum: septic −202±4 versus control −228±2 mV; colon: -195±8 versus −214±1 mV; and liver: -194±3 vs. -210±1 mV, all Ph was unchanged with CLP, while liver and lung Cys/CySS Eh became significantly more reducing (liver: septic = −103±3 versus control −90±2 mV; lung: -101±5 versus −81±1 mV, each P Conclusions Septic peritonitis induced by CLP oxidizes ileal and colonic GSH/GSSG redox but Cys/CySS Eh remains unchanged in these intestinal tissues. In liver, CLP oxidizes the GSH/GSSG redox pool and CyS/CySS Eh becomes more reducing; in lung, CLP does not alter GSH/GSSG Eh, and Cys/CySS Eh is less oxidized. CLP-induced infection/inflammation differentially regulates major thiol-disulfide redox pools in this murine model.

  19. Magnetoelastic Demagnetization of Steel under Cyclic Loading

    Science.gov (United States)

    Muratov, K. R.; Novikov, V. F.; Neradovskii, D. F.; Kazakov, R. Kh.

    2018-01-01

    Magnetoelastic demagnetization of steel samples under cyclic tensile loads has been analyzed. It has been established that values of residual magnetization that correspond to peak loads are characterized by the power-law dependence on the number of loading cycles. In some cases, in the region of high loads, the qualitative transition to exponential dependence has been observed. Coefficients of the power-law approximation of peak magnetization depend on the value of amplitude load and have specific characteristics in the vicinity of characteristic loads. The ratios of approximated slide load coefficients depending on the load are common for the three considered samples, and there is an outburst in the vicinity of the fatigue limit, which can be used as the basis for developing the rapid nondestructive method for determination of this limit.

  20. The cyclic universe: An informal introduction

    International Nuclear Information System (INIS)

    Steinhaxdt, Paul J.; Turok, Neil

    2003-01-01

    The Cyclic Model is a radical, new cosmological scenario which proposes that the Universe undergoes an endless sequence of epochs which begin with a 'big bang' and end in a 'big crunch.' When the Universes bounces from contraction to re-expansion, the temperature and density remain finite. The model does not include a period of rapid inflation, yet it reproduces all of the successful predictions of standard big bang and inflationary cosmology. We point out numerous novel elements that have not been used previously which may open the door to further alternative cosmologies. Although the model is motivated by M-theory, branes and extra dimensions, here we show that the scenario can be described almost entirely in terms of conventional 4d field theory and 4d cosmology

  1. Janus cyclic peptide-polymer nanotubes

    Science.gov (United States)

    Danial, Maarten; My-Nhi Tran, Carmen; Young, Philip G.; Perrier, Sébastien; Jolliffe, Katrina A.

    2013-11-01

    Self-assembled nanotubular structures have numerous potential applications but these are limited by a lack of control over size and functionality. Controlling these features at the molecular level may allow realization of the potential of such structures. Here we report a new generation of self-assembled cyclic peptide-polymer nanotubes with dual functionality in the form of either a Janus or mixed polymeric corona. A ‘relay’ synthetic strategy is used to prepare nanotubes with a demixing or mixing polymeric corona. Nanotube structure is assessed in solution using 1H-1H nuclear Overhauser effect spectroscopy NMR, and in bulk using differential scanning calorimetry. The Janus nanotubes form artificial pores in model phospholipid bilayers. These molecules provide a viable pathway for the development of intriguing nanotubular structures with dual functionality via a demixing or a mixing polymeric corona and may provide new avenues for the creation of synthetic transmembrane protein channel mimics.

  2. Cyclic steps incised on experimental bedrock

    Science.gov (United States)

    Yokokawa, M.; Kyogoku, A.; Kotera, A.; Izumi, N.

    2013-12-01

    In rivers flowing in mountain areas, a series of steps are often observed on bedrock. They are thought to be cyclic steps formed due to erosion of bedrock, which should be driven by abrasion due to bedload sediment transport. We demonstrated a series of flume experiments of the formation of cyclic steps on bedrock by abrasion due to bedload transportation using weak mortar as the model bedrock. We also compared the shapes of the steps reproduced in the experiments with those obtained in the analysis. The experiments were conducted using a 1.5 m long, 2 cm wide, and 20 cm deep flume made of glass in Osaka Institute of Technology. The flume has 10-cm-high weirs at both ends, so that there is a 10-cm-deep reservoir. We put mortar into the reservoir and hardened it. In order to make a highly erodible mortar, we casted the mortar with extremely low amount of cement. The ratio of cement, sand (0.2 mm in diameter), and water is x:150:50 (x ranges 1-3). The flume is tilted by 10 degrees. The water and colored sand is supplied from a head tank to the upstream end of the flume, flows on 'model bedrock' in the flume, and was dropped from the downstream end. We observed morphological changes of the surface of the bedrock by photos. We also used a laser displacement sensor to measure the surface topography of the 'model bedrock' before and after each run. The configuration of steps largely depends on the hardness of model bedrocks. In the case of the softest model bedrock (cement-sand-water ratio is 1:150:50) with small amount of sand, long-drawn potholes tend to be formed. Clear cyclic steps are formed on harder model bedrocks with large cement-sand-water ratios such as 2:150:50 and 3:150:50. When a series of steps are formed on the bed, typical wavelength and wave height are approximately 20 cm, and 2 - 3 cm, respectively. The general shape of a step is characterized by a relatively long downward-inclined slope just upstream of a short upward-inclined slope. The feature of

  3. Protein Misfolding Cyclic Amplification of Infectious Prions.

    Science.gov (United States)

    Moda, Fabio

    2017-01-01

    Transmissible spongiform encephalopathies, or prion diseases, are a group of incurable disorders caused by the accumulation of an abnormally folded prion protein (PrP Sc ) in the brain. According to the "protein-only" hypothesis, PrP Sc is the infectious agent able to propagate the disease by acting as a template for the conversion of the correctly folded prion protein (PrP C ) into the pathological isoform. Recently, the mechanism of PrP C conversion has been mimicked in vitro using an innovative technique named protein misfolding cyclic amplification (PMCA). This technology represents a great tool for studying diverse aspects of prion biology in the field of basic research and diagnosis. Moreover, PMCA can be expanded for the study of the misfolding process associated to other neurodegenerative diseases, including Alzheimer's disease, Parkinson's disease, and frontotemporal lobar degeneration. © 2017 Elsevier Inc. All rights reserved.

  4. Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

    DEFF Research Database (Denmark)

    Diemer, Sanna L.; Kristensen, Morten; Rasmussen, Brian

    2015-01-01

    combinatorial libraries (DCLs) ensuring thermodynamic control over the system. If more than one reversible reaction operates in a single dynamic combinatorial library, the complexity of the system increases dramatically, and so does its possible applications. One can imagine two reversible reactions...... that operate simultaneously or two reversible reactions that operate independently. Both these scenarios have advantages and disadvantages. In this contribution, we show how disulfide exchange and boronic ester transesterification can function simultaneous in dynamic combinatorial libraries under appropriate...... conditions. We describe the detailed studies necessary to establish suitable reaction conditions and highlight the analytical techniques appropriate to study this type of system....

  5. Chemically exfoliated large-area two-dimensional flakes of molybdenum disulfide for device applications

    Directory of Open Access Journals (Sweden)

    Vivek Pachauri

    2013-09-01

    Full Text Available A solution-based exfoliation method for obtaining large-area two-dimensional flakes of molybdenum disulfide, followed by the fabrication of electrical devices is presented in this manuscript. The exfoliation method is based on the use of an aprotic solvent, namely, acetonitrile under mild sonication steps. In order to fabricate devices, a dielectrophoresis technique is used for transferring MoS2 flakes site-specifically on to the electrode pairs pre-written on the glass chips. The devices fabricated thus can be operated as chemical sensor in liquids while investigations under photo illumination indicate that such devices can also efficiently function as photodetectors.

  6. Influence of the degree of crosslinking on the depolymerization of disulfide polymer

    International Nuclear Information System (INIS)

    Rekalicj, J.V.; Radosavljevicj, D.S.; Popovicj, E.M.; Stashicj, L.

    1976-01-01

    The action of nucleophilic reagents (hydrogen sulfide ion, dithionite ion and hydrazine) on disulfide polymers prepd. from bis-2-chloroethyl formal and 1,2,3-trichloropropane, taken in various mol rations is studied. The depolymerization efficiency is higher with hydrazine and dithionite than with a mixt. of sodium hydrogen sulfide and sodium sulfite. An interpretation of the results is given, attempting to correlate the content of SH-groups in the obtained product with the same quantity in some defined compds. which can be present after the depolymerization

  7. Dissecting molecular interactions involved in recognition of target disulfides by the barley thioredoxin system

    DEFF Research Database (Denmark)

    Björnberg, Olof; Maeda, Kenji; Svensson, Birte

    2012-01-01

    thioredoxin reductase. HvTrxh2 M88G and M88A adjacent to the invariant cis-proline lost efficiency in both BASI disulfide reduction and recycling by thioredoxin reductase. These effects were further pronounced in M88P lacking a backbone NH group. Remarkably, HvTrxh2 E86R in the same loop displayed overall...... reductase. The findings support important roles in target recognition of backbone-backbone hydrogen bond and electrostatic interactions and are discussed in relation to earlier structural and functional studies of thioredoxins and related proteins. © 2012 American Chemical Society....

  8. Defect-Mediated Lithium Adsorption and Diffusion on Monolayer Molybdenum Disulfide

    OpenAIRE

    Sun, Xiaoli; Wang, Zhiguo; Fu, Yong Qing

    2015-01-01

    Monolayer Molybdenum Disulfide (MoS2) is a promising anode material for lithium ion batteries because of its high capacities. In this work, first principle calculations based on spin density functional theory were performed to investigate adsorption and diffusion of lithium on monolayer MoS2 with defects, such as single- and few-atom vacancies, antisite, and grain boundary. The values of adsorption energies on the monolayer MoS2 with the defects were increased compared to those on the pristin...

  9. Design of new disulfide-based organic compounds for the improvement of self-healing materials.

    Science.gov (United States)

    Matxain, Jon M; Asua, José M; Ruipérez, Fernando

    2016-01-21

    Self-healing materials are a very promising kind of materials due to their capacity to repair themselves. Among others, diphenyl disulfide-based compounds (Ph2S2) appear to be among the best candidates to develop materials with optimum self-healing properties. However, few is known regarding both the reaction mechanism and the electronic structure that make possible such properties. In this vein, theoretical approaches are of great interest. In this work, we have carried out theoretical calculations on a wide set of different disulfide compounds, both aromatic and aliphatic, in order to elucidate the prevalent reaction mechanism and the necessary electronic conditions needed for improved self-healing properties. Two competitive mechanisms were considered, namely, the metathesis and the radical-mediated mechanism. According to our calculations, the radical-mediated mechanism is the responsible for this process. The formation of sulfenyl radicals strongly depends on the S-S bond strength, which can be modulated chemically by the use of proper derivatives. At this point, amino derivatives appear to be the most promising ones. In addition to the S-S bond strength, hydrogen bonding between disulfide chains seems to be relevant to favour the contact among disulfide units. This is crucial for the reaction to take place. The calculated hydrogen bonding energies are of the same order of magnitude as the S-S bond energies. Finally, reaction barriers have been analysed for some promising candidates. Two reaction mechanisms were compared, namely, the [2+2] metathesis reaction mechanism and the [2+1] radical-mediated mechanism. No computational evidence for the existence of any transition state for the metathesis mechanism was found, which indicates that the radical-mediated mechanism is the one responsible in the self-healing process of these materials. Interestingly, the calculated reaction barriers are around 10 kcal mol(-1) regardless the substituent employed. All these

  10. The Two-Dimensional Nanocomposite of Molybdenum Disulfide and Nitrogen-Doped Graphene Oxide for Efficient Counter Electrode of Dye-Sensitized Solar Cells

    Science.gov (United States)

    Cheng, Chao-Kuang; Lin, Che-Hsien; Wu, Hsuan-Chung; Ma, Chen-Chi M.; Yeh, Tsung-Kuang; Chou, Huei-Yu; Tsai, Chuen-Horng; Hsieh, Chien-Kuo

    2016-02-01

    In this study, we reported the synthesis of the two-dimensional (2D) nanocomposite of molybdenum disulfide and nitrogen-doped graphene oxide (MoS2/nGO) as a platinum-free counter electrode (CE) for dye-sensitized solar cells (DSSCs). X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy were used to examine the characteristics of the 2D nanocomposite of MoS2/nGO. The cyclic voltammetry (CV), electrochemical impedance spectra (EIS), and the Tafel polarization measurements were carried out to examine the electrocatalytic abilities. XPS and Raman results showed the 2D behaviors of the prepared nanomaterials. HRTEM micrographs showed the direct evidence of the 2D nanocomposite of MoS2/nGO. The results of electrocatalytic examinations indicated the MoS2/nGO owning the low charge transfer resistance, high electrocatalytic activity, and fast reaction kinetics for the reduction of triiodide to iodide on the electrolyte-electrode interface. The 2D nanocomposite of MoS2/nGO combined the advantages of the high specific surface of nGO and the plenty edge sites of MoS2 and showed the promoted properties different from those of their individual constituents to create a new outstanding property. The DSSC with MoS2/nGO nanocomposite CE showed a photovoltaic conversion efficiency (PCE) of 5.95 % under an illumination of AM 1.5 (100 mW/cm2), which was up to 92.2 % of the DSSC with the conventional platinum (Pt) CE (PCE = 6.43 %). These results reveal the potential of the MoS2/nGO nanocomposite in the use of low-cost, scalable, and efficient Pt-free CEs for DSSCs.

  11. The Two-Dimensional Nanocomposite of Molybdenum Disulfide and Nitrogen-Doped Graphene Oxide for Efficient Counter Electrode of Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Cheng, Chao-Kuang; Lin, Che-Hsien; Wu, Hsuan-Chung; Ma, Chen-Chi M; Yeh, Tsung-Kuang; Chou, Huei-Yu; Tsai, Chuen-Horng; Hsieh, Chien-Kuo

    2016-12-01

    In this study, we reported the synthesis of the two-dimensional (2D) nanocomposite of molybdenum disulfide and nitrogen-doped graphene oxide (MoS2/nGO) as a platinum-free counter electrode (CE) for dye-sensitized solar cells (DSSCs). X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy were used to examine the characteristics of the 2D nanocomposite of MoS2/nGO. The cyclic voltammetry (CV), electrochemical impedance spectra (EIS), and the Tafel polarization measurements were carried out to examine the electrocatalytic abilities. XPS and Raman results showed the 2D behaviors of the prepared nanomaterials. HRTEM micrographs showed the direct evidence of the 2D nanocomposite of MoS2/nGO. The results of electrocatalytic examinations indicated the MoS2/nGO owning the low charge transfer resistance, high electrocatalytic activity, and fast reaction kinetics for the reduction of triiodide to iodide on the electrolyte-electrode interface. The 2D nanocomposite of MoS2/nGO combined the advantages of the high specific surface of nGO and the plenty edge sites of MoS2 and showed the promoted properties different from those of their individual constituents to create a new outstanding property. The DSSC with MoS2/nGO nanocomposite CE showed a photovoltaic conversion efficiency (PCE) of 5.95 % under an illumination of AM 1.5 (100 mW/cm(2)), which was up to 92.2 % of the DSSC with the conventional platinum (Pt) CE (PCE = 6.43 %). These results reveal the potential of the MoS2/nGO nanocomposite in the use of low-cost, scalable, and efficient Pt-free CEs for DSSCs.

  12. Enhanced Efficiency of Dye-Sensitized Solar Counter Electrodes Consisting of Two-Dimensional Nanostructural Molybdenum Disulfide Nanosheets Supported Pt Nanoparticles

    Directory of Open Access Journals (Sweden)

    Chao-Kuang Cheng

    2017-10-01

    Full Text Available This paper reports architecturally designed nanocomposites synthesized by hybridizing the two-dimensional (2D nanostructure of molybdenum disulfide (MoS2 nanosheet (NS-supported Pt nanoparticles (PtNPs as counter electrodes (CEs for dye-sensitized solar cells (DSSCs. MoS2 NSs were prepared using the hydrothermal method; PtNPs were subsequently reduced on the MoS2 NSs via the water–ethylene method to form PtNPs/MoS2 NSs hybrids. The nanostructures and chemical states of the PtNPs/MoS2 NSs hybrids were characterized by high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Detailed electrochemical characterizations by electrochemical impedance spectroscopy, cyclic voltammetry, and Tafel-polarization measurement demonstrated that the PtNPs/MoS2 NSs exhibited excellent electrocatalytic activities, afforded a higher charge transfer rate, a decreased charge transfer resistance, and an improved exchange current density. The PtNPs/MoS2 NSs hybrids not only provided the exposed layers of 2D MoS2 NSs with a great deal of catalytically active sites, but also offered PtNPs anchored on the MoS2 NSs enhanced I3− reduction. Accordingly, the DSSCs that incorporated PtNPs/MoS2 NSs CE exhibited an outstanding photovoltaic conversion efficiency (PCE of 7.52%, which was 8.7% higher than that of a device with conventional thermally-deposited platinum CE (PCE = 6.92%.

  13. Cyclic Oxidation Behaviour of Domestic Superalloys at Elevated Temperature

    International Nuclear Information System (INIS)

    Kang, S. C.; Kim, G. M.; Chon, Y. G.

    1991-01-01

    The cyclic oxidation behaviour of commercial superalloys produced in Korea was investigated in air at 1000 .deg. C and 1100 .deg. C. Cyclic oxidation test was carried out by cyclically oxidizing the specimens in an apparatus which periodically removed the specimens from the furnace and reinserted them. The influence of growth stress and thermal stress on the cyclic oxidation was studied by examination of the oxide structures, their morphologies, and EDS line scanning of cross-section of cyclically oxidized specimens. The results showed that Inconel 601 was the best in the cyclic oxidation resistance among the tested alloys, followed by Nimonic 80A, Incoloy 825 and Inconel 718 at 1100 .deg. C. As in the case of the isothermal oxidation, relatively pure Cr 2 O 3 was effective in the beginning of cyclic oxidation experiment. But, later on, other oxidation products as well as Cr 2 O 3 were formed, resulting in the spallation of oxide scales. Especially, Nb and Mo in the alloys were determental to the cyclic oxidation behavior

  14. Classifying spaces with virtually cyclic stabilizers for linear groups

    DEFF Research Database (Denmark)

    Degrijse, Dieter Dries; Köhl, Ralf; Petrosyan, Nansen

    2015-01-01

    We show that every discrete subgroup of GL(n, ℝ) admits a finite-dimensional classifying space with virtually cyclic stabilizers. Applying our methods to SL(3, ℤ), we obtain a four-dimensional classifying space with virtually cyclic stabilizers and a decomposition of the algebraic K-theory of its...

  15. Evaluating cyclic fatigue of sealants during outdoor testing

    Science.gov (United States)

    R. Sam Williams; Steven Lacher; Corey Halpin; Christopher White

    2009-01-01

    A computer-controlled test apparatus (CCTA) and other instrumentation for subjecting sealant specimens to cyclic fatigue during outdoor exposure was developed. The CCTA enables us to use weather-induced conditions to cyclic fatigue specimens and to conduct controlled tests in-situ during the outdoor exposure. Thermally induced dimensional changes of an aluminum bar...

  16. Improvements of cyclic somatic embryogenesis of cassava (Manihot esculenta Crantz).

    NARCIS (Netherlands)

    Raemakers, C.J.J.M.; Schavemaker, C.M.; Jacobsen, E.; Visser, R.G.F.

    1993-01-01

    In cassava a cyclic system of somatic embryogenesis was developed. Primary (torpedo shaped or germinated) embryos, originating from leaf lobes, could only be obtained after culture on solid medium. Cyclic embryos, originating from embryos, could be obtained in both liquid and on solid medium. The

  17. Supplementary Material for: The arabidopsis cyclic nucleotide interactome

    KAUST Repository

    Donaldson, Lara

    2016-01-01

    Abstract Background Cyclic nucleotides have been shown to play important signaling roles in many physiological processes in plants including photosynthesis and defence. Despite this, little is known about cyclic nucleotide-dependent signaling mechanisms in plants since the downstream target proteins remain unknown. This is largely due to the fact that bioinformatics searches fail to identify plant homologs of protein kinases and phosphodiesterases that are the main targets of cyclic nucleotides in animals. Methods An affinity purification technique was used to identify cyclic nucleotide binding proteins in Arabidopsis thaliana. The identified proteins were subjected to a computational analysis that included a sequence, transcriptional co-expression and functional annotation analysis in order to assess their potential role in plant cyclic nucleotide signaling. Results A total of twelve cyclic nucleotide binding proteins were identified experimentally including key enzymes in the Calvin cycle and photorespiration pathway. Importantly, eight of the twelve proteins were shown to contain putative cyclic nucleotide binding domains. Moreover, the identified proteins are post-translationally modified by nitric oxide, transcriptionally co-expressed and annotated to function in hydrogen peroxide signaling and the defence response. The activity of one of these proteins, GLYGOLATE OXIDASE 1, a photorespiratory enzyme that produces hydrogen peroxide in response to Pseudomonas, was shown to be repressed by a combination of cGMP and nitric oxide treatment. Conclusions We propose that the identified proteins function together as points of cross-talk between cyclic nucleotide, nitric oxide and reactive oxygen species signaling during the defence response.

  18. Rank equivalent and rank degenerate skew cyclic codes

    DEFF Research Database (Denmark)

    Martinez Peñas, Umberto

    2017-01-01

    Two skew cyclic codes can be equivalent for the Hamming metric only if they have the same length, and only the zero code is degenerate. The situation is completely different for the rank metric. We study rank equivalences between skew cyclic codes of different lengths and, with the aim of finding...

  19. Structure and stability of spiro-cyclic water clusters

    Indian Academy of Sciences (India)

    Administrator

    donates two protons, resulting in an overall stabili- zation of the spiro-cyclic structure. A close scrutiny. Figure 1. Optimized geometries of different spiro- cyclic water clusters obtained using HF/6-311++G** cal- culation. These clusters are found to be stable without any reorganization during energy minimization at DFT.

  20. Development of Pore Pressure and Material Damping during Cyclic Loading

    DEFF Research Database (Denmark)

    Ibsen, Lars Bo

    1994-01-01

    The behaviour of sand during cyclic loading can be characterized as "stabilization", "instant stabilization". "pore pressure buildup" and "liquefaction". The terminologies can be defined exactly by a simple mathematical formulation based on the existence of a cyclic stable state. By introducing...