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Sample records for safety-catch hydrazine linker

  1. Library of biphenyl privileged substructures using a safety-catch linker approach

    DEFF Research Database (Denmark)

    Severinsen, Rune; Bourne, Gregory T; Tran, Tran T

    2008-01-01

    A biphenyl privileged structure library containing three attachment points were synthesized using a catechol-based safety-catch linker strategy. The method requires the attachment of a bromo-acid to the linker, followed by a Pd-catalyzed Suzuki cross-coupling reaction. Further derivatization...

  2. Hydrazine inhalation hepatotoxicity.

    Science.gov (United States)

    Kao, Yung Hsiang; Chong, C H; Ng, W T; Lim, D

    2007-10-01

    Abstract Hydrazine is a hazardous chemical commonly used as a reactant in rocket and jet fuel cells. Animal studies have demonstrated hepatic changes after hydrazine inhalation. Human case reports of hydrazine inhalation hepatotoxicity are rare. We report a case of mild hepatotoxicity following brief hydrazine vapour inhalation in a healthy young man, which resolved completely on expectant management.

  3. Safety catching device for pipes in missile shielding cylinders of nuclear power plants

    International Nuclear Information System (INIS)

    Hering, S.; Doll, B.

    1976-01-01

    The safety catching device consists of a steel wire passed in U-shape around the pipe to be caught and supported by two anchor ties embedded in the concrete of the missile shielding cylinder. This flexible catching device is to cause the energy released in case of a pipe rupture to be absorbed and no dangerous bending shesses to be transferred to the walls of the missile shielding cylinder. (UWI) [de

  4. Safety catching device for pipe lines in missile shielding cylinders of nuclear power plants

    International Nuclear Information System (INIS)

    Hering, S.; Doll, B.

    1975-01-01

    The safety catching device for pipes in the missile shielding cylinders consists of a flexible steel cable surrounding the pipe in a distance in U-shape. The arrester cable - which works as a spring and is freely movable in all directions - is attached to the cylinder wall. For this, the ends of the cable are primarily fastened to anchor boxes which are then inserted in a stay tube with the same axis as the cable ends. The anchor boxes are fastened to the outer wall of the missile shielding cylinder by anchor bolts and holding plates. (DG/AK) [de

  5. Tubing For Sampling Hydrazine Vapor

    Science.gov (United States)

    Travis, Josh; Taffe, Patricia S.; Rose-Pehrsson, Susan L.; Wyatt, Jeffrey R.

    1993-01-01

    Report evaluates flexible tubing used for transporting such hypergolic vapors as those of hydrazines for quantitative analysis. Describes experiments in which variety of tubing materials, chosen for their known compatibility with hydrazine, flexibility, and resistance to heat.

  6. A Photolabile Linker for the Solid-Phase Synthesis of Peptide Hydrazides and Heterocycles

    DEFF Research Database (Denmark)

    Qvortrup, Katrine; Komnatnyy, Vitaly V.; Nielsen, Thomas Eiland

    2014-01-01

    A photolabile hydrazine linker for the solid-phase synthesis of peptide hydrazides and hydrazine-derived heterocycles is presented. The developed protocols enable the efficient synthesis of structurally diverse peptide hydrazides derived from the standard amino adds, including those with side......-chain protected residues at the C-terminal of the resulting peptide hydrazide, and are useful for the synthesis of dihydropyrano[2,3-c]pyrazoles. The linker is compatible with most commonly used coupling reagents and protecting groups for solid-phase peptide synthesis....

  7. Backbone amide linker strategy

    DEFF Research Database (Denmark)

    Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen

    2013-01-01

    In the backbone amide linker (BAL) strategy, the peptide is anchored not at the C-terminus but through a backbone amide, which leaves the C-terminal available for various modifications. This is thus a very general strategy for the introduction of C-terminal modifications. The BAL strategy...

  8. Research on anhydrous hydrazine synthesis

    International Nuclear Information System (INIS)

    Gaussens, G.

    1967-03-01

    The first part of this work concerns the radiolysis of pure liquid ammonia. The fundamental importance of the dose rate and of the dose on the yield of radiolytic products has been demonstrated. By using a capture solute at concentrations of between 10 -3 and 1.2 mole s/litre, it has been possible to determine the yields of radicals and of molecules in the irradiated pure ammonia. During later work, it was possible to determine, by systematically varying the physico-chemical parameters, the most favorable conditions for carrying out the radiosynthesis; the maximum radiochemical yield of the hydrazine obtained has a value: G (N 2 H 4 ) = 2.2/100 eV. An analysis of the molecular yields in the presence of deuterated solutes makes it possible to explain partially the role of the capture species. A project is also described for an installation producing hydrazine continuously; it is followed by an economic study of the process. From this work it appears that the yields of hydrazine obtained justify an industrial application, especially if strong radiation sources are available, for example nuclear reactors. (author) [fr

  9. Detailed Chemical Kinetic Modeling of Hydrazine Decomposition

    Science.gov (United States)

    Meagher, Nancy E.; Bates, Kami R.

    2000-01-01

    The purpose of this research project is to develop and validate a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. Hydrazine is used extensively in aerospace propulsion, and although liquid hydrazine is not considered detonable, many fuel handling systems create multiphase mixtures of fuels and fuel vapors during their operation. Therefore, a thorough knowledge of the decomposition chemistry of hydrazine under a variety of conditions can be of value in assessing potential operational hazards in hydrazine fuel systems. To gain such knowledge, a reasonable starting point is the development and validation of a detailed chemical kinetic mechanism for gas-phase hydrazine decomposition. A reasonably complete mechanism was published in 1996, however, many of the elementary steps included had outdated rate expressions and a thorough investigation of the behavior of the mechanism under a variety of conditions was not presented. The current work has included substantial revision of the previously published mechanism, along with a more extensive examination of the decomposition behavior of hydrazine. An attempt to validate the mechanism against the limited experimental data available has been made and was moderately successful. Further computational and experimental research into the chemistry of this fuel needs to be completed.

  10. Occupational safety considerations with hydrazine fuels

    Science.gov (United States)

    Clewell, H. J.; Haddad, T. S.; George, M. E.; Mcdougal, J. N.; Andersen, M. E.

    1992-01-01

    A simple pharmacokinetic model and a specially designed dermal vapor exposure chamber which provides respiratory protection were used to determine the rate of penetration of hydrazine and 1,1-dimethylhydrazine (UDMH) vapor through the skin of rats. Parameters for the pharmacokinetic model were determined from intravenous and inhalation exposure data. The model was then used to estimate the skin permeation coefficient for hydrazine or UDMH vapor from the dermal-vapor exposure data. This analysis indicates that UDMH vapor has a relatively high permeability through skin (0.7 cm/hr), a value somewhat higher than was obtained for hydrazine by the same procedure (0.09 cm/hr). Based on these skin permeability results, a skin-only vapor exposure limit giving protection equivalent to the inhalation Threshold Limit Value (TLV) could be calculated. The current TLV's for UDMH and hydrazine are 0.5 and 0.1 ppm, respectively. The corresponding skin-only TLV equivalents, for personnel wearing respiratory protection, are 32 ppm for UDMH and 48 ppm for hydrazine. Should the proposed lowering to the TLV's for these compounds to 0.01 ppm be adopted, the equivalent skin-only TLV's would become 0.64 ppm for UDMH and 4.8 for hydrazine.

  11. Ionic Liquids to Replace Hydrazine

    Science.gov (United States)

    Koelfgen, Syri; Sims, Joe; Forton, Melissa; Allan, Barry; Rogers, Robin; Shamshina, Julia

    2011-01-01

    A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

  12. Performance evaluation of a colorimetric hydrazine dosimeter

    Science.gov (United States)

    Brenner, Karen P.; Rose-Pehrsson, Susan L.

    1994-06-01

    A dosimeter for real-time, colorimetric detection of hydrazine in air has been developed. The passive badge consists of a dosimeter card containing a vanillin solution coated on a thin paper substrate. The active patch consists of a thick cellulose substrate coated with a vanillin solution. When placed in a plastic sample holder attached to a personnel pump, up to 5 L/min can be drawn through the active badge substrate. Through a condensation reaction, vanillin reacts with hydrazine to form a colored product that absorbs in the visible region. The hydrazone formed in the reaction is yellow; its intensity is proportional to the dose. When exposed passively to hydrazine, the experimental detection limit is less than 20 ppb-hrs. Extrapolated results indicate a detection limit of less than 5 ppb-hrs for long sampling periods. Actively sampling of hydrazine vapors gives an experimental detection limit of less than 100 ppb-L at a sample rate of 5 L/min. Relative humidity effects on badge response were minor. High humidity enhanced the color development on the vanillin badge; while low humidity had no effect on badge response. Interference testing of the dosimeters revealed a tobacco smoke interference. Preliminary shelf life tests indicated no decrease in sensitivity to hydrazine when stored at room temperature for 6 months.

  13. Treatment for hydrazine-containing waste water solution

    Science.gov (United States)

    Yade, N.

    1986-01-01

    The treatment for waste solutions containing hydrazine is presented. The invention attempts oxidation and decomposition of hydrazine in waste water in a simple and effective processing. The method adds activated charcoal to waste solutions containing hydrazine while maintaining a pH value higher than 8, and adding iron salts if necessary. Then, the solution is aerated.

  14. Hydrazine in the Ugi Tetrazole Reaction

    NARCIS (Netherlands)

    Patil, Pravin; Zhang, Ji; Kurpiewska, Katarzyna; Kalinowska-Tłuścik, Justyna; Dömling, Alexander

    2016-01-01

    We describe the hitherto unknown use of N-Boc-protected hydrazine in the Ugi tetrazole reaction to access a library of highly substituted 5-(hydrazinomethyl)-1-methyl-1H-tetrazoles. The reaction is very versatile and good to high yielding. A one-pot, two-step procedure is given.

  15. Hydrazine Determination in Sludge Samples by High Performance Liquid Chromatography

    Energy Technology Data Exchange (ETDEWEB)

    G. Elias; G. A. Park

    2006-02-01

    A high-performance liquid chromatographic method using ultraviolet (UV) detection was developed to detect and quantify hydrazine in a variety of environmental matrices. The method was developed primarily for sludge samples, but it is also applicable to soil and water samples. The hydrazine in the matrices was derivatized to their hydrazones with benzaldehyde. The derivatized hydrazones were separated using high performance liquid chromatography (HPLC) with a reversed-phase C-18 column in an isocratic mode with methanol-water (95:5, v/v), and detected with UV detection at 313 nm. The detection limit (25 ml) for the new analytical method is 0.0067 mg ml-1of hydrazine. Hydrazine showed low recovery in soil samples because components in soil oxidized hydrazine. Sludge samples that contained relatively high soil content also showed lower recovery. The technique is relatively simple and cost-effective, and is applicable for hydrazine analysis in different environmental matrices.

  16. Automated analysis for nitrate by hydrazine reduction

    Energy Technology Data Exchange (ETDEWEB)

    Kamphake, L J; Hannah, S A; Cohen, J M

    1967-01-01

    An automated procedure for the simultaneous determinations of nitrate and nitrite in water is presented. Nitrite initially present in the sample is determined by a conventional diazotization-coupling reaction. Nitrate in another portion of sample is quantitatively reduced with hydrazine sulfate to nitrite which is then determined by the same diazotization-coupling reaction. Subtracting the nitrite initially present in the sample from that after reduction yields nitrite equivalent to nitrate initially in the sample. The rate of analysis is 20 samples/hr. Applicable range of the described method is 0.05-10 mg/l nitrite or nitrate nitrogen; however, increased sensitivity can be obtained by suitable modifications.

  17. Indirect Spectrophotometric Determination of Trace Quantities of Hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Shabani, A. M. Haji; Dadfarnia, S.; Dehghan, K. [Yazd University, Yazd (Iran, Islamic Republic of)

    2004-02-15

    An indirect, sensitive and accurate method for the determination of trace amounts of hydrazine is described. The method is based on the oxidation of hydrazine by a known excess of iodate in the presence of hydrochloric acid. The unreacted iodate is used in the oxidation of hydroxylamine to nitrite. Sulfanilic acid is diazotized by the nitrite formed. The resulting diazonium ion is coupled with N-(1-naphthyl)ethylenediamine to form a stable azo dye, which shows an absorption maximum at 540 nm. Hydrazine can be determined in the range of 20-400 ng mL{sup -1} with a detection limit of 3.1 ng mL{sup -1}. The relative standard deviation for 50, 200 and 400 ng mL{sup -1} of hydrazine is 2, 1.5 and 1.3%, respectively (n = 10). The method was applied to the determination of hydrazine in water samples

  18. Epoxide reduction with hydrazine on graphene: a first principles study.

    Science.gov (United States)

    Kim, Min Chan; Hwang, Gyeong S; Ruoff, Rodney S

    2009-08-14

    Mechanisms for epoxide reduction with hydrazine on a single-layer graphene sheet are examined using quantum mechanical calculations within the framework of gradient-corrected spin-polarized density-functional theory. We find that the reduction reaction is mainly governed by epoxide ring opening which is initiated by H transfer from hydrazine or its derivatives. In addition, our calculations suggest that the epoxide reduction by hydrazine may predominantly follow a direct Eley-Rideal mechanism rather than a Langmuir-Hinshelwood mechanism. We also discuss the generation of various hydrazine derivatives during the reduction of graphene oxide with hydrazine and their potential contribution to lowering the barrier height of epoxide ring opening.

  19. The platinum catalysed decomposition of hydrazine in acidic media

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.C.

    2000-01-01

    Kinetic study of the hydrazine decomposition in the solutions of HClO 4 , H 2 SO 4 and HNO 3 in the presence of Pt/SiO 2 catalyst has been undertaken. It was shown that the kinetics of the hydrazine catalytic decomposition in HClO 4 and H 2 SO 4 are identical. The process is determined by the heterogeneous catalytic auto-decomposition of N 2 H 4 on the catalyst's surface. The platinum catalysed hydrazine decomposition in the nitric acid solutions is a complex process, including heterogeneous catalytic auto-decomposition of N 2 H 4 , reaction of hydrazine with catalytically generated nitrous acid and the catalytic oxidation of hydrazine by nitric acid. The kinetic parameters of these reactions have been determined. The contribution of each reaction in the total process is determined by the liquid phase composition and by the temperature. (authors)

  20. Upgrading non-oxidized carbon nanotubes by thermally decomposed hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Pen-Cheng, E-mail: wangpc@ess.nthu.edu.tw [Department of Engineering and System Science, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); Graduate Program for Science and Technology of Synchrotron Light Source, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); Liao, Yu-Chun [Department of Engineering and System Science, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); Graduate Program for Science and Technology of Synchrotron Light Source, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Liu, Li-Hung [Department of Engineering and System Science, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); Lai, Yu-Ling; Lin, Ying-Chang [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Hsu, Yao-Jane [Graduate Program for Science and Technology of Synchrotron Light Source, National Tsing Hua University, 101 Section 2, Kuang-Fu Road, Hsinchu 30013, Taiwan (China); National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China)

    2014-06-01

    We found that the electrical properties of conductive thin films based on non-oxidized carbon nanotubes (CNTs) could be further improved when the CNTs consecutively underwent a mild hydrazine adsorption treatment and then a sufficiently effective thermal desorption treatment. We also found that, after several rounds of vapor-phase hydrazine treatments and baking treatments were applied to an inferior single-CNT field-effect transistor device, the device showed improvement in I{sub on}/I{sub off} ratio and reduction in the extent of gate-sweeping hysteresis. Our experimental results indicate that, even though hydrazine is a well-known reducing agent, the characteristics of our hydrazine-exposed CNT samples subject to certain treatment conditions could become more graphenic than graphanic, suggesting that the improvement in the electrical and electronic properties of CNT samples could be related to the transient bonding and chemical scavenging of thermally decomposed hydrazine on the surface of CNTs.

  1. Upgrading non-oxidized carbon nanotubes by thermally decomposed hydrazine

    Science.gov (United States)

    Wang, Pen-Cheng; Liao, Yu-Chun; Liu, Li-Hung; Lai, Yu-Ling; Lin, Ying-Chang; Hsu, Yao-Jane

    2014-06-01

    We found that the electrical properties of conductive thin films based on non-oxidized carbon nanotubes (CNTs) could be further improved when the CNTs consecutively underwent a mild hydrazine adsorption treatment and then a sufficiently effective thermal desorption treatment. We also found that, after several rounds of vapor-phase hydrazine treatments and baking treatments were applied to an inferior single-CNT field-effect transistor device, the device showed improvement in Ion/Ioff ratio and reduction in the extent of gate-sweeping hysteresis. Our experimental results indicate that, even though hydrazine is a well-known reducing agent, the characteristics of our hydrazine-exposed CNT samples subject to certain treatment conditions could become more graphenic than graphanic, suggesting that the improvement in the electrical and electronic properties of CNT samples could be related to the transient bonding and chemical scavenging of thermally decomposed hydrazine on the surface of CNTs.

  2. Structure and Functions of Linker Histones.

    Science.gov (United States)

    Lyubitelev, A V; Nikitin, D V; Shaytan, A K; Studitsky, V M; Kirpichnikov, M P

    2016-03-01

    Linker histones such as variants H1, H5, and other similar proteins play an important role in regulation of chromatin structure and dynamics. However, interactions of linker histones with DNA and proteins, as well as specific functions of their different variants, are poorly studied. This is because they acquire tertiary structure only when interacting with a nucleosome, and because of limitations of currently available methods. However, deeper investigation of linker histones and their interactions with other proteins will address a number of important questions - from structure of compacted chromatin to regulation of early embryogenesis. In this review, structures of histone H1 variants and its interaction with chromatin DNA are considered. A possible functional significance of different H1 variants, a role of these proteins in maintaining interphase chromatin structure, and interactions of linker histones with other cellular proteins are also discussed.

  3. Hydroquinone–pyrrole dyads with varied linkers

    Directory of Open Access Journals (Sweden)

    Hao Huang

    2016-01-01

    Full Text Available A series of pyrroles functionalized in the 3-position with p-dimethoxybenzene via various linkers (CH2, CH2CH2, CH=CH, C≡C has been synthesized. Their electronic properties have been deduced from 1H NMR, 13C NMR, and UV–vis spectra to detect possible interactions between the two aromatic subunits. The extent of conjugation between the subunits is largely controlled by the nature of the linker, with the largest conjugation found with the trans-ethene linker and the weakest with the aliphatic linkers. DFT calculations revealed substantial changes in the HOMO–LUMO gap that correlated with the extent of conjugation found experimentally. The results of this work are expected to open up for use of the investigated compounds as components of redox-active materials in sustainable, organic electrical energy storage devices.

  4. Research on anhydrous hydrazine synthesis; Recherche sur la synthese de l'hydrazine anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Gaussens, G. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-03-15

    The first part of this work concerns the radiolysis of pure liquid ammonia. The fundamental importance of the dose rate and of the dose on the yield of radiolytic products has been demonstrated. By using a capture solute at concentrations of between 10{sup -3} and 1.2 mole s/litre, it has been possible to determine the yields of radicals and of molecules in the irradiated pure ammonia. During later work, it was possible to determine, by systematically varying the physico-chemical parameters, the most favorable conditions for carrying out the radiosynthesis; the maximum radiochemical yield of the hydrazine obtained has a value: G (N{sub 2}H{sub 4}) = 2.2/100 eV. An analysis of the molecular yields in the presence of deuterated solutes makes it possible to explain partially the role of the capture species. A project is also described for an installation producing hydrazine continuously; it is followed by an economic study of the process. From this work it appears that the yields of hydrazine obtained justify an industrial application, especially if strong radiation sources are available, for example nuclear reactors. (author) [French] La premiere partie de l'etude a porte sur la radiolyse de l'ammoniac liquide pur. Le role fondamental du debit de dose et de la dose sur les rendements des produits de radiolyse a ete mise en evidence. L'emploi de solute capteur dont les concentrations sont comprises entre 10{sup -3} et 1,2 mole/litre, a permis de determiner la valeur des rendements radicalaires et moleculaires dans l'ammoniac pur irradie. Au cours d'une etape ulterieure, une variation systematique des parametres physico-chimiques a permis de determiner les conditions les plus favorables a la radiosynthese le rendement radiochimique maximum de l'hydrazine obtenu a pour valeur: G(N{sub 2}H{sub 4}) 2,2/100 eV. L'analyse des rendements moleculaires en presence de solutes deuteres nous permet de rendre compte partiellement du role des

  5. Research on anhydrous hydrazine synthesis; Recherche sur la synthese de l'hydrazine anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Gaussens, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-03-15

    The first part of this work concerns the radiolysis of pure liquid ammonia. The fundamental importance of the dose rate and of the dose on the yield of radiolytic products has been demonstrated. By using a capture solute at concentrations of between 10{sup -3} and 1.2 mole s/litre, it has been possible to determine the yields of radicals and of molecules in the irradiated pure ammonia. During later work, it was possible to determine, by systematically varying the physico-chemical parameters, the most favorable conditions for carrying out the radiosynthesis; the maximum radiochemical yield of the hydrazine obtained has a value: G (N{sub 2}H{sub 4}) = 2.2/100 eV. An analysis of the molecular yields in the presence of deuterated solutes makes it possible to explain partially the role of the capture species. A project is also described for an installation producing hydrazine continuously; it is followed by an economic study of the process. From this work it appears that the yields of hydrazine obtained justify an industrial application, especially if strong radiation sources are available, for example nuclear reactors. (author) [French] La premiere partie de l'etude a porte sur la radiolyse de l'ammoniac liquide pur. Le role fondamental du debit de dose et de la dose sur les rendements des produits de radiolyse a ete mise en evidence. L'emploi de solute capteur dont les concentrations sont comprises entre 10{sup -3} et 1,2 mole/litre, a permis de determiner la valeur des rendements radicalaires et moleculaires dans l'ammoniac pur irradie. Au cours d'une etape ulterieure, une variation systematique des parametres physico-chimiques a permis de determiner les conditions les plus favorables a la radiosynthese le rendement radiochimique maximum de l'hydrazine obtenu a pour valeur: G(N{sub 2}H{sub 4}) 2,2/100 eV. L'analyse des rendements moleculaires en presence de solutes deuteres nous permet de rendre compte partiellement du role des capteurs. Un projet d'une installation

  6. Preparation of fine Ni powders from nickel hydrazine complex

    International Nuclear Information System (INIS)

    Park, Jung Woo; Chae, Eun H.; Kim, Sang H.; Lee, Jong Ho; Kim, Jeong Wook; Yoon, Seon Mi; Choi, Jae-Young

    2006-01-01

    Fine nickel powders with narrow size distribution have been prepared from the reduction of nickel hydrazine complexes in aqueous solution. The pure nickel hydrazine complexes, [Ni(N 2 H 4 ) 3 ]Cl 2 were prepared with the molar ratio of N 2 H 4 /Ni 2+ = 4.5, while a mixture of complexes, such as Ni(N 2 H 4 ) 2 Cl 2 , [Ni(N 2 H 4 ) 3 ]Cl 2 , and [Ni(NH 3 ) 6 ]Cl 2 were formed with N 2 H 4 /Ni 2+ 2+ to metallic Ni powder proceeded via the formation of nickel hydroxide which was reduced by hydrazine liberated from the ligand exchange reaction between the nickel hydrazine complex and NaOH. The standard deviation of the particle size decreased with the decreasing molar concentration of nickel hydrazine complex while the mean particle size increased. As the amount of hydrazine increased, the surface roughness of the particles was improved significantly due to the catalytic decomposition of the excess hydrazine at the surface of the nickel particle. It was found that average particle size could be controlled from 150 to 380 nm by adjusting the reaction molar ratio and temperature

  7. Research about the hydrazine-ammonia system. Untersuchungen am system hydrazin-ammoniak

    Energy Technology Data Exchange (ETDEWEB)

    None

    1967-03-15

    Some qualities of hydrazine-ammonia mixtures are investigated with regard to their use as rocket fuels by means of conventional measuring methods being adapted to the problems of these systems vapor pressures, densities and viscosities of such mixtures are determined as functions of compositions. The findings of these studies show in view to vapor pressure and densities deviations from ideal behavior, which are however, of disadvantage when using this system as fuel for rocket engines.

  8. System of ytterbium nitrate-hydrazine(mono-)dinitrate-water

    International Nuclear Information System (INIS)

    Khisaeva, D.A.; Katamanov, V.L.

    1986-01-01

    Solubility in ternary systems ytterbium nitrate-hydrazine monohydrate-water and ytterbium nitrate-hydrazine dinitrate-water is studied at 25 and 50 deg C. Salt components of both systems do not form with each other double addition compounds in the chosen temperature range. Initial salts are equilibrium solid phases of saturated solutions. Correlation of the range of primary crystallization of nitrate acydocomplexes of lanthanides formed in similar systems with their atomic number is considered. It is shown that hydrazine dinitrate can be used for separation of rare earth elements of cerium group

  9. The reaction of hydrazine nitrate with nitric acid

    International Nuclear Information System (INIS)

    Kida, Takashi; Sugikawa, Susumu

    2004-03-01

    It is known that hydrazine nitrate used in nuclear fuel reprocessing plants is an unstable substance thermochemically like hydroxylamine nitrate. In order to take the basic data regarding the reaction of hydrazine nitrate with nitric acid, initiation temperatures and heats of this reaction, effect of impurity on initiation temperature and self-accelerating reaction when it holds at constant temperature for a long time were measured by the pressure vessel type reaction calorimeter etc. In this paper, the experimental data and evaluation of the safe handling of hydrazine nitrate in nuclear fuel reprocessing plants are described. (author)

  10. Some observations on hydrazine and ammonia based chemistries in PWRs

    International Nuclear Information System (INIS)

    Brunning, J.; Cake, P.; Harper, A.; Sims, H.E.

    1997-01-01

    This paper presents a comparison of factors related to activated corrosion product transport in pressurized water reactors (PWRs) operating hydrazine and ammonia-based chemistries. Measurements of the concentrations of corrosion products in the coolant of reactors operating both chemistry regimes are compared under steady operation and during shutdown. These data allow some comparisons to be drawn of corrosion product transport under ammonia and hydrazine based chemistries. Experimental measurements of electrochemical potential under PWR conditions in the presence and absence of radiation fields and under hydrazine and ammonia chemistries are also presented. (author). 4 refs, 5 figs, 2 tabs

  11. Some observations on hydrazine and ammonia based chemistries in PWRs

    Energy Technology Data Exchange (ETDEWEB)

    Brunning, J; Cake, P; Harper, A; Sims, H E [AEA Technology, Oxon (United Kingdom)

    1997-02-01

    This paper presents a comparison of factors related to activated corrosion product transport in pressurized water reactors (PWRs) operating hydrazine and ammonia-based chemistries. Measurements of the concentrations of corrosion products in the coolant of reactors operating both chemistry regimes are compared under steady operation and during shutdown. These data allow some comparisons to be drawn of corrosion product transport under ammonia and hydrazine based chemistries. Experimental measurements of electrochemical potential under PWR conditions in the presence and absence of radiation fields and under hydrazine and ammonia chemistries are also presented. (author). 4 refs, 5 figs, 2 tabs.

  12. On hydrazine oxidation in nitric acid media

    International Nuclear Information System (INIS)

    Zil'berman, B.Ya.; Lelyuk, G.A.; Mashkin, A.N.; Yasnovitskaya, A.L.

    1988-01-01

    Yield of products of radiolytic ( 60 Co gamma radiation) and chemical hydrazine (HZ) oxidation in nitric acid media is studied. Under radiolyte HZ oxidation by nitric acid hydrazoic acid, ammonia and nitrogen appear to be the reaction products. HN 3 yield maximum under HZN oxidation makes up ∼ 0.35 mol per a mol of oxiduzed HZN. Under chemical oxidation HZN is oxidized by HNO 3 according to reaction catalysed by technetium HN 3 yield makes up ∼ 0.35 mol per a mol of oxidized HZN. Radiation-chemical oxidation of HN 3 proceeds up to its complete decomposition, decomposition rate is comparable with HZ oxidation rate. Under the chemical oxidation HN 3 is more stable, it is slowly decomposed after complete HZ decomposition

  13. Solid colloids with surface-mobile linkers

    International Nuclear Information System (INIS)

    Van der Meulen, Stef A J; Helms, Gesa; Dogterom, Marileen

    2015-01-01

    In this report we review the possibilities of using colloids with surface mobile linkers for the study of colloidal self-assembly processes. A promising route to create systems with mobile linkers is the use of lipid (bi-)layers. These lipid layers can be either used in the form of vesicles or as coatings for hard colloids and emulsion droplets. Inside the lipid bilayers molecules can be inserted via membrane anchors. Due to the fluidity of the lipid bilayer, the anchored molecules remain mobile. The use of different lipid mixtures even allows creating Janus-like particles that exhibit directional bonding if linkers are used which have a preference for a certain lipid phase. In nature mobile linkers can be found e.g. as receptors in cells. Therefore, towards the end of the review, we also briefly address the possibility of using colloids with surface mobile linkers as model systems to mimic cell–cell interactions and cell adhesion processes. (topical review)

  14. Environmental simulation testing of solar cell contamination by hydrazine

    Science.gov (United States)

    Moore, W. W., Jr.

    1972-01-01

    Test results for thermal vacuum and radiation environment simulation of hydrazine contamination are discussed. Solar cell performance degradation, measured by short circuit current, is presented in correlation with the variations used in environmental parameters.

  15. Determination of U(IV) and hydrazine nitrate by volumetry

    International Nuclear Information System (INIS)

    Cao Xi; Wang Nanjie; Zhang Tao; Wang Lin; Guo Yuhua

    2006-01-01

    To be determined U(IV) and hydrazine nitrate in exist together, chromium (VI) and 1,10-phenanthroline is used individually as oxidation titrator and indicator for U(IV), and N-bromineimino and methyl red is used individually as oxidation titrator and indicator for hydrazine nitrate, U(IV) and hydrazine nitrate in the same sample is determined sequentially in the nitric acid by adjusting concentration of nitric acid. Results show that the precision is better than 2.0% when the mass concentration of U(IV) is ranged over 5.5-205 mg/mL; and the precision is better than 2.0% when the concentration of hydrazine nitrate is ranged over 0.05-1.0 mol/L. (authors)

  16. Enthalpy of Formation of N2H4 (Hydrazine) Revisited.

    Science.gov (United States)

    Feller, David; Bross, David H; Ruscic, Branko

    2017-08-17

    In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine, was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57 ± 0.47 kJ/mol at 0 K (97.42 ± 0.47 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and the FPD enthalpy.

  17. Hydrazine - hydrate water regime and operation of fuel elements

    International Nuclear Information System (INIS)

    Pashevitch, V.I.; Pashevitch, D.V.; Bogancs, J.; Tilky, P.

    1997-01-01

    Water chemistries currently used in WWER reactors are potassium based water chemistry (KOH) to adjust the pH with ammonia or hydrazine as oxygen scavenger. Based on the measurements of Zr 95 which is a corrosion product of the zirconium cladding, it is shown in this paper that the amount of corrosion products accompanying the reactor shutdown is smaller when hydrazine is used. This is particularly obvious on PAKS 1 and 2 when Zr 95 measurements are performed before and after switching the water chemistry from ammonia to hydrazine. It is concluded that the main advantage of using the hydrazine water chemistry is to decrease the thickness of the corrosion product layer formed on the fuel cladding, therefore the fuel temperature can be kept low. It is estimated that the fuel temperature increase due to the layer of corrosion products is 120 deg. C for KOLA 3 which is operated with ammonia water chemistry. (author). 5 figs

  18. Hydrazine determination in presence of uranium by modified spectrophotometric method

    International Nuclear Information System (INIS)

    Velavendan, P.; Pandey, N.K.; Kamachi Mudali, U.; Natarajan, R.

    2011-01-01

    In the present work an indirect, sensitive and accurate method for the determination of hydrazine is described. The method is based on the formation of yellow coloured azine complex by post column derivatization of hydrazine with P-dimethylamino benzaldehyde. The formed yellow coloured complex is stable in acidic medium and has a maximum absorption at 460 nm. Interference due to uranium was studied and the method was applied for the determination of hydrazine in presence of uranium in aqueous stream of nuclear fuel reprocessing. A calibration graph was made for the concentration range of hydrazine from 0.05 ppm to 10 ppm with RSD 0.807% and correlation coefficient of 0.99996. (author)

  19. Hydrazine - hydrate water regime and operation of fuel elements

    Energy Technology Data Exchange (ETDEWEB)

    Pashevitch, V I; Pashevitch, D V [Pand Co. (Russian Federation); Bogancs, J; Tilky, P [Paks NPP (Hungary)

    1997-02-01

    Water chemistries currently used in WWER reactors are potassium based water chemistry (KOH) to adjust the pH with ammonia or hydrazine as oxygen scavenger. Based on the measurements of Zr 95 which is a corrosion product of the zirconium cladding, it is shown in this paper that the amount of corrosion products accompanying the reactor shutdown is smaller when hydrazine is used. This is particularly obvious on PAKS 1 and 2 when Zr 95 measurements are performed before and after switching the water chemistry from ammonia to hydrazine. It is concluded that the main advantage of using the hydrazine water chemistry is to decrease the thickness of the corrosion product layer formed on the fuel cladding, therefore the fuel temperature can be kept low. It is estimated that the fuel temperature increase due to the layer of corrosion products is 120 deg. C for KOLA 3 which is operated with ammonia water chemistry. (author). 5 figs.

  20. Mobility Spectrometer Studies on Hydrazine and Ammonia Detection

    Science.gov (United States)

    Niu, William; Eiceman, Gary; Szumlas, Andrew; Lewis, John

    2011-01-01

    An airborne vapor analyzer for detecting sub- to low- parts-per-million (ppm) hydrazine in the presence of higher concentration levels of ammonia has been under development for the Orion program. The detector is based on ambient pressure ionization and ion mobility characterization. The detector encompasses: 1) a membrane inlet to exclude particulate and aerosols from the analyzer inlet; 2) a method to separate hydrazine from ammonia which would otherwise lead to loss of calibration and quantitative accuracy for the hydrazine determination; and 3) response and quantitative determinations for both hydrazine and ammonia. Laboratory studies were made to explore some of these features including mobility measurements mindful of power, size, and weight issues. The study recommended the use of a mobility spectrometer of traditional design with a reagent gas and equipped with an inlet transfer line of bonded phase fused silica tube. The inlet transfer line provided gas phase separation of neutrals of ammonia from hydrazine at 50 C simplifying significantly the ionization chemistry that underlies response in a mobility spectrometer. Performance of the analyzer was acceptable between ranges of 30 to 80 C for both the pre-fractionation column and the drift tube. An inlet comprised of a combined membrane with valve-less injector allowed high speed quantitative determination of ammonia and hydrazine without cross reactivity from common metabolites such as alcohols, esters, and aldehydes. Preliminary test results and some of the design features are discussed.

  1. Interactions of Hydrazine and of Hydrazine Derivatives with Soil Constituents and with Soils

    Science.gov (United States)

    1984-08-23

    the amount of hydrazine adsorbed per meq of A1 3+ was nearly thrice as inch for kaolinite (420 Peq me - 1 ) than for montmorillonite (150 peg -1) showing...1952) Absorption (cm ) Assignment Vapour Liquid 3350 3338 N-H stretching 3325 3314 3280 3200 1628 N-H bending 1587 1493 1275 1280 Table 15 IR spectra of...contrast, the spectrum of the monomethylhydrazine-clay complex when treated in a similar way, still included an absorption at 3350 cm 1 which assigned to

  2. Water-soluble heterobifunctional fluorescent linkers

    Czech Academy of Sciences Publication Activity Database

    Bartoň, Jan; Cígler, Petr

    2017-01-01

    Roč. 15, č. 1 (2017), s. 4 ISSN 2336-7202. [Mezioborové setkání mladých biologů, biochemiků a chemiků /17./. 30.05.2017-01.06.2017, Milovy] Institutional support: RVO:61388963 Keywords : fluorescent probes * heterobifunctional linkers Subject RIV: CA - Inorganic Chemistry

  3. Clustering of amines and hydrazines in atmospheric nucleation

    Science.gov (United States)

    Li, Siyang; Qu, Kun; Zhao, Hailiang; Ding, Lei; Du, Lin

    2016-06-01

    It has been proved that the presence of amines in the atmosphere can enhance aerosol formation. Hydrazine (HD) and its substituted derivatives, monomethylhydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH), which are organic derivatives of amine and ammonia, are common trace atmospheric species that may contribute to the growth of nucleation clusters. The structures of the hydrazine and amine clusters containing one or two common nucleation molecules (ammonia, water, methanol and sulfuric acid) have been optimized using density functional theory (DFT) methods. The clusters growth mechanism has been explored from the thermochemistry by calculating the Gibbs free energies of adding an ammonia, water, methanol or sulfuric acid molecule step by step at room temperature, respectively. The results show that hydrazine and its derivatives could enhance heteromolecular homogeneous nucleation in the earth's atmosphere.

  4. Estimation of Hydrazine Decomposition on Measuring the High-Temperature pH in Hydrazine/ETA Solutions at 553 K

    International Nuclear Information System (INIS)

    Hwang, Jae Sik; Yeon, Jei Won; Yun, Myung Hee; Song, Kyu Seok; Lee, Sang Ill

    2010-01-01

    Hydrazine is one of the most excellent oxygen scavengers used in the secondary circuit of nuclear power plants. Furthermore, in some pants, the hydrazine is used as a source of hydrogen required to suppress radiolysis of the coolant water in the primary loop. When hydrazine was exposed in the high temperature and high pressure water, it can be decomposed into the various products such as NH 3 , N 2 , H 2 , and NO 3 ions. As the result, the pH of solution containing hydrazine in the condition of the high temperature and high pressure can be changed by those decomposed products. In the present work, we investigated the decomposition behavior of hydrazine in ETA (ethanol amine) solution. In addition, we measured the high temperature pH at 553 K on the various hydrazine/ETA solutions for confirming the applicability of the yttria stabilized zirconia (YSZ)- based pH electrode in secondary circuit of the nuclear power plants

  5. Sensitive amperometric determination of hydrazine using a carbon ...

    Indian Academy of Sciences (India)

    Silver-loaded nanozeolite-L-modified carbon paste electrode (Ag/L–CPE) was used as a novel sensing platform for enhanced electrocatalytic oxidation and determination of hydrazine. Zeolite L nanoparticles were synthesized via hydrothermal approach and then characterized using various techniques such as X-ray ...

  6. CU(II): catalyzed hydrazine reduction of ferric nitrate

    International Nuclear Information System (INIS)

    Karraker, D.G.

    1981-11-01

    A method is described for producing ferrous nitrate solutions by the cupric ion-catalyzed reduction of ferric nitrate with hydrazine. The reaction is complete in about 1.5 hours at 40 0 C. Hydrazoic acid is also produced in substantial quantities as a reaction byproduct

  7. hydrazines and their nickel(II) complexes: Syntheses, structures and ...

    Indian Academy of Sciences (India)

    G Narendra Babu

    Abstract. The Schiff bases N-(acyl)-N -(ferrocenylidene)hydrazines (HFcah (1) and HFcbh (2), where acyl = acetyl in 1 and benzoyl in 2 and H represents the dissociable amide proton) were synthesized in high yields (74 and 81%) by condensation reactions of equimolar amounts of ferrocene-carboxaldehyde and the ...

  8. Desmosine-Inspired Cross-Linkers for Hyaluronan Hydrogels

    Science.gov (United States)

    Hagel, Valentin; Mateescu, Markus; Southan, Alexander; Wegner, Seraphine V.; Nuss, Isabell; Haraszti, Tamás; Kleinhans, Claudia; Schuh, Christian; Spatz, Joachim P.; Kluger, Petra J.; Bach, Monika; Tussetschläger, Stefan; Tovar, Günter E. M.; Laschat, Sabine; Boehm, Heike

    2013-06-01

    We designed bioinspired cross-linkers based on desmosine, the cross-linker in natural elastin, to prepare hydrogels with thiolated hyaluronic acid. These short, rigid cross-linkers are based on pyridinium salts (as in desmosine) and can connect two polymer backbones. Generally, the obtained semi-synthetic hydrogels are form-stable, can withstand repeated stress, have a large linear-elastic range, and show strain stiffening behavior typical for biopolymer networks. In addition, it is possible to introduce a positive charge to the core of the cross-linker without affecting the gelation efficiency, or consequently the network connectivity. However, the mechanical properties strongly depend on the charge of the cross-linker. The properties of the presented hydrogels can thus be tuned in a range important for engineering of soft tissues by controlling the cross-linking density and the charge of the cross-linker.

  9. Oxygen consumption by hydrazine in long sample lines

    International Nuclear Information System (INIS)

    Chi, Lisheng; Turner, Carl-W.

    2012-09-01

    In nuclear power plants secondary side system dissolved oxygen concentration is a strictly controlled chemistry parameter intended to minimize corrosion and fouling of steam cycle components. Low dissolved oxygen concentration is maintained by a combination of mechanical de-aeration and chemical reaction. The dissolved oxygen concentration in feedwater is monitored by sampling systems to ensure it remains within station specification during operation. The sample lines in a nuclear power plant's sampling system can be from 5 to nearly 200 meters in length, resulting in sample residence times between the take-off point to the analyzer from a few seconds to several minutes, depending on the flow rate and the length of the sample line. For many chemical parameters the residence time is of no concern. For measurements of dissolved oxygen and hydrazine in the secondary coolant, however, for residence times longer than one minute, it is uncertain whether the sample is representative of conditions in the secondary coolant, especially for samples taken from locations where the temperature is well over 100 deg. C. To address this concern, a series of tests were conducted under both warm-up and power operation conditions, respectively, to investigate the effect of temperature, residence time, sample line length, surface area, hydrazine-to-oxygen ratio, and the concentrations of dissolved oxygen and hydrazine on the consumption of oxygen by hydrazine. The test results revealed that dissolved oxygen measurements in CANDU plants are underestimated to various degrees, depending on the sampling system operating conditions. Two distinct types of behaviours are observed for the oxygen removal rate: 1) the percentage removal of dissolved oxygen is invariant with time during the tests, and increases with increasing residence time in the test section, when the reaction between hydrazine and oxygen is better described by a homogenous reaction mechanism, and 2) the percentage oxygen

  10. Photolabile linker for the synthesis of hydroxamic acids

    DEFF Research Database (Denmark)

    2013-01-01

    a hydroxylamine - functionalized photolabile linker, and the so produced hydroxylamine - functionalized photolabile solid support. The invention further provides a method for synthesizing a one-bead-one compound library of hydroxamic acid derivatives on a photolabile linker, as well as a method for screening...

  11. Determination of hydrazine in technological waters of power plants

    International Nuclear Information System (INIS)

    Novak, M.; Hlatky, J.; Santova, E.; Nadasky, A.

    1991-01-01

    The available commercial automatic analyzers for the determination of hydrazine with spectrophotometric detection are described. Analyzers that are manufactured at present in Czechoslovakia can be divided into two groups. The first group involves the commercially available UPFA IV NH industrial analyzer. Experience in the introduction of this analyzer in the conditions of the nuclear power plant secondary circuit bear out the earlier observation of failures in the injection and dispensing of reagents and frequent failures of the mechanical programmer. For the determination of hydrazine, the reagent was dissolved in sulfuric acid, and in a time the analyzer had to be put out of operation due to corrosion problems. A remedy consists in the replacement of sulfuric acid with the less aggressive oxalic acid. Another group of automatic analyzers for the determination of hydrazine is based on the flow injection analysis (FIA) method. Although exhibiting a high throughput, analyzers of this kind put high demands on the purity of reagents. The instruments are better suited to laboratory work, whereas problems can arise in industrial conditions. Based on experience gained in the use of automatic analyzers of the two groups, two new analyzers were designed. The one is based on the flow analysis principle and is of modular design, whereas the other is based on the stopped-flow FIA principle; an adapted flow cell is accommodated in the detector, and the device uses a hydraulic path whose diameter is 2 to 5 mm. The determination of hydrazine occurs in a closed system, the reagent being protected from contact with air; this extends the lifetime of the facility and minimizes personnel exposure to toxic and/or radioactive substances. (author). 5 figs., 2 tabs., 8 refs

  12. Performances and improvement of copper-hydrazine complexation deoxidising resin

    International Nuclear Information System (INIS)

    Liu Fenfen; Zhang Hao; Sun Haijun; Liu Xiaojie

    2012-01-01

    Copper-hydrazine complexation deoxidising resin is tested to examine its performances including effluent water quality and capacity of deoxidisation. By the means of changing the resin type and regeneration, the deoxidising capacity of the resin can be improved to 13 times more than before. At the same time, physical performances of the resin are also greatly improved while maintaining its velocity of deoxidisation and effluent quality. (authors)

  13. Process for treating waste water containing hydrazine from power stations

    International Nuclear Information System (INIS)

    Hoffmann, W.

    1982-01-01

    A process for treating waste water containing hydrazine from nuclear power stations is proposed, characterized by the fact that the water is taken continuously through a water decomposition cell. If the water does not have sufficient conductivity itself, a substance raising the electrical conductivity is added to the water to be treated. The electrolysis is situated in the waste water tank. (orig./RB) [de

  14. A Helix-Stabilizing Linker Improves Subcutaneous Bioavailability of a Helical Peptide Independent of Linker Lipophilicity

    Science.gov (United States)

    Zhang, Liang; Navaratna, Tejas; Thurber, Greg M.

    2016-01-01

    Stabilized peptides address several limitations to peptide-based imaging agents and therapeutics such as poor stability and low affinity due to conformational flexibility. There is also active research in developing these compounds for intracellular drug targeting, and significant efforts have been invested to determine the effects of helix stabilization on intracellular delivery. However, much less is known about the impact on other pharmacokinetic parameters such as plasma clearance and bioavailability. We investigated the effect of different fluorescent helix-stabilizing linkers with varying lipophilicity on subcutaneous (SC) bioavailability using the glucagon-like peptide-1 (GLP-1) receptor ligand exendin as a model system. The stabilized peptides showed significantly higher protease resistance and increased bioavailability independent of linker hydrophilicity, and all subcutaneously delivered conjugates were able to successfully target the islets of Langerhans with high specificity. The lipophilic peptide variants had slower absorption and plasma clearance than their respective hydrophilic conjugates, and the absolute bioavailability was also lower likely due to the longer residence times in the skin. The ease and efficiency of double-click helix stabilization chemistries is a useful tool for increasing the bioavailability of peptide therapeutics, many of which suffer from rapid in vivo protease degradation. Helix stabilization using linkers of varying lipophilicity can further control SC absorption and clearance rates to customize plasma pharmacokinetics. PMID:27327034

  15. Developing a New Sampling And Analysis Method For Hydrazine And Monomethyl Hydrazine: Using a Derivatizing Agent With Solid Phase Microextraction

    Science.gov (United States)

    Allen, John

    2001-01-01

    Solid phase microextraction (SPME) will be used to develop a method for detecting monomethyl hydrazine (MMH) and hydrazine (Hz). A derivatizing agent, pentafluorobenzoyl chloride (PFBCI), is known to react readily with MMH and Hz. The SPME fiber can either be coated with PFBCl and introduced into a gaseous stream containing MMH, or PFBCl and MMH can react first in a syringe barrel and after a short equilibration period a SPME is used to sample the resulting solution. These methods were optimized and compared. Because Hz and MMH can degrade the SPME, letting the reaction occur first gave better results. Only MMH could be detected using either of these methods. Future research will concentrate on constructing calibration curves and determining the detection limit.

  16. Radiation chemistry of aqueous solutions of hydrazine at elevated temperatures: Pt. 2. Solutions containing oxygen

    International Nuclear Information System (INIS)

    Buxton, G.V.; Stuart, C.R.

    1997-01-01

    Here, we investigate the effects of oxygen on the radiation chemistry of hydrazine at elevated temperatures. The chemistry of this system is important to reactor coolant chemistry, particularly under start-up conditions when hydrazine is added to suppress corrosion which would otherwise be caused by the ingress of oxygen. The radiation chemistry of aqueous solutions of hydrazine has been investigated previously in the presence of oxygen by Ershov et al., but only at room temperature. In those experiments, both steady-state γ-radiolysis and pulse radiolysis were used to deduce the mechanism of decomposition of hydrazine in the presence of oxygen. (author)

  17. Evaluation of consequence due to higher hydrazine content in partitioning stream of PUREX process

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, K. Suresh [Bhabha Atomic Research Centre, Mumbai (India). Special Nuclear Recycle Facility

    2016-07-01

    Hydrazine nitrate is being used as a stabilizer for U(IV) as well as Pu(III) during partitioning of Pu in PUREX process by scavenging the nitrous acid present along with nitric acid. As hydrazine hydrate as well as its salts have been successfully used for scrubbing of degradation products of TBP to aqueous phase, experiments were conducted to evaluate the consequence of hydrazine content during Pu partitioning. It was observed that higher amount of hydrazine nitrate along with uranous nitrate in the partitioning stream of PUREX process leads to build up of DBP in aqueous phase and resulted in precipitation of Pu.

  18. Ag supported on carbon fiber cloth as the catalyst for hydrazine oxidation in alkaline medium

    International Nuclear Information System (INIS)

    Liu, Ran; Ye, Ke; Gao, Yinyi; Zhang, Wenping; Wang, Guiling; Cao, Dianxue

    2015-01-01

    Highlights: • CFC supported microspherical Ag is obtained by square-wave potential method. • Ag/CFC electrode has high catalytic activity toward hydrazine oxidation. • Hydrazine oxidation on the electrode proceeds by a near 4-electron pathway. - Abstract: Silver particles with microspheric structure are directly electrodeposited on carbon fiber cloth (CFC) substrate by square-wave potential electrodeposition method. The electrocatalytic behaviors of the Ag/CFC electrode toward hydrazine oxidation in alkaline solution are examined by cyclic voltammetry and chronoamperometry. An onset oxidation potential of -0.5 V and a peak current density of 30 mA cm −2 are achieved in the solution containing 1.0 mol L −1 KOH and 20.0 mmol L −1 hydrazine. The microspheric structure of the Ag/CFC electrode provides large electroactive surface area, hence, abundant active sites are vacant for hydrazine oxidation. The calculated apparent activation energies at different potentials show that hydrazine electro-oxidation at higher potential has faster kinetics than that at lower potential. In addition, the transfer electron number of hydrazine oxidation reaction on the Ag/CFC electrode is close to four, suggesting hydrazine is almost completely electrooxidized on the electrode and the full use of hydrazine fuel is basically achieved.

  19. Structural Mechanisms of Nucleosome Recognition by Linker Histones.

    Science.gov (United States)

    Zhou, Bing-Rui; Jiang, Jiansheng; Feng, Hanqiao; Ghirlando, Rodolfo; Xiao, T Sam; Bai, Yawen

    2015-08-20

    Linker histones bind to the nucleosome and regulate the structure of chromatin and gene expression. Despite more than three decades of effort, the structural basis of nucleosome recognition by linker histones remains elusive. Here, we report the crystal structure of the globular domain of chicken linker histone H5 in complex with the nucleosome at 3.5 Å resolution, which is validated using nuclear magnetic resonance spectroscopy. The globular domain sits on the dyad of the nucleosome and interacts with both DNA linkers. Our structure integrates results from mutation analyses and previous cross-linking and fluorescence recovery after photobleach experiments, and it helps resolve the long debate on structural mechanisms of nucleosome recognition by linker histones. The on-dyad binding mode of the H5 globular domain is different from the recently reported off-dyad binding mode of Drosophila linker histone H1. We demonstrate that linker histones with different binding modes could fold chromatin to form distinct higher-order structures. Copyright © 2015 Elsevier Inc. All rights reserved.

  20. Nanohashtag structures based on carbon nanotubes and molecular linkers

    Science.gov (United States)

    Frye, Connor W.; Rybolt, Thomas R.

    2018-03-01

    Molecular mechanics was used to study the noncovalent interactions between single-walled carbon nanotubes and molecular linkers. Groups of nanotubes have the tendency to form tight, parallel bundles (||||). Molecular linkers were introduced into our models to stabilize nanostructures with carbon nanotubes held in perpendicular orientations. Molecular mechanics makes it possible to estimate the strength of noncovalent interactions holding these structures together and to calculate the overall binding energy of the structures. A set of linkers were designed and built around a 1,3,5,7-cyclooctatetraene tether with two corannulene containing pincers that extend in opposite directions from the central cyclooctatetraene portion. Each pincer consists of a pairs of "arms." These molecular linkers were modified so that the "hand" portions of each pair of "arms" could close together to grab and hold two carbon nanotubes in a perpendicular arrangement. To illustrate the possibility of more complicated and open perpendicular CNTs structures, our primary goal was to create a model of a nanohashtag (#) CNT conformation that is more stable than any parallel CNT arrangements with bound linker molecules forming clumps of CNTs and linkers in non-hashtag arrangements. This goal was achieved using a molecular linker (C280H96) that utilizes van der Waals interactions to two perpendicular oriented CNTs. Hydrogen bonding was then added between linker molecules to augment the stability of the hashtag structure. In the hashtag structure with hydrogen bonding, four (5,5) CNTs of length 4.46 nm (18 rings) and four linkers (C276H92N8O8) stabilized the hashtag so that the average binding energy per pincer was 118 kcal/mol.

  1. Crystallization of Galectin-8 Linker Reveals Intricate Relationship between the N-terminal Tail and the Linker

    Directory of Open Access Journals (Sweden)

    Yunlong Si

    2016-12-01

    Full Text Available Galectin-8 (Gal-8 plays a significant role in normal immunological function as well as in cancer. This lectin contains two carbohydrate recognition domains (CRD connected by a peptide linker. The N-terminal CRD determines ligand binding specificity, whereas the linker has been proposed to regulate overall Gal-8 function, including multimerization and biological activity. Here, we crystallized the Gal-8 N-terminal CRD with the peptide linker using a crystallization condition that contains Ni2+. The Ni2+ ion was found to be complexed between two CRDs via crystal packing contacts. The coordination between Ni2+ and Asp25 plays an indirect role in determining the structure of β-strand F0 and in influencing the linker conformation which could not be defined due to its dynamic nature. The linker was also shortened in situ and crystallized under a different condition, leading to a higher resolution structure refined to 1.08 Å. This crystal structure allowed definition of a short portion of the linker interacting with the Gal-8 N-terminal tail via ionic interactions and hydrogen bonds. Observation of two Gal-8 N-terminal CRD structures implies that the N-terminal tail and the linker may influence each other’s conformation. In addition, under specific crystallization conditions, glycerol could replace lactose and was observed at the carbohydrate binding site. However, glycerol did not show inhibition activity in hemagglutination assay.

  2. Novel mixing method for cross linker introduction into droplet emulsions

    CSIR Research Space (South Africa)

    Land, KJ

    2013-10-01

    Full Text Available the introduction of cross linker after droplet formation, together with the utilisation of topological microfluidic channel structures, allowing for the novel manufacture of particles. Flow over these structures has been simulated in order to choose the most...

  3. Linker-mediated assembly of gold nanoparticles into multimeric motifs

    Energy Technology Data Exchange (ETDEWEB)

    Sikora, Mateusz; Cieplak, Marek [Institute of Physics, Polish Academy of Sciences, Aleja Lotnikow 32/46, 02-668 Warsaw (Poland); Szymczak, Piotr [Institute of Theoretical Physics, Faculty of Physics, University of Warsaw, ulica Hoza 69, 00-681 Warsaw (Poland); Thompson, Damien, E-mail: mc@ifpan.edu.pl [Tyndall National Institute, Lee Maltings, University College Cork, Cork (Ireland)

    2011-11-04

    We present a theoretical description of linker-mediated self-assembly of gold nanoparticles (Au-NP). Using mesoscale simulations with a coarse-grained model for the Au NPs and dirhenium-based linker molecules, we investigate the conditions under which large clusters can grow and construct a phase diagram that identifies favorable growth conditions in terms of floating and bound linker concentrations. The findings can be considered as generic, as we expect other NP-linker systems to behave in a qualitatively similar way. In particular, we also discuss the case of antibody-functionalised Au NPs connected by the C-reactive proteins (CRPs). We extract some general rules for NP linking that may aid the production of size- and shape-specific NP clusters for technology applications.

  4. Proposed amendment to the final decision document for the hydrazine blending and storage facility, interim response action

    Energy Technology Data Exchange (ETDEWEB)

    1991-02-25

    From April through August 1989, a bench-/pilot-scale testing program was conducted to evaluate whether qualified manufactures of ultraviolet (UV)/chemical oxidation equipment could reduce the concentrations of hydrazine fuel compounds (hydrazine, monomethyl hydrazine (MMH), and unsymmetrical dimethyl hydrazine (UDMH)) and n-nitrosodimethylamine (NDMA) in the wastewater to action levels identified in the Final Decision Document. A secondary objective of this testing program was to generate design and operational information for use during the full-scale startup program.

  5. A rhodol-based fluorescent chemosensor for hydrazine and its application in live cell bioimaging

    Science.gov (United States)

    Tiensomjitr, Khomsan; Noorat, Rattha; Wechakorn, Kanokorn; Prabpai, Samran; Suksen, Kanoknetr; Kanjanasirirat, Phongthon; Pewkliang, Yongyut; Borwornpinyo, Suparerk; Kongsaeree, Palangpon

    2017-10-01

    A rhodol cinnamate fluorescent chemosensor (RC) has been developed for selective detection of hydrazine (N2H4). In aqueous medium, the rhodol-based probe exhibited high selectivity for hydrazine among other molecules. The addition of hydrazine triggered a fluorescence emission with 48-fold enhancement based on hydrazinolysis and a subsequent ring-opening process. The chemical probe also displayed a selective colorimetric response toward N2H4 from colorless solution to pink, readily observed by the naked eye. The detection limit of RC for hydrazine was calculated to be 300 nM (9.6 ppb). RC is membrane permeable and was successfully demonstrated to detect hydrazine in live HepG2 cells by confocal fluorescence microscopy.

  6. Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines

    Directory of Open Access Journals (Sweden)

    Frantisek Sersen

    2017-05-01

    Full Text Available Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene-N′-[2,6-dinitro-4-(trifluoromethyl]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH, galvinoxyl radical (GOR, and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

  7. Destruction of oxalate by reaction with hydrogen peroxide. [Hydrazine oxalate

    Energy Technology Data Exchange (ETDEWEB)

    Mailen, J.C.; Tallent, O.K.; Arwood, P.C.

    1981-09-01

    The destruction of oxalate by oxidation to carbon dioxide using hydrogen peroxide was studied as an alternative method for the disposal of oxalate in connection with the possible use of an aqueous hydrazine oxalate solution as a scrubbing agent for solvent cleanup in processes for the recovery of uranium, plutonium, and thorium by solvent extraction. The rate of oxidation of oxalate by hydrogen peroxide in acid solution at the reflux temperature was adequate for process application; reaction half-times at 100/sup 0/C were less than one hour when the hydrogen peroxide concentration was greater than 0.5 M. The reaction was first order with respect to both the oxalate and hydrogen peroxide concentrations and had an activation energy of 58.7 kJ/g-mol. The rate increased with the hydrogen ion concentration as (H/sup +/)/sup 0/ /sup 3/ but was not significantly affected by the presence of 100 ppM of uranium or copper in solution. In the near-neutral hydrazine oxalate solutions, the reaction of either component with hydrogen peroxide was too slow for process application.

  8. Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines.

    Science.gov (United States)

    Sersen, Frantisek; Gregan, Fridrich; Kotora, Peter; Kmetova, Jarmila; Filo, Juraj; Loos, Dusan; Gregan, Juraj

    2017-05-29

    Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene)-N'-[2,6-dinitro-4-(trifluoromethyl)]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR), and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

  9. Dihydropyrimidine based hydrazine dihydrochloride derivatives as potent urease inhibitors.

    Science.gov (United States)

    Khan, Ajmal; Hashim, Jamshed; Arshad, Nuzhat; Khan, Ijaz; Siddiqui, Naureen; Wadood, Abdul; Ali, Muzaffar; Arshad, Fiza; Khan, Khalid Mohammed; Choudhary, M Iqbal

    2016-02-01

    Four series of heterocyclic compounds 4-dihydropyrimidine-2-thiones 7-12 (series A), N,S-dimethyl-dihydropyrimidines 13-18 (series B), hydrazine derivatives of dihydropyrimidine 19-24 (series C), and tetrazolo dihydropyrimidine derivatives 25-30 (series D), were synthesized and evaluated for in vitro urease inhibitory activity. The series B-D were first time examined for urease inhibition. Series A and C were found to be significantly active with IC50 values between 34.7-42.9 and 15.0-26.0 μM, respectively. The structure-activity relationship showed that the free S atom and hydrazine moiety are the key pharmacophores against urease enzyme. The kinetic studies of the active series A (7-12) and C (19-24) were carried out to determine their modes of inhibition and dissociation constants Ki. Compounds of series A (7-12) and series C (19-24) showed a mixed-type of inhibition with Ki values ranging between 15.76-25.66 and 14.63-29.42 μM, respectively. The molecular docking results showed that all the active compounds of both series have significant binding interactions with the active sites specially Ni-ion of the urease enzyme. Cytotoxicity of all series A-D was also evaluated against mammalian mouse fibroblast 3T3 cell lines, and no toxicity was observed in cellular model. Copyright © 2016 Elsevier Inc. All rights reserved.

  10. Enthalpies of Formation of Hydrazine and Its Derivatives.

    Science.gov (United States)

    Dorofeeva, Olga V; Ryzhova, Oxana N; Suchkova, Taisiya A

    2017-07-20

    Enthalpies of formation, Δ f H 298 ° , in both the gas and condensed phase, and enthalpies of sublimation or vaporization have been estimated for hydrazine, NH 2 NH 2 , and its 36 various derivatives using quantum chemical calculations. The composite G4 method has been used along with isodesmic reaction schemes to derive a set of self-consistent high-accuracy gas-phase enthalpies of formation. To estimate the enthalpies of sublimation and vaporization with reasonable accuracy (5-20 kJ/mol), the method of molecular electrostatic potential (MEP) has been used. The value of Δ f H 298 ° (NH 2 NH 2 ,g) = 97.0 ± 3.0 kJ/mol was determined from 75 isogyric reactions involving about 50 reference species; for most of these species, the accurate Δ f H 298 ° (g) values are available in Active Thermochemical Tables (ATcT). The calculated value is in excellent agreement with the reported results of the most accurate models based on coupled cluster theory (97.3 kJ/mol, the average of six calculations). Thus, the difference between the values predicted by high-level theoretical calculations and the experimental value of Δ f H 298 ° (NH 2 NH 2 ,g) = 95.55 ± 0.19 kJ/mol recommended in the ATcT and other comprehensive reference sources is sufficiently large and requires further investigation. Different hydrazine derivatives have been also considered in this work. For some of them, both the enthalpy of formation in the condensed phase and the enthalpy of sublimation or vaporization are available; for other compounds, experimental data for only one of these properties exist. Evidence of accuracy of experimental data for the first group of compounds was provided by the agreement with theoretical Δ f H 298 ° (g) value. The unknown property for the second group of compounds was predicted using the MEP model. This paper presents a systematic comparison of experimentally determined enthalpies of formation and enthalpies of sublimation or vaporization with the results of

  11. Hydrazine blending and storage facility, interim response action, draft implementation document for rinsewater transfer, phase 2

    Energy Technology Data Exchange (ETDEWEB)

    1991-08-09

    This Draft Implementation Document (ID) for Rinsewater Transfer has been prepared as a requirement for conducting and completing the Interim Response Action (IRA) at the Hydrazine Blending and Storage Facility (HBSF) located at Rocky Mountain Arsenal (RMA) in Commerce City, Colorado. This document has been prepared in accordance with requirements set forth in the October 1988 Final Decision Document for the HBSF IRA (Peer, 1988) and the Amendment to the Final Decision Document (HLA, 1991). The HBSF IRA task was separated into two phases that comprise complete decommissioning of the HBSF as cited in the Federal Facility Agreement. The design portion of Phase I of the HBSF IRA included analytical methods development and laboratory certification for analysis of hydrazine fuel compounds (hydrazine, monomethyl hydrazine) (MMH), and unsymmetrical dimethyl hydrazine (UDMH) and n-nitrosodimethylamine (NDMA) in HBSF rinsewater, chemical characterization of hydrazine rinsewater, bench- and pilot-scale testing of ultraviolet (UV) light/chemical oxidation treatment systems for treatment of hydrazine rinsewater, full-scale startup testing of a UV light/chemical oxidation treatment system, and air monitoring during startup testing as described in the Draft Final Treatment Report (HLA, 1991).

  12. Effect of Water Chemistry Factors on Flow Accelerated Corrosion : pH, DO, Hydrazine

    International Nuclear Information System (INIS)

    Lee, Eun Hee; Kim, Kyung Mo; Kim, Hong Pyo

    2013-01-01

    Flow accelerated corrosion(FAC) of the carbon steel piping in pressurized water reactors(PWRs) has been major issue in nuclear industry. Severe accident at Surry Unit 2 in 1986 initiated the worldwide interest in this area. Major parameters influencing FAC are material composition, microstructure, water chemistry, and hydrodynamics. Qualitative behaviors of FAC have been well understood but quantitative data about FAC have not been published for proprietary reason. In order to minimize the FAC in PWRs, the optimal method is to control water chemistry factors. Chemistry factors influencing FAC such as pH, corrosion potential, and hydrazine contents were reviewed in this paper. FAC rate decreased with pH up to 10 because magnetite solubility decreased with pH. Corrosion potential is generally controlled dissolved oxygen (DO) and hydrazine in secondary water. DO increased corrosion potential. FAC rate decreased with DO by stabilizing magnetite at low DO concentration or by formation of hematite at high DO concentration. Even though hydrazine is generally used to remove DO, hydrazine itself thermally decomposed to ammonia, nitrogen, and hydrogen raising pH. Hydrazine could react with iron and increased FAC rate. Effect of hydrazine on FAC is rather complex and should be careful in FAC analysis. FAC could be managed by adequate combination of pH, corrosion potential, and hydrazine

  13. Reaction kinetics of hydrazine neutralization in steam generator wet lay-up solution: Identifying optimal degradation conditions

    International Nuclear Information System (INIS)

    Schildermans, Kim; Lecocq, Raphael; Girasa, Emmanuel

    2012-09-01

    During a nuclear power plant outage, hydrazine is used as an oxygen scavenger in the steam generator lay-up solution. However, due to the carcinogenic effects of hydrazine, more stringent discharge limits are or will be imposed in the environmental permits. Hydrazine discharge could even be prohibited. Consequently, hydrazine alternatives or hydrazine degradation before discharge is needed. This paper presents the laboratory tests performed to characterize the reaction kinetics of hydrazine neutralization using bleach or hydrogen peroxide, catalyzed with either copper sulfate (CuSO 4 ) or potassium permanganate (KMnO 4 ). The tests are performed on two standard steam generator lay-up solutions based on different pH control agents: ammonia or ethanolamine. Different neutralization conditions are tested by varying temperature, oxidant addition, and catalyst concentration, among others, in order to identify the optimal parameters for hydrazine neutralization in a steam generator wet lay-up solution. (authors)

  14. Improved sensitivity of a graphene FET biosensor using porphyrin linkers

    Science.gov (United States)

    Kawata, Takuya; Ono, Takao; Kanai, Yasushi; Ohno, Yasuhide; Maehashi, Kenzo; Inoue, Koichi; Matsumoto, Kazuhiko

    2018-06-01

    Graphene FET (G-FET) biosensors have considerable potential due to the superior characteristics of graphene. Realizing this potential requires judicious choice of the linker molecule connecting the target-specific receptor molecule to the graphene surface, yet there are few reports comparing linker molecules for G-FET biosensors. In this study, tetrakis(4-carboxyphenyl)porphyrin (TCPP) was used as a linker for surface modification of a G-FET and the properties of the device were compared to those of a G-FET device modified with the conventional linker 1-pyrenebutanoic acid succinimidyl ester (PBASE). TCPP modification resulted in a higher density of receptor immunoglobulin E (IgE) aptamer molecules on the G-FET. The detection limit of the target IgE was enhanced from 13 nM for the PBASE-modified G-FET to 2.2 nM for the TCPP-modified G-FET, suggesting that the TCPP linker is a powerful candidate for G-FET modification.

  15. Initial conformation of kinesin's neck linker

    International Nuclear Information System (INIS)

    Geng Yi-Zhao; Yan Shi-Wei; Ji Qing; Liu Shu-Xia

    2014-01-01

    How ATP binding initiates the docking process of kinesin's neck linker is a key question in understanding kinesin mechanisms. By exploiting a molecular dynamics method, we investigate the initial conformation of kinesin's neck linker in its docking process. We find that, in the initial conformation, the neck linker has interactions with β0 and forms a ‘cover-neck bundle’ structure with β0. From this initial structure, the formation of extra turns and the docking of the cover-neck bundle structure can be achieved. The motor head provides a forward force on the initial cover-neck bundle structure through ATP-induced rotation. This force, together with the hydrophobic interaction of ILE327 with the hydrophobic pocket on the motor head, drives the formation of the extra turn and initiates the neck linker docking process. Based on these findings, a pathway from ATP binding-induced motor head rotation to neck linker docking is proposed. (interdisciplinary physics and related areas of science and technology)

  16. Hematoxylin multi-wall carbon nanotubes modified glassy carbon electrode for electrocatalytic oxidation of hydrazine

    International Nuclear Information System (INIS)

    Zare, Hamid R.; Nasirizadeh, Navid

    2007-01-01

    A new hydrazine sensor has been fabricated by immobilizing hematoxylin at the surface of a glassy carbon electrode (GCE) modified with multi-wall carbon nanotube (MWCNT). The adsorbed thin films of hematoxylin on the MWCNT modified GCE show one pair of peaks with surface confined characteristics. The hematoxylin MWCNT (HMWCNT) modified GCE shows highly catalytic activity toward hydrazine electro-oxidation. The results show that the peak potential of hydrazine at HMWCNT modified GCE surface shifted by about 167 and 255 mV toward negative values compared with that at an MWCNT and activated modified GCE surface, respectively. In addition, at HMWCNT modified electrode surface remarkably improvement the sensitivity of determination of hydrazine. The kinetic parameters, such as the electron transfer coefficient, α, and the standard heterogeneous rate constant, k 0 , for oxidation of hydrazine at the HMWCNT modified GCE were determined and also is shown that the heterogeneous rate constant, k', is strongly potential dependent. The overall number of electron involved in the catalytic oxidation of hydrazine and the number of electrons involved in the rate-determining steps are 2 and 1, respectively. The amperometric detection of hydrazine is carried out at 220 mV in 0.1 M phosphate buffer solution (pH 7) with linear response range 2.0-122.8 μM hydrazine, detection limit of 0.68 μM and sensitivity of 0.0208 μA μM -1 . Finally the amperometric response for hydrazine determination is reproducible, fast and extremely stable, with no loss in sensitivity over a continual 400 s operation

  17. Hydrazine levels in formulations of hydralazine, isoniazid, and phenelzine over a 2-year period.

    Science.gov (United States)

    Lovering, E G; Matsui, F; Curran, N M; Robertson, D L; Sears, R W

    1983-08-01

    Hydrazine levels in formulations of hydralazine, isoniazid, and phenelzine have been measured over a 2-year period under ambient conditions and under temperature and humidity stress. Hydralazine tablets are stable under ambient conditions, but the hydrazine level in an injectable formulation increased from 4.5 to 10 micrograms/ml over a 23-month period. Isoniazid tablets are also stable, but hydrazine levels in an elixir and a pyridoxine combination product doubled to 44 micrograms/ml and 19 micrograms/tablet, respectively. Levels in phenelzine tablets appeared to remain constant at approximately 60 micrograms/tablet, with considerable tablet-to-tablet variation.

  18. Antisymmetric Amino-Wagging Band of Hydrazine up toK‧ = 13 Levels

    Science.gov (United States)

    Gulaczyk, Iwona; Kre, Marek; Valentin, Alain

    1997-12-01

    A newly recorded high-resolution infrared spectrum of hydrazine has been studied in the 729-1198 cm-1region (the ν12antisymmetric wagging band) with a resolution of 0.002 cm-1. About 1350 transitions withK‧ from 7 to 13 have been newly assigned and about 2350 transitions with lower values ofK‧ reanalyzed with the improved precision. The effective parameters have been calculated separately for each value ofK‧ using the Hougen-Ohashi hamiltonian for hydrazine. The extended assignment completes the analysis of the ν12band of hydrazine.

  19. The CEGB programme on comparative assessment of alternatives to hydrazine for oxygen removal from aqueous systems

    International Nuclear Information System (INIS)

    Case, B.; Wall, K.H.; Wates, R.W.

    1994-01-01

    The principal conclusion from the programme of work carried out by the CEGB was that Carbohydrazide appeared to be the most promising alternative to hydrazine for boiler feedwater conditioning. It is an effective oxygen scavenger at higher feedwater temperatures, its breakdown products are not a serious threat to circuit materials and it is safer to handle than hydrazine. The main disadvantages, at the time of the study, appeared to be the lack of a simple reliable method for measuring residual carbohydrazide in feedwater and a cost for the alternative chemical of up to 20 times that of hydrazine. (orig.)

  20. Hydrazine reagents as derivatizing agents in environmental analysis--a critical review.

    Science.gov (United States)

    Vogel, M; Büldt, A; Karst, U

    2000-04-01

    Hydrazine reagents are a well-known group of derivatizing agents for the determination of aldehydes and ketones in liquid and gaseous samples. Within this article, the most important hydrazine reagents are critically summarized, and their major applications in different fields, including environmental analysis, food chemistry and industrial analysis are introduced. As 2,4-dinitrophenylhydrazine (DNPH) is the basic reagent for several international standard procedures, its properties are discussed in detail. Particular focus is directed on the chemistry of the hydrazine reagents, and chemical interferences are considered. Recent methods for the determination of various oxidants using hydrazine reagents are presented as well. Due to limited space, this review does not cover the related field of carbohydrate analysis, although many chemical aspects are similar.

  1. Enthalpy of Formation of N 2 H 4 (Hydrazine) Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Feller, David [Department; Bross, David H. [Chemical; Ruscic, Branko [Chemical; Computation

    2017-08-02

    In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57 ± 0.47 kJ/mol at 0 K (97.41 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and FPD enthalpies.

  2. A new potentiometric determination of hydrazine in the presence of uranium(IV)

    International Nuclear Information System (INIS)

    Singh, N.S.; Mohan, S.V.

    1996-01-01

    The present method describes the determination of hydrazine by making use of potentiometric titration technique. The underlying principle is back titration of unreacted excess cerium remaining after the complete oxidation of hydrazine. Standardized ferrous ammonium sulfate was used for titration. This method was applied to 'real samples' generated from a nuclear reprocessing plant wherein control of hydrazine is of paramount importance. The interference of U(IV), Cr(III), U(VI), nitrite, and chloride was studied and of all these ions the way to eliminate the interference of U(IV) was only attempted. The relative standard deviations (RSD) for synthetic as well as 'real samples' were determined. The method gives RSD of less than 1% in the range of 1 mg to 20 mg of hydrazine. The error in the range 3 mg to 17 mg was found to be less than 1%. (author). 5 refs., 3 tabs

  3. Hydrazine selective dual signaling chemodosimetric probe in physiological conditions and its application in live cells

    Energy Technology Data Exchange (ETDEWEB)

    Nandi, Sandip; Sahana, Animesh; Mandal, Sandip [Department of Chemistry, The University of Burdwan, Burdwan, 713104 West Bengal (India); Sengupta, Archya; Chatterjee, Ansuman [Department of Zoology, Visva Bharati University, Santiniketan, West Bengal (India); Safin, Damir A., E-mail: damir.a.safin@gmail.com [Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium); Babashkina, Maria G.; Tumanov, Nikolay A.; Filinchuk, Yaroslav [Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium); Das, Debasis, E-mail: ddas100in@yahoo.com [Department of Chemistry, The University of Burdwan, Burdwan, 713104 West Bengal (India)

    2015-09-17

    A rhodamine–cyanobenzene conjugate, (E)-4-((2-(3′,6′-bis(diethylamino)-3-oxospiro[isoindoline-1,9′-xanthene] -2-yl)ethylimino)methyl)benzonitrile (1), which structure has been elucidated by single crystal X-ray diffraction, was synthesized for selective fluorescent “turn-on” and colorimetric recognition of hydrazine at physiological pH 7.4. It was established that 1 detects hydrazine up to 58 nM. The probe is useful for the detection of intracellular hydrazine in the human breast cancer cells MCF-7 using a fluorescence microscope. Spirolactam ring opening of 1, followed by its hydrolysis, was established as a probable mechanism for the selective sensing of hydrazine. - Highlights: • A selective rhodamine–cyanobenzene conjugate is synthesized. • The conjugate is a selective dual signaling chemodosimetric probe towards hydrazine. • Spirolactam ring opening of the probe, followed by its hydrolysis, is the sensing mechanism. • The probe detects hydrazine in the human breast cancer cells MCF-7 imaging.

  4. A streptavidin linker layer that functions after drying.

    Science.gov (United States)

    Xia, Nan; Shumaker-Parry, Jennifer S; Zareie, M Hadi; Campbell, Charles T; Castner, David G

    2004-04-27

    The ability of streptavidin (SA) to simultaneously bind four biotins is often used in linker layers, where a biotinylated molecule is linked to a biotin-functionalized surface via SA. For biosensor and array applications, it is desirable that the SA linker layer be stable to drying and rehydration. In this study it was observed that a significant decrease in binding capacity of a SA layer occurred when that layer was dried. For this study a SA linker layer was constructed by binding SA to a biotin-containing alkylthiolate monolayer (BAT/OEG) self-assembled onto gold. Its stability after drying was investigated using surface plasmon resonance (SPR). Approximately a quarter of the SA layer was removed from the BAT/OEG surface upon drying and rehydration, suggesting disruption of SA-biotin binding when dry. This resulted in the dried SA layer losing approximately 40% of its biotinylated ferritin (BF) binding capacity. Coating the layer with trehalose before drying was found to inhibit the loss of SA from the BAT/OEG surface. SPR showed that the trehalose-protected SA linker layer retained approximately 91% of its original BF binding capacity after drying and rehydration. Atomic force microscopy, which was used to image individual surface-bound SA and BF molecules, qualitatively confirmed these observations.

  5. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

    KAUST Repository

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J.; Zhou, Hong-Cai

    2018-01-01

    strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores

  6. Open and Closed: The Roles of Linker Histones in Plants and Animals

    OpenAIRE

    Over, Ryan S.; Michaels, Scott D.

    2014-01-01

    Linker histones play key roles alongside core histones in the regulation and maintenance of chromatin. Here, we illustrate our current understanding of the contributions of linker histones to the cell cycle, development, and chromatin structure in plants and animals.

  7. Synthesis and structural studies of Cp{sup *} rhodium and Cp{sup *} iridium complexes of picolinic hydrazine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Palepu, Narasinga Rao; Kollipara, Mohan Rao [Centre for Advanced Studies in Chemistry, North-Eastern Hill University, Shillong (India); Kaminsky Werner [Dept. of Chemistry, University of Washington, Seattle (United States)

    2017-01-15

    A series of Cp{sup *}Rh and Cp{sup *}Ir complexes of picolinic hydrazine ligand are synthesized and characterized. Picolinic hydrazine has yielded only dinuclear complexes in the case of rhodium metal whereas both mono and dinuclear complexes with iridium metal. Iridium complexes are formed as quaternary salts by the migration of the N–H proton onto the adjacent amine group of the hydrazine after binding to the metal. Picolinic hydrazine acts as nitrogen and oxygen donor ligand in the form of bi and tetradentate bonding modes.

  8. Dipolar cross-linkers for PDMS networks with enhanced dielectric permittivity and low dielectric loss

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Daugaard, Anders Egede; Hvilsted, Søren

    2013-01-01

    -(4-((4-nitrophenyl)diazenyl)phenoxy)-prop-1-yn-1-ylium, with a synthesized silicone compatible azide-functional cross-linker by click chemistry. The thermal, mechanical and electromechanical properties were investigated for PDMS films with 0 to 3.6 wt% of dipole-cross-linker. The relative dielectric permittivity......Dipole grafted cross-linkers were utilized to prepare polydimethylsiloxane (PDMS) elastomers with various chain lengths and with various concentrations of functional cross-linker. The grafted cross-linkers were prepared by reaction of two alkyne-functional dipoles, 1-ethynyl-4-nitrobenzene and 3...

  9. Optimization of wet lay-up conditions for steam generators hydrazine chemical treatment

    International Nuclear Information System (INIS)

    Long, A.; Organista, M.; Brun, C.; Combrade, P.

    2002-01-01

    Since a long time, hydrazine is used as a chemical agent to prevent corrosion of unalloyed steels. This is a conventional treatment widely used by nuclear power plant operators. But its application in SG lay-up at French nuclear power plants has, however, lead to some drawbacks. Effluent releases: Due to regulation relative to release of hydrazine and alkaline chemical compounds, some plant operators limit the concentrations of reagents to levels that could lead to insufficient protection of materials. Safety hazards associated with SG nitrogen blanketing: Prohibiting use of nitrogen blankets for SG wet lay-up due to associated safety hazards could likewise jeopardize corrosion protection at normally specified hydrazine levels. As the exact limits of hydrazine action against corrosion during SG lay-up are not well known, it is sometimes difficult to evaluate the risk associated to low dosage of N 2 H 4 . In order to answer to these problems, Framatome ANP (France) decided to carry out a test program aimed to determine the limit conditions for use of hydrazine in a wet lay-up environment. (authors)

  10. Hydrazine-mediated construction of nanocrystal self-assembly materials.

    Science.gov (United States)

    Zhou, Ding; Liu, Min; Lin, Min; Bu, Xinyuan; Luo, Xintao; Zhang, Hao; Yang, Bai

    2014-10-28

    Self-assembly is the basic feature of supramolecular chemistry, which permits to integrate and enhance the functionalities of nano-objects. However, the conversion of self-assembled structures to practical materials is still laborious. In this work, on the basis of studying one-pot synthesis, spontaneous assembly, and in situ polymerization of aqueous semiconductor nanocrystals (NCs), NC self-assembly materials are produced and applied to design high performance white light-emitting diode (WLED). In producing self-assembly materials, the additive hydrazine (N2H4) is curial, which acts as the promoter to achieve room-temperature synthesis of aqueous NCs by favoring a reaction-controlled growth, as the polyelectrolyte to weaken inter-NC electrostatic repulsion and therewith facilitate the one-dimensional self-assembly, and in particular as the bifunctional monomers to polymerize with mercapto carboxylic acid-modified NCs via in situ amidation reaction. This strategy is versatile for mercapto carboxylic acid-modified aqueous NCs, for example CdS, CdSe, CdTe, CdSe(x)Te(1-x), and Cd(y)Hg(1-y)Te. Because of the multisite modification with carboxyl, the NCs act as macromonomers, thus producing cross-linked self-assembly materials with excellent thermal, solvent, and photostability. The assembled NCs preserve strong luminescence and avoid unpredictable fluorescent resonance energy transfer, the main problem in design WLED from multiple NC components. These advantages allow the fabrication of NC-based WLED with high color rendering index (86), high luminous efficacy (41 lm/W), and controllable color temperature.

  11. Gas chromatographic determination of residual hydrazine and morpholine in boiler feed water and steam condensates

    International Nuclear Information System (INIS)

    Vatsala, S.; Bansal, V.; Tuli, D.K.; Rai, M.M.; Jain, S.K.; Srivastava, S.P.; Bhatnagar, A.K.

    1994-01-01

    Hydrazine, an oxygen scavenger in boiler water, was derivatised to the corresponding acetone azine and determined at the ng ml -1 level by gas chromatography. Morpholine, a corrosion inhibitor used in steam boilers, was estimated either directly (if >2.0 μg ml -1 ) or by quantitative preconcentration (0.1 ng-2.0 μg ml -1 ). To obtain symmetrical peaks for these amines, the column packing was coated with KOH. Use of a nitrogen-specific detector improved accuracy of estimation of hydrazine and morpholine, giving a RSD of 1.9-3.6%. Chromatographic analysis of these amines in boiler feed water and steam condensate samples collected from boilers servicing a pertroleum refinery is described. Environmental safety regulations calls for monitoring of hydrazine and the methods developed can easily be adapted for this purpose. (orig.)

  12. A Fluorescent Probe for Sensitive Detection of Hydrazine and Its Application in Red Wine and Water.

    Science.gov (United States)

    Wang, Jialin; Wang, Hao; Yang, Shaoxiang; Tian, Hongyu; Liu, Yongguo; Hao, Yanfeng; Zhang, Jie; Sun, Baoguo

    2018-01-01

    A fluorescent probe, 7-(diethylamino)-2-oxo-2H-chromene-4-carbaldehyde (probe 1), was designed and synthesized for the sensitive detection of hydrazine. The addition of N 2 H 4 caused the fluorescence intensity of probe 1 to decrease. The probe's fluorescence was turn-off after adding N 2 H 4 , which could be observed under UV light at 365 nm. Moreover, once treated with different concentrations N 2 H 4 solutions, the solution color change could be distinguished, which indicates that probe 1 could be used as a visual sensor for hydrazine. Moreover, probe 1 can be used as a signal tool to determine hydrazine levels in solutions, such as red wine and water.

  13. Proceedings of the Conference on the Environmental Chemistry of Hydrazine Fuels (3rd) Held in Panama City Beach, Florida on 15-17 September 1987

    Science.gov (United States)

    1988-01-01

    aqueous or alcoholic hydrazine. It is interesting to note that no chromium (II) hydrazine complex has been prepared directly from a chromium (III...S.E. Bowden, " Oxydation of Hydrazine in Aqueous Solutions", CEEDO-TR-78-11 (1978). AD-A058239. N72-12242. 117p VIBRATIONAL SPECTROSCOPIC STUDY OF THE...phthalocyanlne. Stearyl alcohol was added to improve the transfer, The response to hydrazine was fast, but the sensors were very slow to recover.(3) The

  14. Control and management of the chemical risk linked with hydrazine hydrate storage, unloading and injection across French nuclear fleet

    International Nuclear Information System (INIS)

    Spahic, Mersiha; Dzemidzic Aida; Dijoux, Michel; Pages, Danielle; Rigal, Jean-Francois; Boize, Magali

    2012-09-01

    Across the EDF nuclear fleet, the chemical risk linked with hydrazine hydrate storage, unloading and injection has received much attention in the past decades. Since 1997, continuous investigation into the substitution of dangerous and carcinogenic chemicals has been conducted and regularly updated by EDF. As a downstream user of hydrazine hydrate, EDF is concerned by REACH legislation, in force since 1 June 2007. As part of the compliance process with REACH, EDF provided its hydrazine hydrate suppliers with information regarding the uses of the chemical. This was done by the end of 2008, as per REACH deadline. On the other hand, EDF contributed throughout European Chemicals Agency consultation phase by submitting data relating to hydrazine hydrate uses across nuclear sites. The absence of a suitable hydrazine hydrate replacement product, able to satisfy the entirety of technical requirements, entails rigorous arrangements to be implemented in order to segregate the zones where use of hydrazine is made and therefore eradicate the risk to personnel regarding hydrazine effects. Consequently, a number of engineering changes and modifications are to be carried out on the chemical injection systems of 58 French nuclear power plants over the next few years as part of the EDF Hydrazine Fleet Programme. (authors)

  15. Concentric-Electrode Organic Electrochemical Transistors: Case Study for Selective Hydrazine Sensing

    Directory of Open Access Journals (Sweden)

    Sébastien Pecqueur

    2017-03-01

    Full Text Available We report on hydrazine-sensing organic electrochemical transistors (OECTs with a design consisting of concentric annular electrodes. The design engineering of these OECTs was motivated by the great potential of using OECT sensing arrays in fields such as bioelectronics. In this work, poly(3,4-ethylenedioxythiophene:poly(styrenesulfonate (PEDOT:PSS-based OECTs have been studied as aqueous sensors that are specifically sensitive to the lethal hydrazine molecule. These amperometric sensors have many relevant features for the development of hydrazine sensors, such as a sensitivity down to 10−5 M of hydrazine in water, an order of magnitude higher selectivity for hydrazine than for nine other water-soluble common analytes, the capability to entirely recover its base signal after water flushing, and a very low operation voltage. The specificity for hydrazine to be sensed by our OECTs is caused by its catalytic oxidation at the gate electrode, and enables an increase in the output current modulation of the devices. This has permitted the device-geometry study of the whole series of 80 micrometric OECT devices with sub-20-nm PEDOT:PSS layers, channel lengths down to 1 µm, and a specific device geometry of coplanar and concentric electrodes. The numerous geometries unravel new aspects of the OECT mechanisms governing the electrochemical sensing behaviours of the device—more particularly the effect of the contacts which are inherent at the micro-scale. By lowering the device cross-talk, micrometric gate-integrated radial OECTs shall contribute to the diminishing of the readout invasiveness and therefore further promote the development of OECT biosensors.

  16. Chemical reactions in organic monomolecular layers. Condensation of hydrazine on carbonyl functions

    International Nuclear Information System (INIS)

    Rosilio, Charles; Ruaudel-Teixier, Annie.

    1976-01-01

    Evidence is given for chemical reactions of hydrazine (NH 2 -NH 2 ) with different carbonyl functional groups of organic molecules in the solid state, in monomolecular layer structures. The condensation of hydrazine with these molecules leads to conjugated systems by bridging the N-N links, to cyclizations, and also to polycondensations. The reactions investigated were followed up by infrared spectrophotometry, by transmission and metallic reflection. These chemical reactions revealed in the solid phase constitute a polycondensation procedure which is valuable in obtaining organized polymers in monomolecular layers [fr

  17. Solvent properties of hydrazine in the preparation of metal chalcogenide bulk materials and films.

    Science.gov (United States)

    Yuan, Min; Mitzi, David B

    2009-08-21

    A combination of unique solvent properties of hydrazine enables the direct dissolution of a range of metal chalcogenides at ambient temperature, rendering this an extraordinarily simple and soft synthetic approach to prepare new metal chalcogenide-based materials. The extended metal chalcogenide parent framework is broken up during this process, and the resulting metal chalcogenide building units are re-organized into network structures (from 0D to 3D) based upon their interactions with the hydrazine/hydrazinium moieties. This Perspective will review recent crystal and materials chemistry developments within this family of compounds and will briefly discuss the utility of this approach in metal chalcogenide thin-film deposition.

  18. Preparation of 3,5-disubstituted pyrazoles and isoxazoles from terminal alkynes, aldehydes, hydrazines, and hydroxylamine.

    Science.gov (United States)

    Harigae, Ryo; Moriyama, Katsuhiko; Togo, Hideo

    2014-03-07

    The reaction of terminal alkynes with n-BuLi, and then with aldehydes, followed by the treatment with molecular iodine, and subsequently hydrazines or hydroxylamine provided the corresponding 3,5-disubstituted pyrazoles or isoxazoles in good yields with high regioselectivity, through the formations of propargyl secondary alkoxides and α-alkynyl ketones. The present reactions are one-pot preparation of 3,5-disubstituted pyrazoles from terminal alkynes, aldehydes, molecular iodine, and hydrazines, and 3,5-disubstituted isoxazoles from terminal alkynes, aldehydes, molecular iodine, and hydroxylamine.

  19. Enhanced biodegradation of methylhydrazine and hydrazine contaminated NASA wastewater in fixed-film bioreactor.

    Science.gov (United States)

    Nwankwoala, A U; Egiebor, N O; Nyavor, K

    2001-01-01

    The aerobic biodegradation of National Aeronautics and Space Administration (NASA) wastewater that contains mixtures of highly concentrated methylhydrazine/hydrazine, citric acid and their reaction product was studied on a laboratory-scale fixed film trickle-bed reactor. The degrading organisms, Achromobacter sp., Rhodococcus B30 and Rhodococcus J10, were immobilized on coarse sand grains used as support-media in the columns. Under continuous flow operation, Rhodococcus sp. degraded the methylhydrazine content of the wastewater from a concentration of 10 to 2.5 mg/mL within 12 days and the hydrazine from approximately 0.8 to 0.1 mg/mL in 7 days. The Achromobacter sp. was equally efficient in degrading the organics present in the wastewater, reducing the concentration of the methylhydrazine from 10 to approximately 5 mg/mL within 12 days and that of the hydrazine from approximately 0.8 to 0.2 mg/mL in 7 days. The pseudo first-order rate constants of 0.137 day(-1) and 0.232 day(-1) were obtained for the removal of methylhydrazine and hydrazine, respectively, in wastewater in the reactor column. In the batch cultures, rate constants for the degradation were 0.046 and 0.079 day(-1) for methylhydrazine and hydrazine respectively. These results demonstrate that the continuous flow bioreactor afford greater degradation efficiencies than those obtained when the wastewater was incubated with the microbes in growth-limited batch experiments. They also show that wastewater containing hydrazine is more amenable to microbial degradation than one that is predominant in methylhydrazine, in spite of the longer lag period observed for hydrazine containing wastewater. The influence of substrate concentration and recycle rate on the degradation efficiency is reported. The major advantages of the trickle-bed reactor over the batch system include very high substrate volumetric rate of turnover, higher rates of degradation and tolerance of the 100% concentrated NASA wastewater. The

  20. Synthesis, characterization and antioxidant study of N,N’-bis(2-chlorobenzamidothiocarbonyl)hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Firdausiah, Syadza; Hasbullah, Siti Aishah; Yamin, Bohari M. [School of Chemical Science and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)

    2015-09-25

    N,N’-bis(2-chlorobenzamidothiocarbonyl)hydrazine was synthesized from 2-chlorobenzoylisothiocyanate and hydrazine in acetone. The compound was characterized by infrared, {sup 1}H and {sup 13}C NMR, and UV-Vis spectroscopies. X-ray crystallography study showed the molecule adopt trans configuration at both N-N and C-N bonds. The compound showed high antioxidant activity, EC{sub 50} of 374.89 µM, compared to ascorbic acid (EC{sub 50} of 561.36 µM)

  1. Selective fluorescent detection of aspartic acid and glutamic acid employing dansyl hydrazine dextran conjugate.

    Science.gov (United States)

    Nasomphan, Weerachai; Tangboriboonrat, Pramuan; Tanapongpipat, Sutipa; Smanmoo, Srung

    2014-01-01

    Highly water soluble polymer (DD) was prepared and evaluated for its fluorescence response towards various amino acids. The polymer consists of dansyl hydrazine unit conjugated into dextran template. The conjugation enhances higher water solubility of dansyl hydrazine moiety. Of screened amino acids, DD exhibited selective fluorescence quenching in the presence of aspartic acid (Asp) and glutamic acid (Glu). A plot of fluorescence intensity change of DD against the concentration of corresponding amino acids gave a good linear relationship in the range of 1 × 10(-4) M to 25 × 10(-3) M. This establishes DD as a potential polymeric sensor for selective sensing of Asp and Glu.

  2. The flexibility of modified-linker MIL-53 materials.

    Science.gov (United States)

    Munn, Alexis S; Pillai, Renjith S; Biswas, Shyam; Stock, Norbert; Maurin, Guillaume; Walton, Richard I

    2016-03-14

    The flexibility of eight aluminium hydroxo terephthalates [Al(OH)(BDC-X)]·n(guest) (BDC = 1,4-benzene-dicarboxylate; X = -H, -CH3, -Cl, -Br, -NH2, -NO2, -(OH)2, -CO2H) crystallising in the MIL-53-type structure was investigated upon thermal dehydration of as-made samples, superhydration and methanol adsorption/desorption using in situ powder X-ray diffraction (PXRD). Profile fitting was used to determine lattice parameters as a function of time and/or temperature to describe their structural evolution. It has thus been shown that while methanol vapour adsorption induces an opening of all the modified frameworks, except the -NH2 material, superhydration only leads to open structures for Al-MIL-53-NO2, -Br and -(OH)2. All the MIL-53 solids, except Al-MIL-53-(OH)2 are present in the open structures upon thermal dehydration. In addition to the exploration of the breathing behavior of this MIL-53 series, the issue of disorder in the distribution of the functional groups between the organic linkers was explored. As a typical illustration, density functional theory calculations were carried out on different structures of Al-MIL-53-Cl, in which the distribution of -Cl within two adjacent BDC linkers is varied. The results show that the most energetically stable configuration leads to the best agreement with the experimental PXRD pattern. This observation supports that the distribution of the selected linker substituent in the functionalised solid is governed by energetics and that there is a preference for an ordering of this arrangement.

  3. Investigation of the Linker Swing Motion in the Zeolitic Imidazolate Framework ZIF-90

    KAUST Repository

    Zheng, Bin

    2018-03-13

    The linker swing motion in the zeolitic imidazolate framework ZIF-90 is investigated by density functional theory (DFT) calculation, molecular dynamics (MD) and grand-canonical Monte Carlo (GCMC) simulations. The relation between the terminal aldehyde group rotation and the linker swing motion is revealed. The extremely high activation energy of the linker swing motion in ZIF-90 can be attributed to the asymmetric geometry and electron distribution of aldehyde groups. The change in the gate structure resulting from the linker rotation is used to understand the guest adsorption in ZIF-90. This study shows that it is possible to tune the linker swing motion and then the properties of ZIF-90 by manipulating the terminal group rotation. The results highlight the importance of considering the internal freedom effects to correctly describe the linker swing motion and the flexibility of metal-organic frameworks (MOFs).

  4. Open and closed: the roles of linker histones in plants and animals.

    Science.gov (United States)

    Over, Ryan S; Michaels, Scott D

    2014-03-01

    Histones package DNA in all eukaryotes and play key roles in regulating gene expression. Approximately 150 base pairs of DNA wraps around an octamer of core histones to form the nucleosome, the basic unit of chromatin. Linker histones compact chromatin further by binding to and neutralizing the charge of the DNA between nucleosomes. It is well established that chromatin packing is regulated by a complex pattern of posttranslational modifications (PTMs) to core histones, but linker histone function is less well understood. In this review, we describe the current understanding of the many roles that linker histones play in cellular processes, including gene regulation, cell division, and development, while putting the linker histone in the context of other nuclear proteins. Although intriguing roles for plant linker histones are beginning to emerge, much of our current understanding comes from work in animal systems. Many unanswered questions remain and additional work is required to fully elucidate the complex processes mediated by linker histones in plants.

  5. Specific distribution of the Saccharomyces cerevisiae linker histone homolog HHO1p in the chromatin

    OpenAIRE

    Freidkin, Ilya; Katcoff, Don J.

    2001-01-01

    In virtually all eukaryotic organisms, linker DNA between nucleosomes is associated with a histone termed linker histone or histone H1. In Saccharomyces cerevisiae, HHO1 encodes a putative linker histone with very significant homology to histone H1. The encoded protein is expressed in the nucleus, but has not been shown to affect global chromatin structure, nor has its deletion shown any detectable phenotype. In vitro chromatin assembly experiments with recombinant HHO1p have shown that it is...

  6. X-ray absorption spectroscopy study on the thermal and hydrazine reduction of graphene oxide

    International Nuclear Information System (INIS)

    Liang, Xianqing; Wang, Yu; Zheng, Huiyuan; Wu, Ziyu

    2014-01-01

    Highlights: • XAS study of GO and reduced GO was performed. • Detailed evolution of the electronic structures and chemical bonding of GO was revealed. • A new efficient route for the reduction of GO is proposed. - Abstract: X-ray absorption spectroscopy (XAS) was applied to systemically investigate the deoxygenation of graphene oxide (GO) via annealing and hydrazine treatment. Detailed evolution of the electronic structures and chemical bonding of GO was presented. The enhanced intensity of π * resonance and the appearance of splitting σ * resonance in C K-edge XAS spectra suggest high extents of recoveries of π-conjugation upon reduction using thermal annealing or hydrazine. Experimental results revealed that the carboxyl as well as epoxide and hydroxyl groups on the surface of GO were thermally reduced first, followed by the more difficult removal of carbonyl and cyclic ether groups at higher temperatures. The hydrazine reduction could remove epoxide, hydroxyl and carboxyl groups effectively, whereas the carbonyl groups were partially reduced with the incorporation of nitrogen species simultaneously. The residual oxygen functional groups on hydrazine-reduced GO could be further removed after modest thermal annealing. It was proposed that a combination of both types of reductions would give the best deoxygenation efficiency for the production of graphene

  7. Metabolomics of Hydrazine-Induced Hepatotoxicity in Rats for Discovering Potential Biomarkers

    Directory of Open Access Journals (Sweden)

    Zhuoling An

    2018-01-01

    Full Text Available Metabolic pathway disturbances associated with drug-induced liver injury remain unsatisfactorily characterized. Diagnostic biomarkers for hepatotoxicity have been used to minimize drug-induced liver injury and to increase the clinical safety. A metabolomics strategy using rapid-resolution liquid chromatography/tandem mass spectrometry (RRLC-MS/MS analyses and multivariate statistics was implemented to identify potential biomarkers for hydrazine-induced hepatotoxicity. The global serum and urine metabolomics of 30 hydrazine-treated rats at 24 or 48 h postdosing and 24 healthy rats were characterized by a metabolomics approach. Multivariate statistical data analyses and receiver operating characteristic (ROC curves were performed to identify the most significantly altered metabolites. The 16 most significant potential biomarkers were identified to be closely related to hydrazine-induced liver injury. The combination of these biomarkers had an area under the curve (AUC > 0.85, with 100% specificity and sensitivity, respectively. This high-quality classification group included amino acids and their derivatives, glutathione metabolites, vitamins, fatty acids, intermediates of pyrimidine metabolism, and lipids. Additionally, metabolomics pathway analyses confirmed that phenylalanine, tyrosine, and tryptophan biosynthesis as well as tyrosine metabolism had great interactions with hydrazine-induced liver injury in rats. These discriminating metabolites might be useful in understanding the pathogenesis mechanisms of liver injury and provide good prospects for drug-induced liver injury diagnosis clinically.

  8. Hydrazine and hydroxylamine as probes for O2-reduction site of mitochondrial cytochrome c oxidase.

    Science.gov (United States)

    Kubota, T; Yoshikawa, S

    1993-01-01

    Reactions of hydrazine and hydroxylamine with bovine heart cytochrome c oxidase in the fully reduced state were investigated under anaerobic conditions following the visible-Soret spectral change. Hydrazine gave a sharp band at 575 nm with 20% decrease in the alpha band at 603 nm, and hydroxylamine induced a 2 nm blue-shift for the alpha band without any clear splitting. The Soret band at 443 nm was decreased significantly in intensity, with the concomitant appearance of a shoulder with hydrazine or a peak with hydroxylamine, both near 430 nm. The dependence on pH of the affinity of these reagents for the enzyme indicates that only the deprotonated forms of these reagents bind to the enzyme, suggesting a highly hydrophobic environment of the haem ligand-biding site. These spectral changes were largely removed by addition of cyanide or CO. However, detailed analysis of these spectral changes indicates that hydrazine perturbs the shape of the spectral change induced by cyanide and hydroxylamine perturbs that induced by CO. These results suggest that these aldehyde reagents bind to haem a3 iron as well as to a second site which is most likely to be the formyl group on the haem periphery, and that these two sites bind these reagents anti-cooperatively with each other. PMID:8389138

  9. Redox conditions effect on flow accelerated corrosion: Influence of hydrazine and oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Bouvier, O. de [EDF, R and D Div., Moret sur Loing (France); Bouchacourt, M. [EDF, Engineering and Service Div., Villeurbanne (France); Fruzzetti, K. [EPRI, Science and Technology Div., Palo Alto, CA (United States)

    2002-07-01

    Flow accelerated corrosion (FAC) of carbon steels has been studied world-wide for more than twenty years and is now fairly well understood. The influence of several parameters like water chemistry (i.e. pH and oxygen content), temperature, hydrodynamic or mass transfer conditions (i.e. flow velocity, geometry, steam quality..) and steel composition on the corrosion kinetics has been demonstrated both theoretically and experimentally. However, the effect of a reducing environment and variable redox conditions have not yet been fully explored. It's well known that a reducing environment is effective in increasing the resistance of steam generator tubing to intergranular attack / stress corrosion cracking (IGA/SCC) and pitting. In that way, secondary water chemistry specifications have been modified from low hydrazine to high hydrazine chemistry in the steam-water circuit. Nevertheless, increasing hydrazine levels up to 200 {mu}g/kg could have a detrimental effect by potentially enhancing the FAC process. Moreover, in order to have a complete understanding of the possible impact of the water chemistry environment it is also important to consider the impact of redox conditions during shutdowns (cold and/or hot shutdowns) and start up periods when aerated water injections are made to maintain a constant water level in the Steam Generators from the auxiliary feedwater circuit. Therefore, a common EDF and EPRI R and D effort has been recently carried out to study the effects of hydrazine and oxygen on FAC. The results are presented as follows. (authors)

  10. The development of hydrazine-processed Cu(In,Ga)(Se,S){sub 2} solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Bob, Brion; Lei, Bao; Chung, Choong-Heui; Yang, Wenbing; Hsu, Wan-Ching; Duan, Hsin-Sheng; Hou, William Wei-Jen; Li, Sheng-Han; Yang, Yang [Department of Materials Science and Engineering, University of California, Los Angeles, CA (United States)

    2012-05-15

    The hydrazine-based deposition of Cu(In,Ga)(S,Se){sub 2} (CIGS) thin films has attracted considerable attention in recent years due to its potential for the high-throughput production of photovoltaic devices based on this absorber material. This article provides an introduction as well as presenting a complete picture of the current status of hydrazine-based CIGS solar-cell fabrication, including the three major steps of this deposition process: dissolution of the precursor materials in hydrazine, deposition of a film from the resulting precursor solution, and the completion and characterization of a photovoltaic device following absorber deposition. Recent discoveries are then discussed, regarding the dissolution chemistry of the relevant precursor complexes in hydrazine, which together represent the true foundation of this processing method. Recent studies on CIGS film formation are then summarized, including the control and analysis of the crystalline phase, electronic bandgap, and film morphology. Finally, the latest progress in high-performance device fabrication is highlighted, with a focus on optoelectronic characterization including current-voltage, junction capacitance, and minority carrier lifetime measurements. Finally, a discussion and future outlook is provided. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Hydrazine-induced thermo-reversible optical shifts in silver-gelatin bionanocomposites

    Science.gov (United States)

    Aimé, Carole; Rietveld, Ivo B.; Coradin, Thibaud

    2011-03-01

    Bionanocomposites formed by in situ growth of silver nanoparticles within gelatin gels exhibit large (up to 100 nm) thermo-reversible optical shifts resulting from the enhancement of gel matrix scattering by the interaction of the biopolymer with the hydrazine reducing agent.

  12. Studies on the Mechanism of Action of Hydrazine-Induced Methylation of DNA Guanne

    Science.gov (United States)

    1984-10-03

    and 7-methylguanine was detectable in the DNA. In another in vitro study hydrazine, formaldehyde, monomethythydrazine, methyl- nitrosourea , and...methyl- nitrosourea ; DEN, diethylnitrosamine; concentrations are expressed as millimoles per liter incubation medium. ** Ethylguanines, rather than...2436-2455. Griffith, O.W. and A. Meister, (1979), Potent and specific inhibition of glutathione synthesis by buthionine sulfoximine (S-n

  13. Electron transport and electrocatalytic properties of MWCNT/nickel nanocomposites: hydrazine and diethylaminoethanethiol as analytical probes

    CSIR Research Space (South Africa)

    Adekunle, AS

    2010-06-01

    Full Text Available of the electrodes with the Ni and NiO nanoparticles was confirmed by techniques such as FTIR, FESEM, HRSEM, TEM, XRD, EDX and cyclic voltammetry (CV). The electrocatalytic oxidation of DEAET and hydrazine on the modified electrodes was investigated using CV...

  14. and Silver(I) Complexes of Hydrazine-Bridged Diphosphine Ligands

    African Journals Online (AJOL)

    NICO

    Gold(I), silver(I), hydrazine, diphosphine, antitumour, anticancer, mitochondrial membrane potential. 1. Introduction. The use of inorganic compounds as cancer treatment became well established with the FDA approval of cisplatin in 1978.1. Cisplatin, carboplatin and oxaliplatin are widely used in clinical settings today.

  15. Local charge transport properties of hydrazine reduced monolayer graphene oxide sheets prepared under pressure condition

    DEFF Research Database (Denmark)

    Ryuzaki, Sou; Meyer, Jakob Abild Stengaard; Petersen, Søren Vermehren

    2014-01-01

    Charge transport properties of chemically reduced graphene oxide (RGO) sheets prepared by treatment with hydrazine were examined using conductive atomic force microscopy. The current-voltage (I-V) characteristics of monolayer RGO sheets prepared under atmospheric pressure followed an exponentially...

  16. Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks

    KAUST Repository

    Thompson, Joshua A.

    2013-04-25

    The incorporation of accessible amine functionality in zeolitic imidazolate frameworks (ZIFs) is used to improve the adsorption selectivity for CO 2/CH4 gas separation applications. Two synthetic approaches are described in this work to introduce functionality into the ZIF: (i) mixed-linker ZIF synthesis with 2-aminobenzimidazole as a substitution linker and (ii) postsynthetic modification of a mixed-linker ZIF with ethylenediamine. Using 2-aminobenzimidazole, a linker with a primary amine functional group, substitution of the ZIF-8 linker during synthesis allows for control over the adsorption properties while maintaining the ZIF-8 structure with up to nearly 50% substitution in the mixed-linker ZIF framework, producing a material with tunable pore size and amine functionality. Alternatively, postsynthetic modification of a mixed-linker ZIF containing an aldehyde functional group produces a ZIF material with a primary amine without detrimental loss of micropore volume by controlling the amount of functional group sites for modification. Both approaches using mixed-linker ZIFs yield new materials that show improvement in adsorption selectivity for the CO 2/CH4 gas pair over ZIF-8 and commercially available adsorbents as well as an increase in the heat of adsorption for CO2 without significant changes to the crystal structure. These results indicate that tuning the surface properties of ZIFs by either mixed-linker synthesis and/or postsynthetic modification may generate new materials with improved gas separation properties, thereby providing a new method for tailoring metal-organic frameworks. © 2013 American Chemical Society.

  17. Tunable CO 2 Adsorbents by Mixed-Linker Synthesis and Postsynthetic Modification of Zeolitic Imidazolate Frameworks

    KAUST Repository

    Thompson, Joshua A.; Brunelli, Nicholas A.; Lively, Ryan P.; Johnson, J. R.; Jones, Christopher W.; Nair, Sankar

    2013-01-01

    The incorporation of accessible amine functionality in zeolitic imidazolate frameworks (ZIFs) is used to improve the adsorption selectivity for CO 2/CH4 gas separation applications. Two synthetic approaches are described in this work to introduce functionality into the ZIF: (i) mixed-linker ZIF synthesis with 2-aminobenzimidazole as a substitution linker and (ii) postsynthetic modification of a mixed-linker ZIF with ethylenediamine. Using 2-aminobenzimidazole, a linker with a primary amine functional group, substitution of the ZIF-8 linker during synthesis allows for control over the adsorption properties while maintaining the ZIF-8 structure with up to nearly 50% substitution in the mixed-linker ZIF framework, producing a material with tunable pore size and amine functionality. Alternatively, postsynthetic modification of a mixed-linker ZIF containing an aldehyde functional group produces a ZIF material with a primary amine without detrimental loss of micropore volume by controlling the amount of functional group sites for modification. Both approaches using mixed-linker ZIFs yield new materials that show improvement in adsorption selectivity for the CO 2/CH4 gas pair over ZIF-8 and commercially available adsorbents as well as an increase in the heat of adsorption for CO2 without significant changes to the crystal structure. These results indicate that tuning the surface properties of ZIFs by either mixed-linker synthesis and/or postsynthetic modification may generate new materials with improved gas separation properties, thereby providing a new method for tailoring metal-organic frameworks. © 2013 American Chemical Society.

  18. Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum

    International Nuclear Information System (INIS)

    Cames, B.

    1997-01-01

    In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media (≤ 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 ≤ E ≤ 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

  19. Germline-specific H1 variants: the "sexy" linker histones.

    Science.gov (United States)

    Pérez-Montero, Salvador; Carbonell, Albert; Azorín, Fernando

    2016-03-01

    The eukaryotic genome is packed into chromatin, a nucleoprotein complex mainly formed by the interaction of DNA with the abundant basic histone proteins. The fundamental structural and functional subunit of chromatin is the nucleosome core particle, which is composed by 146 bp of DNA wrapped around an octameric protein complex formed by two copies of each core histone H2A, H2B, H3, and H4. In addition, although not an intrinsic component of the nucleosome core particle, linker histone H1 directly interacts with it in a monomeric form. Histone H1 binds nucleosomes near the exit/entry sites of linker DNA, determines nucleosome repeat length and stabilizes higher-order organization of nucleosomes into the ∼30 nm chromatin fiber. In comparison to core histones, histone H1 is less well conserved through evolution. Furthermore, histone H1 composition in metazoans is generally complex with most species containing multiple variants that play redundant as well as specific functions. In this regard, a characteristic feature is the presence of specific H1 variants that replace somatic H1s in the germline and during early embryogenesis. In this review, we summarize our current knowledge about their structural and functional properties.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-06-04

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

  1. Comparative metabonomics of differential hydrazine toxicity in the rat and mouse

    International Nuclear Information System (INIS)

    Bollard, Mary E.; Keun, Hector C.; Beckonert, Olaf; Ebbels, Tim M.D.; Antti, Henrik; Nicholls, Andrew W.; Shockcor, John P.; Cantor, Glenn H.; Stevens, Greg; Lindon, John C.; Holmes, Elaine; Nicholson, Jeremy K.

    2005-01-01

    Interspecies variation between rats and mice has been studied for hydrazine toxicity using a novel metabonomics approach. Hydrazine hydrochloride was administered to male Sprague-Dawley rats (30 mg/kg, n = 10 and 90 mg/kg, n = 10) and male B6C3F mice (100 mg/kg, n = 8 and 250 mg/kg, n = 8) by oral gavage. In each species, the high dose was selected to produce the major histopathologic effect, hepatocellular lipid accumulation. Urine samples were collected at sequential time points up to 168 h post dose and analyzed by 1 H NMR spectroscopy. The metabolites of hydrazine, namely diacetyl hydrazine and 1,4,5,6-tetrahydro-6-oxo-3-pyridazine carboxylic acid (THOPC), were detected in both the rat and mouse urine samples. Monoacetyl hydrazine was detected only in urine samples from the rat and its absence in the urine of the mouse was attributed to a higher activity of N-acetyl transferases in the mouse compared with the rat. Differential metabolic effects observed between the two species included elevated urinary β-alanine, 3-D-hydroxybutyrate, citrulline, N-acetylcitrulline, and reduced trimethylamine-N-oxide excretion unique to the rat. Metabolic principal component (PC) trajectories highlighted the greater degree of toxic response in the rat. A data scaling method, scaled to maximum aligned and reduced trajectories (SMART) analysis, was used to remove the differences between the metabolic starting positions of the rat and mouse and varying magnitudes of effect, to facilitate comparison of the response geometries between the rat and mouse. Mice followed 'biphasic' open PC trajectories, with incomplete recovery 7 days after dosing, whereas rats followed closed 'hairpin' time profiles, indicating functional reversibility. The greater magnitude of metabolic effects observed in the rat was supported by the more pronounced effect on liver pathology in the rat when compared with the mouse

  2. Cyclic voltammetry deposition of copper nanostructure on MWCNTs modified pencil graphite electrode: An ultra-sensitive hydrazine sensor

    Energy Technology Data Exchange (ETDEWEB)

    Heydari, Hamid [Faculty of Sciences, Razi University, Kermanshah (Iran, Islamic Republic of); Gholivand, Mohammad B., E-mail: mbgholivand@razi.ac.ir [Faculty of Sciences, Razi University, Kermanshah (Iran, Islamic Republic of); Abdolmaleki, Abbas [Department of Chemistry, Malek Ashtar University of Technology, Tehran (Iran, Islamic Republic of)

    2016-09-01

    In this study, Copper (Cu) nanostructures (CuNS) were electrochemically deposited on a film of multiwall carbon nanotubes (MWCNTs) modified pencil graphite electrode (MWCNTs/PGE) by cyclic voltammetry method to fabricate a CuNS–MWCNTs composite sensor (CuNS–MWCNT/PGE) for hydrazine detection. Scanning electron microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDX) were used for the characterization of CuNS on the MWCNTs matrix. The composite of CuNS-MWCNTs was characterized with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The preliminary studies showed that the proposed sensor have a synergistic electrocatalytic activity for the oxidation of hydrazine in phosphate buffer. The catalytic currents of square wave voltammetry had a linear correlation with the hydrazine concentration in the range of 0.1 to 800 μM with a low detection limit of 70 nM. Moreover, the amperometric oxidation current exhibited a linear correlation with hydrazine concentration in the concentration range of 50–800 μM with the detection limit of 4.3 μM. The proposed electrode was used for the determination of hydrazine in real samples and the results were promising. Empirical results also indicated that the sensor had good reproducibility, long-term stability, and the response of the sensor to hydrazine was free from interferences. Moreover, the proposed sensor benefits from simple preparation, low cost, outstanding sensitivity, selectivity, and reproducibility for hydrazine determination. - Highlights: • The Copper nanostructures (CuNS) were prepared by cyclic voltammetry deposition. • The CuNS-MWCNT/PGE sensor shows high activity toward hydrazine (N{sub 2}H{sub 4}). • The proposed sensor exhibits a wide linear range (0.1 to 800 μM), low detection limit (70 nM), high sensitivity and stability for hydrazine.

  3. Effect of hydrazine on general corrosion of carbon and low-alloyed steels in pressurized water reactor secondary side water

    Energy Technology Data Exchange (ETDEWEB)

    Järvimäki, Sari [Fortum Ltd, Loviisa Power Plant, Loviisa (Finland); Saario, Timo; Sipilä, Konsta [VTT Technical Research Centre of Finland Ltd., Nuclear Safety, P.O. Box 1000, FIN-02044 VTT (Finland); Bojinov, Martin, E-mail: martin@uctm.edu [Department of Physical Chemistry, University of Chemical Technology and Metallurgy, Kl. Ohridski Blvd, 8, 1756 Sofia (Bulgaria)

    2015-12-15

    Highlights: • The effect of hydrazine on the corrosion of steel in secondary side water investigated by in situ and ex situ techniques. • Oxide grown on steel in 100 ppb hydrazine shows weaker protective properties – higher corrosion rates. • Possible explanation of the accelerating effect of higher concentrations of hydrazine on flow assisted corrosion offered. - Abstract: The effect of hydrazine on corrosion rate of low-alloyed steel (LAS) and carbon steel (CS) was studied by in situ and ex situ techniques under pressurized water reactor secondary side water chemistry conditions at T = 228 °C and pH{sub RT} = 9.2 (adjusted by NH{sub 3}). It is found that hydrazine injection to a maximum level of 5.06 μmol l{sup −1} onto surfaces previously oxidized in ammonia does not affect the corrosion rate of LAS or CS. This is confirmed also by plant measurements at Loviisa NPP. On the other hand, hydrazine at the level of 3.1 μmol l{sup −1} decreases markedly the amount and the size of deposited oxide crystals on LAS and CS surface. In addition, the oxide grown in the presence of 3.1 μmol l{sup −1} hydrazine is somewhat less protective and sustains a higher corrosion rate compared to an oxide film grown without hydrazine. These observations could explain the accelerating effect of higher concentrations of hydrazine found in corrosion studies of LAS and CS.

  4. Morpho-functional Blood Changes Under the Influence of Hydrazine and Correction with “Salsokollin” Drug

    Directory of Open Access Journals (Sweden)

    Marat R. Khanturin

    2012-09-01

    Full Text Available Hydrazine derivatives are used in different areas: airspace industry, healthcare, laboratory-diagnostic activity, that’s why the environment is subjected to contamination by hydrazines. For Kazakhstan, which houses the "Baikonur" Cosmodrome, the problem of environmental pollution by rocket fuel and its components is a burning issue nowadays. This article deals with the impacts by industrial hydrazines on biochemical data of the blood and its correction with the “Salsokollin” Drug. The samples of bilirubin, the whole protein, urea, creatinine, cholesterol, glucose, aminotransferase a-amylases, α-amylase were taken. The thymol test was carried out.

  5. Cellulase linkers are optimized based on domain type and function: insights from sequence analysis, biophysical measurements, and molecular simulation.

    Directory of Open Access Journals (Sweden)

    Deanne W Sammond

    Full Text Available Cellulase enzymes deconstruct cellulose to glucose, and are often comprised of glycosylated linkers connecting glycoside hydrolases (GHs to carbohydrate-binding modules (CBMs. Although linker modifications can alter cellulase activity, the functional role of linkers beyond domain connectivity remains unknown. Here we investigate cellulase linkers connecting GH Family 6 or 7 catalytic domains to Family 1 or 2 CBMs, from both bacterial and eukaryotic cellulases to identify conserved characteristics potentially related to function. Sequence analysis suggests that the linker lengths between structured domains are optimized based on the GH domain and CBM type, such that linker length may be important for activity. Longer linkers are observed in eukaryotic GH Family 6 cellulases compared to GH Family 7 cellulases. Bacterial GH Family 6 cellulases are found with structured domains in either N to C terminal order, and similar linker lengths suggest there is no effect of domain order on length. O-glycosylation is uniformly distributed across linkers, suggesting that glycans are required along entire linker lengths for proteolysis protection and, as suggested by simulation, for extension. Sequence comparisons show that proline content for bacterial linkers is more than double that observed in eukaryotic linkers, but with fewer putative O-glycan sites, suggesting alternative methods for extension. Conversely, near linker termini where linkers connect to structured domains, O-glycosylation sites are observed less frequently, whereas glycines are more prevalent, suggesting the need for flexibility to achieve proper domain orientations. Putative N-glycosylation sites are quite rare in cellulase linkers, while an N-P motif, which strongly disfavors the attachment of N-glycans, is commonly observed. These results suggest that linkers exhibit features that are likely tailored for optimal function, despite possessing low sequence identity. This study suggests

  6. Hemidesmosomal linker proteins regulate cell motility, invasion and tumorigenicity in oral squamous cell carcinoma derived cells.

    Science.gov (United States)

    Chaudhari, Pratik Rajeev; Charles, Silvania Emlit; D'Souza, Zinia Charlotte; Vaidya, Milind Murlidhar

    2017-11-15

    BPAG1e and Plectin are hemidesmosomal linker proteins which anchor intermediate filament proteins to the cell surface through β4 integrin. Recent reports indicate that these proteins play a role in various cellular processes apart from their known anchoring function. However, the available literature is inconsistent. Further, the previous study from our laboratory suggested that Keratin8/18 pair promotes cell motility and tumor progression by deregulating β4 integrin signaling in oral squamous cell carcinoma (OSCC) derived cells. Based on these findings, we hypothesized that linker proteins may have a role in neoplastic progression of OSCC. Downregulation of hemidesmosomal linker proteins in OSCC derived cells resulted in reduced cell migration accompanied by alterations in actin organization. Further, decreased MMP9 activity led to reduced cell invasion in linker proteins knockdown cells. Moreover, loss of these proteins resulted in reduced tumorigenic potential. SWATH analysis demonstrated upregulation of N-Myc downstream regulated gene 1 (NDRG1) in linker proteins downregulated cells as compared to vector control cells. Further, the defects in phenotype upon linker proteins ablation were rescued upon loss of NDRG1 in linker proteins knockdown background. These data together indicate that hemidesmosomal linker proteins regulate cell motility, invasion and tumorigenicity possibly through NDRG1 in OSCC derived cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Description of a cellulose-binding domain and a linker sequence from Aspergillus fungi

    NARCIS (Netherlands)

    Quentin, M; Ebbelaar, M; Derksen, J; Mariani, C; van der Valk, H

    A family I cellulose-binding domain (CBD) and a serine- and threonine-rich linker peptide were cloned from the fungi Aspergillus japonicus and Aspergillus aculeatus. A glutathione S-transferase (GST) fusion protein comprising GST and a peptide linker with the CBD fused to its C-terminus, was

  8. Novel silicone compatible cross-linkers for controlled functionalization of PDMS networks

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Daugaard, Anders Egede; Hvilsted, Søren

    2013-01-01

    . In order to improve the dielectric properties of PDMS a novel system is developed where push-pull dipoles are grafted to a new silicone compatible cross-linker. The grafted cross-linkers are prepared by reaction of two different push-pull dipole alkynes as well as a fluorescent alkyne with the new azide...

  9. P-Link: A method for generating multicomponent cytochrome P450 fusions with variable linker length

    DEFF Research Database (Denmark)

    Belsare, Ketaki D.; Ruff, Anna Joelle; Martinez, Ronny

    2014-01-01

    Fusion protein construction is a widely employed biochemical technique, especially when it comes to multi-component enzymes such as cytochrome P450s. Here we describe a novel method for generating fusion proteins with variable linker lengths, protein fusion with variable linker insertion (P...

  10. The Abl SH2-kinase linker naturally adopts a conformation competent for SH3 domain binding.

    Science.gov (United States)

    Chen, Shugui; Brier, Sébastien; Smithgall, Thomas E; Engen, John R

    2007-04-01

    The core of the Abelson tyrosine kinase (c-Abl) is structurally similar to Src-family kinases where SH3 and SH2 domains pack against the backside of the kinase domain in the down-regulated conformation. Both kinase families depend upon intramolecular association of SH3 with the linker joining the SH2 and kinase domains for suppression of kinase activity. Hydrogen deuterium exchange (HX) and mass spectrometry (MS) were used to probe intramolecular interaction of the c-Abl SH3 domain with the linker in recombinant constructs lacking the kinase domain. Under physiological conditions, the c-Abl SH3 domain undergoes partial unfolding, which is stabilized by ligand binding, providing a unique assay for SH3:linker interaction in solution. Using this approach, we observed dynamic association of the SH3 domain with the linker in the absence of the kinase domain. Truncation of the linker before W254 completely prevented cis-interaction with SH3, while constructs containing amino acids past this point showed SH3:linker interactions. The observation that the Abl linker sequence exhibits SH3-binding activity in the absence of the kinase domain is unique to Abl and was not observed with Src-family kinases. These results suggest that SH3:linker interactions may have a more prominent role in Abl regulation than in Src kinases, where the down-regulated conformation is further stabilized by a second intramolecular interaction between the C-terminal tail and the SH2 domain.

  11. Linkers, resins, and general procedures for solid-phase peptide synthesis

    DEFF Research Database (Denmark)

    Shelton, Anne Pernille Tofteng; Jensen, Knud Jørgen

    2013-01-01

    and linkers for solid-phase synthesis is a key parameter for successful peptide synthesis. This chapter provides an overview of the most common and useful resins and linkers for the synthesis of peptides with C-terminal amides, carboxylic acids, and more. The chapter finishes with robust protocols for general...

  12. Synthesis, structurale elucidation and antioxidant study of Ortho-substituted N,N’-bis(benzamidothiocarbonyl)hydrazine derivatives

    Science.gov (United States)

    Firdausiah, Syadza; Hasbullah, S. A.; Yamin, B. M.

    2018-03-01

    Some bis(thiourea) compounds have been reported to posses excellent performance in pharmaceutical and environmental fields because of their ability to form chelating complexes with various anions and metal ions. Structurally for carbonyl thiourea derivatives, to become a chelating agent, it must adopt cis-configuration. In the present study, four new bis(thiourea) derivatives namely N,N’-bis(o-fluorobenzamidothiocarbonyl)hydrazine (1), N,N’- bis(o-chloro-benzamidothiocarbonyl)hydrazine (2), N,N’-bis(o-nitrobenzamidothiocarbonyl)-hydrazine (3), and N,N’-bis(o-methylbenzamidothiocarbonyl)hydrazine (4) were successfully synthesized and characterized by CHNS microelemental analysis, FTIR, UV-Vis, and 1H and 13C NMR spectroscopy. However chemical crystallography study showed that both thiourea moieties in compound (2) and (3) adopt trans geometry. Therefore they are potential monodentate ligand with two active moieties. DPPH radical scavenging experiment showed that compound (1), (2), and (4) exhibited higher antioxidant activity than ascorbic acid (Vitamin C).

  13. Micro-Electro-Analytical Sensor for Sensitive, Selective and Rapid Monitoring of Hydrazine in the Presence of Ammonia, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Hydrazine, a volatile and flammable colorless liquid, is classified as a carcinogen by the US Environmental Protection Agency. It can cause chromosome aberrations...

  14. Construction of hierarchically porous metal-organic frameworks through linker labilization

    Science.gov (United States)

    Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai

    2017-05-01

    A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

  15. The Reduction Reaction of Dissolved Oxygen in Water by Hydrazine over Platinum Catalyst Supported on Activated Carbon Fiber

    Energy Technology Data Exchange (ETDEWEB)

    Park, K.K.; Moon, J.S. [Korea Electric Power Research Institute, Taejon (Korea)

    1999-07-01

    The reduction reaction of dissolved oxygen (DO) by hydrazine was investigated on activated carbon fiber (ACF) and Pt/ACF catalysts using a batch reactor with an external circulating loop. The ACF itself showed catalytic activity and this was further improved by supporting platinum on ACF. The catalytic role platinum is ascribed to its acceleration of hydrazine decomposition, based on electric potential and current measurements as well as the kinetic study. (author). 15 refs., 13 figs.

  16. A chromogenic and fluorogenic rhodol-based chemosensor for hydrazine detection and its application in live cell bioimaging

    Science.gov (United States)

    Tiensomjitr, Khomsan; Noorat, Rattha; Chomngam, Sinchai; Wechakorn, Kanokorn; Prabpai, Samran; Kanjanasirirat, Phongthon; Pewkliang, Yongyut; Borwornpinyo, Suparerk; Kongsaeree, Palangpon

    2018-04-01

    A rhodol-based fluorescent probe has been developed as a selective hydrazine chemosensor using levulinate as a recognition site. The rhodol levulinate probe (RL) demonstrated high selectivity and sensitivity toward hydrazine among other molecules. The chromogenic response of RL solution to hydrazine from colorless to pink could be readily observed by the naked eye, while strong fluorescence emission could be monitored upon excitation at 525 nm. The detection process occurred via a ring-opening process of the spirolactone initiated by hydrazinolysis, triggering the fluorescence emission with a 53-fold enhancement. The probe rapidly reacted with hydrazine in aqueous medium with the detection limit of 26 nM (0.83 ppb), lower than the threshold limit value (TLV) of 10 ppb suggested by the U.S. Environmental Protection Agency. Furthermore, RL-impregnated paper strips could detect hydrazine vapor. For biological applicability of RL, its membrane-permeable property led to bioimaging of hydrazine in live HepG2 cells by confocal fluorescence microscopy.

  17. Determination of hydrazine in third loops of China experimental fast reactor by spectrophotometry

    International Nuclear Information System (INIS)

    Huang Wenjie; Wang Mi; Gao Yaopeng; Xie Chun; Yu Xiaochen

    2013-01-01

    The method for the determination of hydrazine by Uv-vis spectrophotometer was proposed. The coloration conditions and instrument parameters were also optimized. In HCl, hydrazine formed a yellow azine with para-dimethyl aminobenzaldehyde ((CH 3 ) 2 NC 6 H 4 CHO), and then determined by spectrophotometer. The complex's maximum absorption was exhibited at 458 nm. The coloration effect was excellent in conditions of 1% HCl, 10 mL para-dimethyl aminobenzaldehyde and 10 minutes' developing time. A good liner relationship was obtained in the range of 5∼200 μg/L, and the recovery was (101.1±1.9)%. This method was used in the third loop of China experimental fast reactor with satisfactory results. (authors)

  18. 2-(Hetero(aryl)methylene)hydrazine-1-carbothioamides as potent urease inhibitors.

    Science.gov (United States)

    Saeed, Aamer; Imran, Aqeel; Channar, Pervaiz A; Shahid, Mohammad; Mahmood, Wajahat; Iqbal, Jamshed

    2015-02-01

    A small series of 2-(hetero(aryl)methylene) hydrazine-1-carbothioamides including two aryl derivatives was synthesized and tested for their inhibitory activity against urease. Compound (E)-2-(Furan-2-ylmethylene) hydrazine-1-carbothioamide (3f), having a furan ring, was the most potent inhibitor of urease with an IC50 value of 0.58 μM. Molecular modeling was carried out through docking the designed compounds into the urease binding site to predict whether these derivatives have analogous binding mode to the urease inhibitors. The study revealed that all of the tested compounds bind with both metal atoms at the active site of the enzyme. The aromatic ring of the compounds forms ionic interactions with the residues, Ala(440), Asp(494), Ala(636), and Met(637). © 2014 John Wiley & Sons A/S.

  19. Confidence Testing of Shell 405 and S-405 Catalysts in a Monopropellant Hydrazine Thruster

    Science.gov (United States)

    McRight, Patrick; Popp, Chris; Pierce, Charles; Turpin, Alicia; Urbanchock, Walter; Wilson, Mike

    2005-01-01

    As part of the transfer of catalyst manufacturing technology from Shell Chemical Company (Shell 405 catalyst manufactured in Houston, Texas) to Aerojet (S-405 manufactured in Redmond, Washington), Aerojet demonstrated the equivalence of S-405 and Shell 405 at beginning of life. Some US aerospace users expressed a desire to conduct a preliminary confidence test to assess end-of-life characteristics for S-405. NASA Marshall Space Flight Center (MSFC) and Aerojet entered a contractual agreement in 2004 to conduct a confidence test using a pair of 0.2-lbf MR-103G monopropellant hydrazine thrusters, comparing S-405 and Shell 405 side by side. This paper summarizes the formulation of this test program, explains the test matrix, describes the progress of the test, and analyzes the test results. This paper also includes a discussion of the limitations of this test and the ramifications of the test results for assessing the need for future qualification testing in particular hydrazine thruster applications.

  20. Interactions of hydrazine, ferrous sulfamate, sodium nitrite, and nitric acid in nuclear fuel processing solutions

    International Nuclear Information System (INIS)

    Gray, L.W.

    1977-03-01

    Hydrazine and ferrous sulfamate are used as reductants in a variety of nuclear fuel processing solutions. An oxidant, normally sodium nitrite, must frequently be added to these nitric acid solutions before additional processing can proceed. The interactions of these four chemicals have been studied under a wide variety of conditions using a 2/sup p/ factorial experimental design to determine relative reaction rates for desired reactions and side reactions. Evidence for a hydrazine-stabilized, sulfamic acid--nitrous acid intermediate was obtained; this intermediate can hydrolyze to ammonia or decompose to nitrogen. The oxidation of Fe 2+ by NO 2 - was shown to proceed at about the same rate as the scavenging of NO 2 - by sulfamic acid. Various side reactions are discussed

  1. Dose response of hydrazine - Deproteinated tooth enamel under blue light stimulation

    Energy Technology Data Exchange (ETDEWEB)

    Yuece, Ulkue Rabia, E-mail: ulkuyuce@hotmail.co [Ankara University, Faculty of Engineering, Department of Engineering Physics, 06100, Tandogan - Ankara (Turkey); Meric, Niyazi, E-mail: meric@ankara.edu.t [Ankara University, Faculty of Engineering, Department of Engineering Physics, 06100, Tandogan - Ankara (Turkey); Atakol, Orhan, E-mail: atakol@science.ankara.edu.t [Ankara University, Science Faculty, Department of Chemistry, 06100, Tandogan - Ankara (Turkey); Yasar, Fusun, E-mail: ab121310@adalet.gov.t [Council of Forensic Medicine, Ankara Branch, Ankara (Turkey)

    2010-08-15

    The beta dose response and Optically Stimulated Luminescence (OSL) signal stability characteristics of human tooth enamel deproteinated by hydrazine reagent under blue photon stimulation are reported. Removal of the protein organic component of tooth enamel resulted in a higher OSL sensitivity and slower fading of OSL signals. The effect of chemical sample preparation on the enamel sample sensitivity is discussed and further steps to make this deproteinization treatment suitable for in vitro dose reconstruction studies are suggested.

  2. Recent developments in Cope-type hydroamination reactions of hydroxylamine and hydrazine derivatives.

    Science.gov (United States)

    Beauchemin, André M

    2013-11-07

    Cope-type hydroaminations are versatile for the direct amination of alkenes, alkynes and allenes using hydroxylamines and hydrazine derivatives. These reactions occur via a concerted, 5-membered cyclic transition state that is the microscopic reverse of the Cope elimination. This article focuses on recent developments, including intermolecular variants, directed reactions, and asymmetric variants using aldehydes as tethering catalysts, and their applications in target-oriented synthesis.

  3. Dose response of hydrazine - Deproteinated tooth enamel under blue light stimulation

    International Nuclear Information System (INIS)

    Yuece, Ulkue Rabia; Meric, Niyazi; Atakol, Orhan; Yasar, Fusun

    2010-01-01

    The beta dose response and Optically Stimulated Luminescence (OSL) signal stability characteristics of human tooth enamel deproteinated by hydrazine reagent under blue photon stimulation are reported. Removal of the protein organic component of tooth enamel resulted in a higher OSL sensitivity and slower fading of OSL signals. The effect of chemical sample preparation on the enamel sample sensitivity is discussed and further steps to make this deproteinization treatment suitable for in vitro dose reconstruction studies are suggested.

  4. Reaction of hydrazine hydrate with oxalic acid: synthesis and crystal structure of dihydrazinium oxalate

    OpenAIRE

    Selvakumar, Rajendran; Premkumar, Thathan; Manivannan, Vadivelu; Saravanan, Kaliannan; Govindarajan, Subbiah

    2014-01-01

    The reaction of oxalic acid with hydrazine hydrate (in appropriate mole ratio) forms the dihydrazinium oxalate under specific experimental condition. The title compound is a molecular salt containing two discrete hydrazinium cations and an oxalate anion. The oxalate anion is perfectly planar and there is a crystallographic centre of symmetry in the middle of the C-C bond. The C-O bond distances are almost equal indicating the presence of resonance in the oxalate ion. The crystal packing is st...

  5. Alkalization of steam and condensate with 2-amino-1-butanol and hydrazine; Alkalisering av aanga och kondensat med butanolamin och hydrazin

    Energy Technology Data Exchange (ETDEWEB)

    Falk, I [Studsvik Material AB, Nykoeping (Sweden)

    1996-04-01

    To maintain a low corrosion level in steam- and condensate systems at power and industrial plants, an alkalization of the steam is needed. A low corrosion level lowers the risk of operation disturbances and reduces the cost of the condensate clean up. A better knowledge in the behavior of the alkalis will improve the possibilities to avoid the corrosion attacks. In this work experimental measurements have been carried out during steam boiler conditions as temperature, continuous steam generation and condensation. It has been found that the volatility of 2-amino-1-butanol is very low during stationary dynamic conditions at 250 deg C and 120 deg C. To achieve a high ph-value in the final condensate a very high concentration of 2-amino-1-butanol is thus needed especially when the steam contains acidic compounds. The alkalization effect is obtained from ammonia which is created by thermal decomposition of hydrazine in the boiler water. It is necessary to carry out experimental investigations showing the thermal stability of organic compounds in boiler water before it is possible to recommend them as better volatile alkalis than ammonia and hydrazine. 6 refs, 13 figs

  6. Amperometric detection of hydrazine utilizing synergistic action of prussian blue @ silver nanoparticles / graphite felt modified electrode

    International Nuclear Information System (INIS)

    Zhao, Jihua; Liu, Jianxin; Tricard, Simon; Wang, Lei; Liang, Yanling; Cao, Linghua; Fang, Jian; Shen, Weiguo

    2015-01-01

    Highlights: • Prussian Blue (PB) deposition on Ag/GF for electrochemical hydrazine sensing; • Lower detection limit of 4.9 × 10 −7 mol L −1 , stable over 24 days; • High sensitivity: 26.06 A mol −1 L. -- Abstract: In this study, a triple-component hydrazine sensor (PB@Ag/GF) was fabricated with freestanding graphite felt (GF), silver nanoparticles (Ag) and prussian blue (PB). The Ag nanoparticles were electrodeposited on GF ultrasonically (Ag/GF), and acted as a catalyst of the chemical deposition of PB. The electrode was characterized by scanning election microscopy (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), and energy-dispersive X-ray spectroscopy (EDS). The electrochemical behavior of PB@Ag/GF was measured by cyclic voltammetry and amperometric measurements. The sensor displayed a prominent electrocatalytic activity toward hydrazine oxidation, with a fast response time of 2 s, a low detection limit of 4.9 × 10 −7 mol L −1 and very high detection sensitivity of 26.06 A mol −1 L

  7. Influence of hydrazine primary water chemistry on corrosion of fuel cladding and primary circuit components

    International Nuclear Information System (INIS)

    Iourmanov, V.; Pashevich, V.; Bogancs, J.; Tilky, P.; Schunk, J.; Pinter, T.

    1999-01-01

    Earlier at Paks 1-4 NPP standard ammonia chemistry was in use. The following station performance indicators were improved when hydrazine primary water chemistry was introduced: occupational radiation exposures of personnel; gamma-radiation dose rates near primary system components during refuelling and maintenance outages. The reduction of radiation exposures and radiation fields were achieved without significant expenses. Recent results of experimental studies allowed to explain the mechanism of hydrazine dosing influence on: corrosion rate of structure materials in primary coolant; behaviour of soluble and insoluble corrosion products including long-life corrosion-induced radionuclides in primary system during steady-state and transient operation modes; radiolytic generation of oxidising radiolytic products in core and its corrosion activity in primary system; radiation situation during refuelling and maintenance outages; foreign material degradation and removal (including corrosion active oxidant species) from primary system during abnormal events. Operational experience and experimental data have shown that hydrazine primary water chemistry allows to reduce corrosion wear and thereby makes it possible to extend the life-time of plant components in primary system. (author)

  8. Electrochemical behavior of rhodium acetamidate immobilized on a carbon paste electrode: a hydrazine sensor

    Directory of Open Access Journals (Sweden)

    Gil Eric de S.

    2000-01-01

    Full Text Available The electrochemical behavior of rhodium acetamidate immobilized in carbon paste electrode and the consequences for sensor construction were evaluated. The electrode showed good stability and redox properties. Two reversible redox couples with midpoint potentials between 0.15 and 0.55 V vs SCE were observed. However, peak resolution in voltammetric studies was very dependent on the supporting electrolyte. The correlation between coordinating power of the electrolyte and peak potential suggests that the electrolyte can coordinate through the axial position of the complexes. Furthermore, the axial position may be also the catalytic site, as a catalytical response was observed for hydrazine oxidation. A good linear response range for hydrazine was fit by the equation i = 23.13 (± 0.34 c , where i = current in mA and c = concentration in mol dm-3 in the range of 10-5 up to 10-2 mol dm-3. The low applied potential (<300 mV indicates a good device for hydrazine sensor, minimizing interference problems. The short response time (~1 s may be useful in flow injection analysis. Furthermore, this system was very stable presenting good repeatability even after 30 measurements with a variance of 0.5 %.

  9. Redox Response of Reduced Graphene Oxide-Modified Glassy Carbon Electrodes to Hydrogen Peroxide and Hydrazine

    Directory of Open Access Journals (Sweden)

    Jun-ichi Anzai

    2013-05-01

    Full Text Available The surface of a glassy carbon (GC electrode was modified with reduced graphene oxide (rGO to evaluate the electrochemical response of the modified GC electrodes to hydrogen peroxide (H2O2 and hydrazine. The electrode potential of the GC electrode was repeatedly scanned from −1.5 to 0.6 V in an aqueous dispersion of graphene oxide (GO to deposit rGO on the surface of the GC electrode. The surface morphology of the modified GC electrode was characterized by scanning electron microscopy (SEM and atomic force microscopy (AFM. SEM and AFM observations revealed that aggregated rGO was deposited on the GC electrode, forming a rather rough surface. The rGO-modified electrodes exhibited significantly higher responses in redox reactions of H2O2 as compared with the response of an unmodified GC electrode. In addition, the electrocatalytic activity of the rGO-modified electrode to hydrazine oxidation was also higher than that of the unmodified GC electrode. The response of the rGO-modified electrode was rationalized based on the higher catalytic activity of rGO to the redox reactions of H2O2 and hydrazine. The results suggest that rGO-modified electrodes are useful for constructing electrochemical sensors.

  10. Hydrazine-hydrothermal method to synthesize three-dimensional chalcogenide framework for photocatalytic hydrogen generation

    International Nuclear Information System (INIS)

    Liu Yi; Kanhere, Pushkar D.; Wong, Chui Ling; Tian Yuefeng; Feng Yuhua; Boey, Freddy; Wu, Tom; Chen Hongyu; White, Tim J.; Chen Zhong; Zhang Qichun

    2010-01-01

    A novel chalcogenide, [Mn 2 Sb 2 S 5 (N 2 H 4 ) 3 ] (1), has been synthesized by the hydrazine-hydrothermal method. X-ray crystallography study reveals that the new compound 1 crystallizes in space group P1-bar (no. 2) of the triclinic system. The structure features an open neutral three-dimensional framework, where two-dimensional mesh-like inorganic layers are bridged by intra- and inter-layer hydrazine ligands. Both two Mn1 and Mn2 sites adopt distorted octahedral coordination. While two Sb1 and Sb2 sites exhibit two different coordination geometries, the Sb1 site is coordinated with three S atoms to generate a SbS 3 trigonal-pyramidal geometry, and the Sb2 site adopts a SbS 4 trigonal bipyramidal coordination geometry. It has an optical band gap of about ∼2.09 eV, which was deduced from the diffuse reflectance spectrum, and displays photocatalytic behaviors under visible light irradiation. Magnetic susceptibility measurements show compound 1 obeys the Curie-Weiss law in the range of 50-300 K. -- Graphical abstract: A novel chalcogenide, [Mn 2 Sb 2 S 5 (N 2 H 4 ) 3 ] (1), synthesized by hydrazine-hydrothermal method, has a band gap of about ∼2.09 eV and displays photocatalytic behaviors under visible light irradiation. Display Omitted

  11. Isolation of N-linked glycopeptides by hydrazine-functionalized magnetic particles.

    Science.gov (United States)

    Sun, Shisheng; Yang, Ganglong; Wang, Ting; Wang, Qinzhe; Chen, Chao; Li, Zheng

    2010-04-01

    We introduce a novel combination of magnetic particles with hydrazine chemistry, dubbed as hydrazine-functionalized magnetic particles (HFMP) for isolation of glycopeptides. Four methods have been developed and compared for the production of HFMP by hydrazine modification of the surface of the carboxyl and epoxy-silanized magnetic particles, respectively. The evaluation of the capability and specificity of HFMP as well as the optimization of the coupling condition for capturing of glycoproteins were systematically investigated. The results showed that HFMP prepared by adipic dihydrazide functionalization from carboxyl-silanized magnetic particles (HFCA) displayed the maximum capture capacity and isolated efficiency for glycoprotein. When measured with glycoproteins, the capacity of the HFCA (1 g) for coupling bovine fetuin was 130 +/- 5.3 mg. The capability of this method was also confirmed by successful isolation of all formerly glycosylated peptides from standard glycoproteins and identification of their glycosylation sites, which demonstrated the feasibility of the HFCA as an alternative solid support for isolation of glycoproteins/glycopeptides.

  12. Effect of the linkers between the zinc fingers in zinc finger protein 809 on gene silencing and nuclear localization

    Energy Technology Data Exchange (ETDEWEB)

    Ichida, Yu, E-mail: ichida-y@ncchd.go.jp; Utsunomiya, Yuko; Onodera, Masafumi

    2016-03-18

    Zinc finger protein 809 (ZFP809) belongs to the Kruppel-associated box-containing zinc finger protein (KRAB-ZFP) family and functions in repressing the expression of Moloney murine leukemia virus (MoMLV). ZFP809 binds to the primer-binding site (PBS)located downstream of the MoMLV-long terminal repeat (LTR) and induces epigenetic modifications at integration sites, such as repressive histone modifications and de novo DNA methylation. KRAB-ZFPs contain consensus TGEKP linkers between C2H2 zinc fingers. The phosphorylation of threonine residues within linkers leads to the inactivation of zinc finger binding to target sequences. ZFP809 also contains consensus linkers between zinc fingers. However, the function of ZFP809 linkers remains unknown. In the present study, we constructed ZFP809 proteins containing mutated linkers and examined their ability to silence transgene expression driven by MLV, binding ability to MLV PBS, and cellular localization. The results of the present study revealed that the linkers affected the ability of ZFP809 to silence transgene expression. Furthermore, this effect could be partly attributed to changes in the localization of ZFP809 proteins containing mutated linkers. Further characterization of ZFP809 linkers is required for understanding the functions and features of KRAB-ZFP-containing linkers. - Highlights: • ZFP809 has three consensus linkers between the zinc fingers. • Linkers are required for ZFP809 to silence transgene expression driven by MLV-LTR. • Linkers affect the precise nuclear localization of ZFP809.

  13. Charged Triazole Cross-Linkers for Hyaluronan-Based Hybrid Hydrogels

    Directory of Open Access Journals (Sweden)

    Maike Martini

    2016-09-01

    Full Text Available Polyelectrolyte hydrogels play an important role in tissue engineering and can be produced from natural polymers, such as the glycosaminoglycan hyaluronan. In order to control charge density and mechanical properties of hyaluronan-based hydrogels, we developed cross-linkers with a neutral or positively charged triazole core with different lengths of spacer arms and two terminal maleimide groups. These cross-linkers react with thiolated hyaluronan in a fast, stoichiometric thio-Michael addition. Introducing a positive charge on the core of the cross-linker enabled us to compare hydrogels with the same interconnectivity, but a different charge density. Positively charged cross-linkers form stiffer hydrogels relatively independent of the size of the cross-linker, whereas neutral cross-linkers only form stable hydrogels at small spacer lengths. These novel cross-linkers provide a platform to tune the hydrogel network charge and thus the mechanical properties of the network. In addition, they might offer a wide range of applications especially in bioprinting for precise design of hydrogels.

  14. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks.

    Science.gov (United States)

    Feng, Liang; Yuan, Shuai; Zhang, Liang-Liang; Tan, Kui; Li, Jia-Luo; Kirchon, Angelo; Liu, Ling-Mei; Zhang, Peng; Han, Yu; Chabal, Yves J; Zhou, Hong-Cai

    2018-02-14

    Sufficient pore size, appropriate stability, and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization, and catalysis involving large molecules. Herein, we report a powerful and general strategy, linker thermolysis, to construct ultrastable hierarchically porous metal-organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxylation process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultrasmall metal oxide nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid-catalyzed reactions. Most importantly, this work provides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on probing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  15. Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal-Organic Frameworks

    KAUST Repository

    Feng, Liang

    2018-01-18

    Sufficient pore size, appropriate stability and hierarchical porosity are three prerequisites for open frameworks designed for drug delivery, enzyme immobilization and catalysis involving large molecules. Herein, we report a powerful and general strate-gy, linker thermolysis, to construct ultra-stable hierarchically porous metal−organic frameworks (HP-MOFs) with tunable pore size distribution. Linker instability, usually an undesirable trait of MOFs, was exploited to create mesopores by generating crystal defects throughout a microporous MOF crystal via thermolysis. The crystallinity and stability of HP-MOFs remain after thermolabile linkers are selectively removed from multivariate metal-organic frameworks (MTV-MOFs) through a decarboxyla-tion process. A domain-based linker spatial distribution was found to be critical for creating hierarchical pores inside MTV-MOFs. Furthermore, linker thermolysis promotes the formation of ultra-small metal oxide (MO) nanoparticles immobilized in an open framework that exhibits high catalytic activity for Lewis acid catalyzed reactions. Most importantly, this work pro-vides fresh insights into the connection between linker apportionment and vacancy distribution, which may shed light on prob-ing the disordered linker apportionment in multivariate systems, a long-standing challenge in the study of MTV-MOFs.

  16. A Traceless Aryl-Triazene Linker for DNA-Directed Chemistry

    DEFF Research Database (Denmark)

    Hejesen, Christian; Pedersen, Lars Kolster; Gothelf, Kurt Vesterager

    2013-01-01

    DNA-directed synthesis of encoded combinatorial libraries of small organic compounds most often involves transfer of organic building blocks from one DNA strand to another. This requires cleavable linkers to enable cleavage of the link to the original DNA strand from which the building block...... is transferred. Relatively few cleavable linkers are available for DNA-directed synthesis and most often they leave an amino group at the organic molecule. Here we have extended the application of 10 aryltriazenes as traceless linkers for DNA-directed synthesis. After reaction of one building block...

  17. Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Xiao-Ping; Dai, Hong-Bin, E-mail: mshbdai@scut.edu.cn; Wu, Lin-Song; Wang, Ping, E-mail: mspwang@scut.edu.cn

    2017-07-01

    Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N{sub 2}H{sub 4} electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N{sub 2}H{sub 4} as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

  18. Electroless plating of Ni–B film as a binder-free highly efficient electrocatalyst for hydrazine oxidation

    International Nuclear Information System (INIS)

    Wen, Xiao-Ping; Dai, Hong-Bin; Wu, Lin-Song; Wang, Ping

    2017-01-01

    Graphical abstract: A Ni–B film was grown on Ni foam to form a binder-free highly efficient electrocatalyst for hydrazine oxidation in alkaline medium. The newly-developed Ni–B/Ni foam electrocatalyst may promote the practical application of hydrazine as a viable energy carrier for fuel cells. - Highlights: • A Ni–B film grown on Ni foam electrocatalyst is prepared by the electrless plating. • The Ni–B film shows high activity and stability for N_2H_4 electrooxidation reaction. • The improved catalytic property is ascribed to B-tuned electronic structure of Ni. • The resultant catalyst may promote application of N_2H_4 as a viable energy carrier. - Abstract: Hydrazine is a promising energy carrier for fuel cells owing to its combined advantages of high theoretical cell voltage, high-power density, and no greenhouse gas emission. By using an electroless plating process, we have prepared a robust Ni–B film grown on Ni foam that is highly effective for hydrazine electrooxidation in alkaline media. The effects of reaction temperature, concentrations of hydrous hydrazine and sodium hydroxide in the fuel solution on performance of hydrazine electrooxidation reaction are investigated. The mechanistic reason for the property advantage of as-prepared Ni–B/Ni foam catalyst over the relevant catalysts is discussed based on careful kinetics studies and characterization. The facile synthesis of Ni-based catalyst with high activity and good stability is of clear significance for the development of hydrous hydrazine as a viable energy carrier.

  19. 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.

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

    KAUST Repository

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

    2014-01-01

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

  1. High-Flux Zeolitic Imidazolate Framework Membranes for Propylene/Propane Separation by Postsynthetic Linker Exchange.

    Science.gov (United States)

    Lee, Moon Joo; Kwon, Hyuk Taek; Jeong, Hae-Kwon

    2018-01-02

    While zeolitic imidazolate framework, ZIF-8, membranes show impressive propylene/propane separation, their throughput needs to be greatly improved for practical applications. A method is described that drastically reduces the effective thickness of ZIF-8 membranes, thereby substantially improving their propylene permeance (that is, flux). The new strategy is based on a controlled single-crystal to single-crystal linker exchange of 2-methylimidazole in ZIF-8 membrane grains with 2-imidazolecarboxaldehyde (ZIF-90 linker), thereby enlarging the effective aperture size of ZIF-8. The linker-exchanged ZIF-8 membranes showed a drastic increase in propylene permeance by about four times, with a negligible loss in propylene/propane separation factor when compared to as-prepared membranes. The linker-exchange effect depends on the membrane synthesis method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Investigation of the Linker Swing Motion in the Zeolitic Imidazolate Framework ZIF-90

    KAUST Repository

    Zheng, Bin; Fu, Fang; Wang, Lian Li; Yang, Limin; Zhu, Yihan; Du, Huiling

    2018-01-01

    The linker swing motion in the zeolitic imidazolate framework ZIF-90 is investigated by density functional theory (DFT) calculation, molecular dynamics (MD) and grand-canonical Monte Carlo (GCMC) simulations. The relation between the terminal

  3. Composite materials with metal oxide attached to lead chalcogenide nanocrystal quantum dots with linkers

    Science.gov (United States)

    Fuke, Nobuhiro; Koposov, Alexey Y; Sykora, Milan; Hoch, Laura

    2014-12-16

    Composite materials useful for devices such as photoelectrochemical solar cells include a substrate, a metal oxide film on the substrate, nanocrystalline quantum dots (NQDs) of lead sulfide, lead selenide, and lead telluride, and linkers that attach the NQDs to the metal oxide film. Suitable linkers preserve the 1s absorption peak of the NQDs. A suitable linker has a general structure A-B-C where A is a chemical group adapted for binding to a MO.sub.x and C is a chemical group adapted for binding to a NQD and B is a divalent, rigid, or semi-rigid organic spacer moiety. Other linkers that preserve the 1s absorption peak may also be used.

  4. LRRC45 Is a Centrosome Linker Component Required for Centrosome Cohesion

    Directory of Open Access Journals (Sweden)

    Runsheng He

    2013-09-01

    Full Text Available During interphase, centrosomes are connected by a proteinaceous linker between the proximal ends of the centrioles, which is important for the centrosomes to function as a single microtubule-organizing center. However, the composition and regulation of centrosomal linker remain largely unknown. Here, we show that LRRC45 is a centrosome linker that localizes at the proximal ends of the centrioles and forms fiber-like structures between them. Depletion of LRRC45 results in centrosome splitting during interphase. Moreover, LRRC45 interacts with both C-Nap1 and rootletin and is phosphorylated by Nek2A at S661 during mitosis. After phosphorylation, both LRRC45 centrosomal localization and fiber-like structures are significantly reduced, which subsequently leads to centrosome separation. Thus, LRRC45 is a critical component of the proteinaceous linker between two centrioles and is required for centrosome cohesion.

  5. Identification of novel post-translational modifications in linker histones from chicken erythrocytes.

    Science.gov (United States)

    Sarg, Bettina; Lopez, Rita; Lindner, Herbert; Ponte, Inma; Suau, Pedro; Roque, Alicia

    2015-01-15

    Chicken erythrocyte nuclei were digested with micrococcal nuclease and fractionated by centrifugation in low-salt buffer into soluble and insoluble fractions. Post-translational modifications of the purified linker histones of both fractions were analyzed by LC-ESI-MS/MS. All six histone H1 subtypes (H1.01, H1.02, H1.03, H1.10, H1.1L and H1.1R) and histone H5 were identified. Mass spectrometry analysis enabled the identification of a wide range of PTMs, including N(α)-terminal acetylation, acetylation, formylation, phosphorylation and oxidation. A total of nine new modifications in chicken linker histones were mapped, most of them located in the N-terminal and globular domains. Relative quantification of the modified peptides showed that linker histone PTMs were differentially distributed among both chromatin fractions, suggesting their relevance in the regulation of chromatin structure. The analysis of our results combined with previously reported data for chicken and some mammalian species showed that most of the modified positions were conserved throughout evolution, highlighting their importance in specific linker histone functions and epigenetics. Post-translational modifications of linker histones could have a role in the regulation of gene expression through the modulation of chromatin higher-order structure and chromatin remodeling. Finding new PTMs in linker histones is the first step to elucidate their role in the histone code. In this manuscript we report nine new post-translational modifications of the linker histones from chicken erythrocytes, one in H5 and eight in the H1 subtypes. Chromatin fractionated by centrifugation in low-salt buffer resulted in two fractions with different contents and compositions of linker histones and enriched in specific core histone PTMs. Of particular interest is the fact that linker histone PTMs were differentially distributed in both chromatin fractions, suggesting specific functions. Future studies are needed to

  6. An Improved Calibration Method for Hydrazine Monitors for the United States Air Force

    Energy Technology Data Exchange (ETDEWEB)

    Korsah, K

    2003-07-07

    This report documents the results of Phase 1 of the ''Air Force Hydrazine Detector Characterization and Calibration Project''. A method for calibrating model MDA 7100 hydrazine detectors in the United States Air Force (AF) inventory has been developed. The calibration system consists of a Kintek 491 reference gas generation system, a humidifier/mixer system which combines the dry reference hydrazine gas with humidified diluent or carrier gas to generate the required humidified reference for calibrations, and a gas sampling interface. The Kintek reference gas generation system itself is periodically calibrated using an ORNL-constructed coulometric titration system to verify the hydrazine concentration of the sample atmosphere in the interface module. The Kintek reference gas is then used to calibrate the hydrazine monitors. Thus, coulometric titration is only used to periodically assess the performance of the Kintek reference gas generation system, and is not required for hydrazine monitor calibrations. One advantage of using coulometric titration for verifying the concentration of the reference gas is that it is a primary standard (if used for simple solutions), thereby guaranteeing, in principle, that measurements will be traceable to SI units (i.e., to the mole). The effect of humidity of the reference gas was characterized by using the results of concentrations determined by coulometric titration to develop a humidity correction graph for the Kintek 491 reference gas generation system. Using this calibration method, calibration uncertainty has been reduced by 50% compared to the current method used to calibrate hydrazine monitors in the Air Force inventory and calibration time has also been reduced by more than 20%. Significant findings from studies documented in this report are the following: (1) The Kintek 491 reference gas generation system (generator, humidifier and interface module) can be used to calibrate hydrazine detectors. (2) The

  7. Monte Carlo analysis of neck linker extension in kinesin molecular motors.

    Directory of Open Access Journals (Sweden)

    Matthew L Kutys

    2010-11-01

    Full Text Available Kinesin stepping is thought to involve both concerted conformational changes and diffusive movement, but the relative roles played by these two processes are not clear. The neck linker docking model is widely accepted in the field, but the remainder of the step--diffusion of the tethered head to the next binding site--is often assumed to occur rapidly with little mechanical resistance. Here, we investigate the effect of tethering by the neck linker on the diffusive movement of the kinesin head, and focus on the predicted behavior of motors with naturally or artificially extended neck linker domains. The kinesin chemomechanical cycle was modeled using a discrete-state Markov chain to describe chemical transitions. Brownian dynamics were used to model the tethered diffusion of the free head, incorporating resistive forces from the neck linker and a position-dependent microtubule binding rate. The Brownian dynamics and chemomechanical cycle were coupled to model processive runs consisting of many 8 nm steps. Three mechanical models of the neck linker were investigated: Constant Stiffness (a simple spring, Increasing Stiffness (analogous to a Worm-Like Chain, and Reflecting (negligible stiffness up to a limiting contour length. Motor velocities and run lengths from simulated paths were compared to experimental results from Kinesin-1 and a mutant containing an extended neck linker domain. When tethered by an increasingly stiff spring, the head is predicted to spend an unrealistically short amount of time within the binding zone, and extending the neck is predicted to increase both the velocity and processivity, contrary to experiments. These results suggest that the Worm-Like Chain is not an adequate model for the flexible neck linker domain. The model can be reconciled with experimental data if the neck linker is either much more compliant or much stiffer than generally assumed, or if weak kinesin-microtubule interactions stabilize the diffusing

  8. Effective generation of transgenic pigs and mice by linker based sperm-mediated gene transfer.

    OpenAIRE

    Chang, Keejong; Qian, Jin; Jiang, MeiSheng; Liu, Yi-Hsin; Wu, Ming-Che; Chen, Chi-Dar; Lai, Chao-Kuen; Lo, Hsin-Lung; Hsiao, Chin-Ton; Brown, Lucy; Bolen, James; Huang, Hsiao-I; Ho, Pei-Yu; Shih, Ping Yao; Yao, Chen-Wen

    2002-01-01

    Abstract Background Transgenic animals have become valuable tools for both research and applied purposes. The current method of gene transfer, microinjection, which is widely used in transgenic mouse production, has only had limited success in producing transgenic animals of larger or higher species. Here, we report a linker based sperm-mediated gene transfer method (LB-SMGT) that greatly improves the production efficiency of large transgenic animals. Results The linker protein, a monoclonal ...

  9. Lecithin-linker formulations for self-emulsifying delivery of nutraceuticals.

    Science.gov (United States)

    Chu, Jacquelene; Cheng, Yu-Ling; Rao, A Venketeshwer; Nouraei, Mehdi; Zarate-Muñoz, Silvia; Acosta, Edgar J

    2014-08-25

    Lecithin-linker microemulsions are formulations produced with soybean lecithin in combination with a highly lipophilic (lipophilic linker) and highly hydrophilic (hydrophilic linkers) surfactant-like additives. In this work, lecithin-linker systems were formulated to produce self-emulsifying delivery systems for β-carotene and β-sitosterol. The concentration of the lipophilic linker, sorbitan monooleate, was adjusted to minimize the formation of liquid crystals. The concentration of hydrophilic linkers, decaglyceryl caprylate/caprate and PEG-6-caprylic/capric glycerides, was gradually increased (scanned) until single phase clear microemulsions were obtained. For these scans, the oil (ethyl caprate) to water ratio was set to 1. The single phase, clear microemulsions were diluted with fed-state simulated intestinal fluid (FeSSIF) and produced stable emulsions, with drop sizes close to 200 nm. Using pseudo-ternary phase diagrams to evaluate the process of dilution of microemulsion preconcentrates (mixtures of oil, lecithin and linkers with little or no water) with FeSSIF, it was determined that self-emulsifying systems are obtained when the early stages of the dilution produce single phase microemulsions. If liquid crystals or multiple phase systems are obtained during those early stages, then the emulsification yields unstable emulsions with large drop sizes. An in vitro permeability study conducted using a Flow-Thru Dialyzer revealed that stable emulsions with drop sizes of 150-300 nm produce large and irreversible permeation of β-carotene to sheep intestine. On the other hand, unstable emulsions produced without the linker combination separated in the dialyzer chamber. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Stability and function of interdomain linker variants of glucoamylase 1 from Aspergillus niger.

    Science.gov (United States)

    Sauer, J; Christensen, T; Frandsen, T P; Mirgorodskaya, E; McGuire, K A; Driguez, H; Roepstorff, P; Sigurskjold, B W; Svensson, B

    2001-08-07

    Several variants of glucoamylase 1 (GA1) from Aspergillus niger were created in which the highly O-glycosylated peptide (aa 468--508) connecting the (alpha/alpha)(6)-barrel catalytic domain and the starch binding domain was substituted at the gene level by equivalent segments of glucoamylases from Hormoconis resinae, Humicola grisea, and Rhizopus oryzae encoding 5, 19, and 36 amino acid residues. Variants were constructed in which the H. resinae linker was elongated by proline-rich sequences as this linker itself apparently was too short to allow formation of the corresponding protein variant. Size and isoelectric point of GA1 variants reflected differences in linker length, posttranslational modification, and net charge. While calculated polypeptide chain molecular masses for wild-type GA1, a nonnatural proline-rich linker variant, H. grisea, and R. oryzae linker variants were 65,784, 63,777, 63,912, and 65,614 Da, respectively, MALDI-TOF-MS gave values of 82,042, 73,800, 73,413, and 90,793 Da, respectively, where the latter value could partly be explained by an N-glycosylation site introduced near the linker C-terminus. The k(cat) and K(m) for hydrolysis of maltooligodextrins and soluble starch, and the rate of hydrolysis of barley starch granules were essentially the same for the variants as for wild-type GA1. beta-Cyclodextrin, acarbose, and two heterobidentate inhibitors were found by isothermal titration calorimetry to bind to the catalytic and starch binding domains of the linker variants, indicating that the function of the active site and the starch binding site was maintained. The stability of GA1 linker variants toward GdnHCl and heat, however, was reduced compared to wild-type.

  11. Rational design of molecularly imprinted polymer: the choice of cross-linker.

    Science.gov (United States)

    Muhammad, Turghun; Nur, Zohre; Piletska, Elena V; Yimit, Osmanjan; Piletsky, Sergey A

    2012-06-07

    The paper describes a rational approach for the selection of cross-linkers during the development of molecularly imprinted polymers (MIPs). As a model system for this research MIPs specific for the drug zidovudine (AZT) were designed and tested. Three cross-linkers trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) were studied. The analogue of zidovudine (AZT) ester (AZT-ES) was used as a dummy template. The imprinting factors for all of the polymers in the static adsorption experiments were calculated. The data on the AZT adsorption by control polymers (CP), which were prepared with different cross-linkers without a functional monomer, was also analyzed. DVB was found to be more inert towards zidovudine than EGDMA and TRIM, which was confirmed by both molecular modelling and adsorption experiments. It was demonstrated that DVB-based polymers had a higher imprinting factor (I = 1.85) compared with other tested cross-linked polymers. It was suggested that the selection of the cross-linker should be based on the strength of the interaction with the template: the cross-linker which displays lower binding of the template should be preferential because it generates MIPs with lower non-specific binding and a higher imprinting factor, and therefore specificity. Which cross-linker to use for the preparation of any particular MIP can be determined by analysis of the interactions between the cross-linker and template. This could be done either virtually using computational modelling or by template adsorption using a small library of polymers prepared using different cross-linkers.

  12. Novel Concepts of MS-Cleavable Cross-linkers for Improved Peptide Structure Analysis

    Science.gov (United States)

    Hage, Christoph; Falvo, Francesco; Schäfer, Mathias; Sinz, Andrea

    2017-10-01

    The chemical cross-linking/mass spectrometry (MS) approach is gaining increasing importance as an alternative method for studying protein conformation and for deciphering protein interaction networks. This study is part of our ongoing efforts to develop innovative cross-linking principles for a facile and efficient assignment of cross-linked products. We evaluate two homobifunctional, amine-reactive, and MS-cleavable cross-linkers regarding their potential for automated analysis of cross-linked products. We introduce the bromine phenylurea (BrPU) linker that possesses a unique structure yielding a distinctive fragmentation pattern on collisional activation. Moreover, BrPU delivers the characteristic bromine isotope pattern and mass defect for all cross-linker-decorated fragments. We compare the fragmentation behavior of the BrPU linker with that of our previously described MS-cleavable TEMPO-Bz linker (which consists of a 2,2,6,6-tetramethylpiperidine-1-oxy moiety connected to a benzyl group) that was developed to perform free-radical-initiated peptide sequencing. Comparative collisional activation experiments (collision-induced dissociation and higher-energy collision-induced dissociation) with both cross-linkers were conducted in negative electrospray ionization mode with an Orbitrap Fusion mass spectrometer using five model peptides. As hypothesized in a previous study, the presence of a cross-linked N-terminal aspartic acid residue seems to be the prerequisite for the loss of an intact peptide from the cross-linked products. As the BrPU linker combines a characteristic mass shift with an isotope signature, it presents a more favorable combination for automated assignment of cross-linked products compared with the TEMPO-Bz linker. [Figure not available: see fulltext.

  13. Ultra-high sensitive hydrazine chemical sensor based on low-temperature grown ZnO nanoparticles

    International Nuclear Information System (INIS)

    Mehta, S.K.; Singh, Kulvinder; Umar, Ahmad; Chaudhary, G.R.; Singh, Sukhjinder

    2012-01-01

    Graphical abstract: Systematic representation of the fabricated amperometric hydrazine chemical sensor based on ZnO NPs/Au modified electrode. Highlights: ► Synthesis of well-crystalline ZnO NPs has been achieved in aqueous solution. ► ZnO NPs act as efficient electron mediators for hydrazine sensor. ► Extremely high sensitivity and low-detection limit have been obtained. - Abstract: Using well-crystalline ZnO nanoparticles (NPs), an ultra high sensitive hydrazine amperometric sensor has been fabricated and reported in this paper. The ZnO NPs have been synthesized by very simple aqueous solution process at 90 °C and characterized in detail in terms of their morphological, compositional, structural and optical properties. The detailed investigations reveal that the synthesized products are well-crystalline NPs, possessing wurtzite hexagonal phase and exhibit good optical properties. The fabricated amperometric hydrazine sensor exhibits ultra-high sensitivity of ∼97.133 μA cm −2 μM −1 and very low-detection limit of 147.54 nM. To the best of our knowledge, this is the first report in which an ultra-high sensitivity and low-detection limit have been obtained for the hydrazine chemical sensor based on ZnO nanostructures.

  14. Thionine-Bromate as a New Reaction System for Kinetic Spectrophotometric Determination of Hydrazine in Cooling Tower Water Samples

    Directory of Open Access Journals (Sweden)

    Masoud Reza Shishehbore

    2013-01-01

    Full Text Available A simple, selective, and inexpensive kinetic method was developed for the determination of hydrazine based on its inhibitory effect on the thionine-bromate system in sulfuric acid media. The reaction was monitored spectrophotometrically at 601 nm by a fixed time method. The effect of different parameters such as concentration of reactants, ionic strength, temperature, and time on the rate of reaction was investigated, and the optimum conditions were obtained. Under optimum conditions, the calibration curve was linear in the concentration range from 0.8–23.0 μg mL−1 of hydrazine, and the detection limit of the method was 0.22 μg mL−1. The relative standard deviation for five replicate determinations of 1.0 μg mL−1 of hydrazine was 0.74%. The potential of interfering effect of foreign species on the hydrazine determination was studied. The proposed method was successfully applied for the determination of hydrazine in different water samples.

  15. The influence of tertiary butyl hydrazine as a co-reactant on the atomic layer deposition of silver

    Energy Technology Data Exchange (ETDEWEB)

    Golrokhi, Zahra; Marshall, Paul A.; Romani, Simon [Centre for Materials and Structures, School of Engineering,The University of Liverpool, Liverpool L69 3GH (United Kingdom); Rushworth, Simon [EpiValence, The Wilton Centre, Redcar, Cleveland, TS10 4RF (United Kingdom); Chalker, Paul R. [Centre for Materials and Structures, School of Engineering,The University of Liverpool, Liverpool L69 3GH (United Kingdom); Potter, Richard J., E-mail: rjpott@liverpool.ac.uk [Centre for Materials and Structures, School of Engineering,The University of Liverpool, Liverpool L69 3GH (United Kingdom)

    2017-03-31

    Highlights: • We demonstrate metallic silver growth by direct liquid injection thermal ALD. • A substituted hydrazine is used as a powerful reducing agent for the first time. • The hydrazine extends the ALD temperature window compared with alcohol. • Hydrazine promotes a more planar growth mode compared to alcohol. • Film adhesion is improved using hydrazine compared with alcohol. - Abstract: Ultra-thin conformal silver films are the focus of development for applications such as anti-microbial surfaces, optical components and electronic devices. In this study, metallic silver films have been deposited using direct liquid injection thermal atomic layer deposition (ALD) using (hfac)Ag(1,5-COD) ((hexafluoroacetylacetonato)silver(I)(1,5-cyclooctadiene)) as the metal source and tertiary butyl hydrazine (TBH) as a co-reactant. The process provides a 23 °C wide ‘self-limiting’ ALD temperature window between 105 and 128 °C, which is significantly wider than is achievable using alcohol as a co-reactant. A mass deposition rate of ∼20 ng/cm{sup 2}/cycle (∼0.18 Å/cycle) is observed under self-limiting growth conditions. The resulting films are crystalline metallic silver with a near planar film-like morphology which are electrically conductive. By extending the temperature range of the ALD window by the use of TBH as a co-reactant, it is envisaged that the process will be exploitable in a range of new low temperature applications.

  16. Effect of gold nanoparticle as a novel nanocatalyst on luminol-hydrazine chemiluminescence system and its analytical application

    International Nuclear Information System (INIS)

    Safavi, A.; Absalan, G.; Bamdad, F.

    2008-01-01

    In this work the catalytic role of unsupported gold nanoparticles on the luminol-hydrazine reaction is investigated. Gold nanoparticles catalyze the reaction of hydrazine and dissolved oxygen to generate hydrogen peroxide and also catalyze the oxidation of luminol by the produced hydrogen peroxide. The result is an intense chemiluminescence (CL) due to the excited 3-aminophthalate anion. In the absence of gold nanoparticles no detectable CL was observed by the reaction of luminol and hydrazine unless an external oxidant is present in the system. The size effect of gold nanoparticles on the CL intensity was investigated. The most intensive CL signals were obtained with 15-nm gold nanoparticles. UV-vis spectra and transmission electron microscopy studies were used to investigate the CL mechanism. The luminol and hydroxide ion concentration, gold nanoparticles size and flow rate were optimized. The proposed method was successfully applied to the determination of hydrazine in boiler feed water samples. Between 0.1 and 30 μM of hydrazine could be determined with a detection limit of 30 nM

  17. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, Guy [Univ. of California, San Diego, CA (United States)

    2012-06-29

    The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry” since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH3 and NH2NH2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH3- and NH2NH2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require

  18. Synthesis of the row of new functional derivatives of 7-arylalkyl-8-hydrazine theophyllines

    Directory of Open Access Journals (Sweden)

    Dmytro Korobko

    2016-03-01

    Full Text Available Hydrazine functional derivatives are widely used in medical practice as remedies applied for pharmacotherapy of depression, infection diseases, hypertension, diabetes, etc. It is worth mentioning that among obtained 7-R-8-hydrazine derivatives of 1,3-dimethylxantine promising substances have been identified. Due to the fact that literature sources display only results of occasional studies of the reactions between 7-R-8-hydrazine theophyllines and mono- or dicarbonyle substances, the use of other keto reagents for xanthine bicycle at 8th position functionalization will allow to explore synthetic potential of the last one, and with high probability may lead to obtaining original biologically active substances.Aim. To study types of reaction between 8-hydrazinyl-1,3-dimethyl-7-aryl alkyl-1H-purine-2,6(3H,7H-diones and a number of carbonyl containing reagents.Methods. A nucleophilic addition reaction followed by dehydration or ethanol splitting was used, as well as the complex of the modern analysis methods to confirm the structure and individuality of the synthesized substances.Results. Different directions of 8-hydrazinyl-1,3,-dimethyl-7(fenetyl-, 3-phenylpropyl-, 3-phenylalyl-1H-purine-2,6(3H,7H-diones chemical transformations in reactions with the appropriate carbonyl containing compounds have been studied experimentally. The structure of synthesized substances was confirmed by chromatography/mass and 1H NMR spectroscopy.Conclusion. The group of 7-arylalkyl-8-(3,5-R,R1-pyrazole-1-yltheophyllines, consisting of two functionally substituted bioactive heterocycles, has been synthesized by reaction between initial substances and selected mono- and dicarbonyl compounds

  19. Characterization of Anammox Hydrazine Dehydrogenase, a Key N2-producing Enzyme in the Global Nitrogen Cycle.

    Science.gov (United States)

    Maalcke, Wouter J; Reimann, Joachim; de Vries, Simon; Butt, Julea N; Dietl, Andreas; Kip, Nardy; Mersdorf, Ulrike; Barends, Thomas R M; Jetten, Mike S M; Keltjens, Jan T; Kartal, Boran

    2016-08-12

    Anaerobic ammonium-oxidizing (anammox) bacteria derive their energy for growth from the oxidation of ammonium with nitrite as the electron acceptor. N2, the end product of this metabolism, is produced from the oxidation of the intermediate, hydrazine (N2H4). Previously, we identified N2-producing hydrazine dehydrogenase (KsHDH) from the anammox organism Kuenenia stuttgartiensis as the gene product of kustc0694 and determined some of its catalytic properties. In the genome of K. stuttgartiensis, kustc0694 is one of 10 paralogs related to octaheme hydroxylamine (NH2OH) oxidoreductase (HAO). Here, we characterized KsHDH as a covalently cross-linked homotrimeric octaheme protein as found for HAO and HAO-related hydroxylamine-oxidizing enzyme kustc1061 from K. stuttgartiensis Interestingly, the HDH trimers formed octamers in solution, each octamer harboring an amazing 192 c-type heme moieties. Whereas HAO and kustc1061 are capable of hydrazine oxidation as well, KsHDH was highly specific for this activity. To understand this specificity, we performed detailed amino acid sequence analyses and investigated the catalytic and spectroscopic (electronic absorbance, EPR) properties of KsHDH in comparison with the well defined HAO and kustc1061. We conclude that HDH specificity is most likely derived from structural changes around the catalytic heme 4 (P460) and of the electron-wiring circuit comprising seven His/His-ligated c-type hemes in each subunit. These nuances make HDH a globally prominent N2-producing enzyme, next to nitrous oxide (N2O) reductase from denitrifying microorganisms. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

  20. Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

    International Nuclear Information System (INIS)

    Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.

    2015-01-01

    Liquid natural rubber (LNR) with molecular weight of lower than 10 5 and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA)

  1. Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

    Science.gov (United States)

    Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M.

    2015-09-01

    Liquid natural rubber (LNR) with molecular weight of lower than 105 and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA).

  2. Hydrogenation of liquid natural rubber via diimide reduction in hydrazine hydrate/hydrogen peroxide system

    Energy Technology Data Exchange (ETDEWEB)

    Yusof, Muhammad Jefri Mohd; Jamaluddin, Naharullah; Abdullah, Ibrahim; Yusoff, Siti Fairus M. [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor (Malaysia)

    2015-09-25

    Liquid natural rubber (LNR) with molecular weight of lower than 10{sup 5} and shorter polymeric chain than natural rubber was prepared. LNR was then hydrogenated via diimide reduction by oxidation of hydrazine hydrate with hydrogen peroxide. The unsaturated units of the rubber were converted into saturated hydrocarbon to strengthen the backbone of the polymer so it was able to resist thermal degradation. The results indicated that hydrogenation degree of the product (HLNR) could be extended to 91.2% conversion under appropriate conditions. The hydrogenated LNR (HLNR) was characterized using Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The physical characteristics of HLNR were analyzed with Termogravimetric Analysis (TGA)

  3. Synthesis and Characterization of New Polyamides from 1,2-Bis hydrazine Derivatives

    International Nuclear Information System (INIS)

    Salaha, A.; Abdel-Bary, E.M.; Kandilea, N.G.

    2005-01-01

    Preparation of polyamides having different chemical structures allows obtaining new materials with different mechanical and physical properties. The difference in the chemical structure depends mainly on the starting reactants used in condensation polymerization of polyamides. In this paper the synthesis of new polyamides based on the condensation polymerization of 1,2- Bis(3-carboxyacryloyl or carboxybenzoyl) hydrazine derivatives and various diamines has been described. The polymers obtained were characterized using spectroscopic and X-ray analysis. Besides thermal stability and electrical conductivity have been evaluated and correlated with the chemical structure of the polyamides obtained

  4. Spectral properties of ultrasmall CdS nanoparticles Stabilized by mercaptoacids and hydrazine

    International Nuclear Information System (INIS)

    Solonenko, Dmytro I.; Rayevska, Oleksandra Ye.; Stroyuk, Oleksandr L.; Kuchmiy, Stepan Ya.

    2013-01-01

    Ultrasmall colloidal CdS quantum dots (QDs) were synthesized in water at room temperature by using a combination of two low-molecular-weight stabilizers - hydrazine and a mercaptoacid, particularly, mercaptoacetic and mercaptopropionic-2 acids. The average size of QDs was found to depend on the Cd-to-S ratio at the synthesis and be as small as 2,5 nm at 80% cadmium(II) excess. The CdS QDs emit broadband photoluminescence in the visible spectrum range with a relative quantum yield of around 5% and the radiative life time of around 100 ns. (authors)

  5. Standard and hydrazine water chemistry in primary circuit of VVER 440 units

    International Nuclear Information System (INIS)

    Burclova, J.

    1992-01-01

    Standard ammonia-potassium-boron water chemistry of 8 units with VVER 440 in CSFR is discussed as well as the corrosion product activity in the coolant during steady state and shut-down period and surface activity, dose rate build-up and occupational radiation exposure. Available data on hydrazine application (USSR, Hungary) indicate the possibility of the radiation field decreasing. Nevertheless the detailed analysis of 55 cycles of operation under standard water chemistry in Czechoslovakia allows to expect the comparable results for both water chemistries. (author)

  6. Electrocatalytic oxidation of hydrazine and hydroxylamine by graphene oxide-Pd nanoparticle-modified glassy carbon electrode.

    Science.gov (United States)

    Lee, Eunhee; Kim, Daekun; You, Jung-Min; Kim, Seul Ki; Yun, Mira; Jeon, Seungwon

    2012-12-01

    Pd nanoparticle catalysts supported by thiolated graphene oxide (tGO) on a glassy carbon electrode (GCE), and denoted as tGO-Pd/GCE, are used in this study for the electrochemical determination of hydroxylamine and hydrazine. The physicochemical properties of tGO-Pd were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). They showed strong catalytic activity toward the oxidation of hydroxylamine and hydrazine. Cyclic voltammetry (CV) and amperometry were used to characterize the sensors' performances. The detection limits of hydroxylamine and hydrazine by tGO-Pd/GCE were 0.31 and 0.25 microM (s/n = 3), respectively. The sensors' sensitivity, selectivity, and stability were also investigated.

  7. Structural properties of the linkers connecting the N- and C- terminal domains in the MocR bacterial transcriptional regulators

    Directory of Open Access Journals (Sweden)

    Teresa Milano

    2016-12-01

    Full Text Available Peptide inter-domain linkers are peptide segments covalently linking two adjacent domains within a protein. Linkers play a variety of structural and functional roles in naturally occurring proteins. In this work we analyze the sequence properties of the predicted linker regions of the bacterial transcriptional regulators belonging to the recently discovered MocR subfamily of the GntR regulators. Analyses were carried out on the MocR sequences taken from the phyla Actinobacteria, Firmicutes, Alpha-, Beta- and Gammaproteobacteria. The results suggest that MocR linkers display phylum-specific characteristics and unique features different from those already described for other classes of inter-domain linkers. They show an average length significantly higher: 31.8 ± 14.3 residues reaching a maximum of about 150 residues. Compositional propensities displayed general and phylum-specific trends. Pro is dominating in all linkers. Dyad propensity analysis indicate Pro–Pro as the most frequent amino acid pair in all linkers. Physicochemical properties of the linker regions were assessed using amino acid indices relative to different features: in general, MocR linkers are flexible, hydrophilic and display propensity for β-turn or coil conformations. Linker sequences are hypervariable: only similarities between MocR linkers from organisms related at the level of species or genus could be found with sequence searches. The results shed light on the properties of the linker regions of the new MocR subfamily of bacterial regulators and may provide knowledge-based rules for designing artificial linkers with desired properties.

  8. The development of a non-cryogenic nitrogen/oxygen supply system. [using hydrazine/water electrolysis

    Science.gov (United States)

    Greenough, B. M.; Mahan, R. E.

    1974-01-01

    A hydrazine/water electrolysis process system module design was fabricated and tested to demonstrate component and module performance. This module is capable of providing both the metabolic oxygen for crew needs and the oxygen and nitrogen for spacecraft leak makeup. The component designs evolved through previous R and D efforts, and were fabricated and tested individually and then were assembled into a complete module which was successfully tested for 1000 hours to demonstrate integration of the individual components. A survey was made of hydrazine sensor technology and a cell math model was derived.

  9. Reactivity of nanoaggregations of platinum on supports of different nature in reactions of catalytic decomposition of hydrazine in acid media

    International Nuclear Information System (INIS)

    Anan'ev, A.V.; Boltoeva, M.Yu.; Grigor'ev, M.S.; Shilov, V.P.; Sharygin, L.M.

    2006-01-01

    Platinized catalysts on the basis of supports of different chemical nature are tested in reactions of catalytic hydrazine decomposition in perchloric and nitric acid solutions. In perchloric acid catalytic activity of catalysts on the basis of ceramic materials of Termoksid brand is higher of activity of catalysts on the basis of amorphous silica gel. In nitric acid solutions opposite dependence is observed. Tendency of ceramic supports to peptization in acid solutions is pointed out. Results obtained are interpreted using conceptions of energetic heterogeneity of surface atoms and hydrazine catalytic decomposition mechanisms in different media [ru

  10. Liquid-Phase Heat-Release Rates of the Systems Hydrazine-Nitric Acid and Unsymmetrical Dimethylhydrazine-Nitric Acid

    Science.gov (United States)

    Somogyi, Dezso; Feiler, Charles E.

    1960-01-01

    The initial rates of heat release produced by the reactions of hydrazine and unsymmetrical dimethylhydrazine with nitric acid were determined in a bomb calorimeter under conditions of forced mixing. Fuel-oxidant weight ratio and injection velocity were varied. The rate of heat release apparently depended on the interfacial area between the propellants. Above a narrow range of injection velocities representing a critical amount of interfacial area, the rates reached a maximum and were almost constant with injection velocity. The maximum rate for hydrazine was about 70 percent greater than that for unsymmetrical dimethylhydrazine. The total heat released did not vary with mixture ratio over the range studied.

  11. Meiotic changes in Vicia faba L. subsequent to treatments of hydrazine hydrate and maleic hydrazide

    Directory of Open Access Journals (Sweden)

    Shaheen Husain

    2013-01-01

    Full Text Available Assessing the impact of mutagens for creating variations in crops like faba bean (Vicia faba L. is an important criterion in the contemporary world where food insecurity and malnutrition is alarming at the doors of various nations. Impact of two chemical mutagens viz. hydrazine hydrate (HZ and maleic hydrazide (MH on the two varieties (NDF-1 and HB-405 of Vicia faba were analysed in terms of meiotic behavior and pollen sterility. Since there are not enough data about the effect of these mutagens on the chromosomal behaviors of Vicia faba, this study presents the role of hydrazine hydrate and maleic hydrazide as well as various types of chromosomal aberrations in crop improvement. The lower concentration of mutagens showed less pollen sterility compared to the higher concentrations. Manipulation of plant structural component to induce desirable alternations provides valuable material for the breeders and could be used favorably for increasing mutation rate and obtaining a desirable spectrum of mutation in faba beans based on preliminary studies of cell division.

  12. Chemical and enzymatic stability of amino acid prodrugs containing methoxy, ethoxy and propylene glycol linkers.

    Science.gov (United States)

    Gupta, Deepak; Gupta, Sheeba Varghese; Lee, Kyung-Dall; Amidon, Gordon L

    2009-01-01

    We evaluated the chemical and enzymatic stabilities of prodrugs containing methoxy, ethoxy and propylene glycol linkers in order to find a suitable linker for prodrugs of carboxylic acids with amino acids. l-Valine and l-phenylalanine prodrugs of model compounds (benzoic acid and phenyl acetic acid) containing methoxy, ethoxy and propylene glycol linkers were synthesized. The hydrolysis rate profile of each compound was studied at physiologically relevant pHs (1.2, 4, 6 and 7.4). Enzymatic hydrolysis of propylene glycol containing compounds was studied using Caco-2 homogenate as well as purified enzyme valacyclovirase. It was observed that the stability of the prodrugs increases with the linker length (propyl > ethyl > methyl). The model prodrugs were stable at acidic pH as compared to basic pH. It was observed that the prodrug with the aliphatic amino acid promoiety was more stable compared to its aromatic counterpart. The comparison between benzyl and the phenyl model compounds revealed that the amino acid side chain is significant in determining the stability of the prodrug whereas the benzyl or phenyl carboxylic acid had little or no effect on the stability. The enzymatic activation studies of propylene glycol linker prodrug in the presence of valacyclovirase and cell homogenate showed faster generation of the parent drug at pH 7.4. The half-life of prodrugs at pH 7.4 was more than 12 h, whereas in the presence of cell homogenate the half-lives were less than 1 h. Hydrolysis by Caco-2 homogenate generated the parent compound in two steps, where the prodrug was first converted to the intermediate, propylene glycol benzoate, which was then converted to the parent compound (benzoic acid). Enzymatic hydrolysis of propylene glycol containing prodrugs by valacyclovirase showed hydrolysis of the amino acid ester part to generate the propylene glycol ester of model compound (propylene glycol benzoate) as the major product. The amino acid prodrugs containing methoxy

  13. The measles virus phosphoprotein interacts with the linker domain of STAT1

    International Nuclear Information System (INIS)

    Devaux, Patricia; Priniski, Lauren; Cattaneo, Roberto

    2013-01-01

    The measles virus (MV) phosphoprotein (P) and V proteins block the interferon (IFN) response by impeding phosphorylation of the signal transducer and activator of transcription 1 (STAT1) by the Janus kinase 1 (JAK1). We characterized how STAT1 mutants interact with P and JAK1 phosphorylation. Certain mutants of the linker, the Src-homology 2 domain (SH2), or the transactivation domain had reduced or abolished phosphorylation through JAK1 after IFN treatment. Other mutants, mainly localized in the linker, failed to interact with P as documented by the lack of interference with nuclear translocation. Thus the functional footprint of P on STAT1 localizes mainly to the linker domain; there is also some overlap with the STAT1 phosphorylation functional footprint on the SH2 domain. Based on these observations, we discuss how the MV-P might operate to inhibit the JAK/STAT pathway. - Highlights: • Residue in the linker and SH2 domains of STAT1 are important for MV-P interaction. • Residue in the linker and SH2 domains of STAT1 are important for STAT1 phosphorylation. • Residues interferring with both functions have similar location on STAT1. • The viral P and V proteins may operate in concert to inhibit the JAK/STAT pathway

  14. The measles virus phosphoprotein interacts with the linker domain of STAT1

    Energy Technology Data Exchange (ETDEWEB)

    Devaux, Patricia, E-mail: devaux.patricia@mayo.edu; Priniski, Lauren; Cattaneo, Roberto

    2013-09-15

    The measles virus (MV) phosphoprotein (P) and V proteins block the interferon (IFN) response by impeding phosphorylation of the signal transducer and activator of transcription 1 (STAT1) by the Janus kinase 1 (JAK1). We characterized how STAT1 mutants interact with P and JAK1 phosphorylation. Certain mutants of the linker, the Src-homology 2 domain (SH2), or the transactivation domain had reduced or abolished phosphorylation through JAK1 after IFN treatment. Other mutants, mainly localized in the linker, failed to interact with P as documented by the lack of interference with nuclear translocation. Thus the functional footprint of P on STAT1 localizes mainly to the linker domain; there is also some overlap with the STAT1 phosphorylation functional footprint on the SH2 domain. Based on these observations, we discuss how the MV-P might operate to inhibit the JAK/STAT pathway. - Highlights: • Residue in the linker and SH2 domains of STAT1 are important for MV-P interaction. • Residue in the linker and SH2 domains of STAT1 are important for STAT1 phosphorylation. • Residues interferring with both functions have similar location on STAT1. • The viral P and V proteins may operate in concert to inhibit the JAK/STAT pathway.

  15. A High-Throughput Small Molecule Screen for C. elegans Linker Cell Death Inhibitors.

    Directory of Open Access Journals (Sweden)

    Andrew R Schwendeman

    Full Text Available Programmed cell death is a ubiquitous process in metazoan development. Apoptosis, one cell death form, has been studied extensively. However, mutations inactivating key mammalian apoptosis regulators do not block most developmental cell culling, suggesting that other cell death pathways are likely important. Recent work in the nematode Caenorhabditis elegans identified a non-apoptotic cell death form mediating the demise of the male-specific linker cell. This cell death process (LCD, linker cell-type death is morphologically conserved, and its molecular effectors also mediate axon degeneration in mammals and Drosophila. To develop reagents to manipulate LCD, we established a simple high-throughput screening protocol for interrogating the effects of small molecules on C. elegans linker cell death in vivo. From 23,797 compounds assayed, 11 reproducibly block linker cell death onset. Of these, five induce animal lethality, and six promote a reversible developmental delay. These results provide proof-of principle validation of our screening protocol, demonstrate that developmental progression is required for linker cell death, and suggest that larger scale screens may identify LCD-specific small-molecule regulators that target the LCD execution machinery.

  16. Effect of the SH3-SH2 domain linker sequence on the structure of Hck kinase.

    Science.gov (United States)

    Meiselbach, Heike; Sticht, Heinrich

    2011-08-01

    The coordination of activity in biological systems requires the existence of different signal transduction pathways that interact with one another and must be precisely regulated. The Src-family tyrosine kinases, which are found in many signaling pathways, differ in their physiological function despite their high overall structural similarity. In this context, the differences in the SH3-SH2 domain linkers might play a role for differential regulation, but the structural consequences of linker sequence remain poorly understood. We have therefore performed comparative molecular dynamics simulations of wildtype Hck and of a mutant Hck in which the SH3-SH2 domain linker is replaced by the corresponding sequence from the homologous kinase Lck. These simulations reveal that linker replacement not only affects the orientation of the SH3 domain itself, but also leads to an alternative conformation of the activation segment in the Hck kinase domain. The sequence of the SH3-SH2 domain linker thus exerts a remote effect on the active site geometry and might therefore play a role in modulating the structure of the inactive kinase or in fine-tuning the activation process itself.

  17. Disruption of the IS6-AID linker affects voltage-gated calcium channel inactivation and facilitation.

    Science.gov (United States)

    Findeisen, Felix; Minor, Daniel L

    2009-03-01

    Two processes dominate voltage-gated calcium channel (Ca(V)) inactivation: voltage-dependent inactivation (VDI) and calcium-dependent inactivation (CDI). The Ca(V)beta/Ca(V)alpha(1)-I-II loop and Ca(2+)/calmodulin (CaM)/Ca(V)alpha(1)-C-terminal tail complexes have been shown to modulate each, respectively. Nevertheless, how each complex couples to the pore and whether each affects inactivation independently have remained unresolved. Here, we demonstrate that the IS6-alpha-interaction domain (AID) linker provides a rigid connection between the pore and Ca(V)beta/I-II loop complex by showing that IS6-AID linker polyglycine mutations accelerate Ca(V)1.2 (L-type) and Ca(V)2.1 (P/Q-type) VDI. Remarkably, mutations that either break the rigid IS6-AID linker connection or disrupt Ca(V)beta/I-II association sharply decelerate CDI and reduce a second Ca(2+)/CaM/Ca(V)alpha(1)-C-terminal-mediated process known as calcium-dependent facilitation. Collectively, the data strongly suggest that components traditionally associated solely with VDI, Ca(V)beta and the IS6-AID linker, are essential for calcium-dependent modulation, and that both Ca(V)beta-dependent and CaM-dependent components couple to the pore by a common mechanism requiring Ca(V)beta and an intact IS6-AID linker.

  18. Sol-gel process preparation and evaluation of the analytical performances of an hydrazine specific chemical sensor; Preparation par procede sol-gel et evaluation des performances analytiques d`un capteur chimique specifique de l`hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Gojon, C

    1996-12-01

    The realisation of optical fibers active chemical collector to analyze hydrazine in line, in the spent fuel reprocessing process is the subject of this work. The p.dimethyl-amino-benzaldehyde has been chosen as reagent for its chemical and optical properties. 186 refs.

  19. Crystal structures of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper and chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper

    Energy Technology Data Exchange (ETDEWEB)

    Chumakov, Yu. M. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Paholnitcaia, A. Yu. [State University of Moldova (Moldova, Republic of); Petrenko, P. A. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I., E-mail: vtsapkov@gmail.com [State University of Moldova (Moldova, Republic of); Poirier, D. [Centre Hospitalier Universitaire de Quebec (Canada); Gulea, A. P. [State University of Moldova (Moldova, Republic of)

    2015-01-15

    Two crystal modifications of nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper (I and II) and two modifications of chloro-(2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) copper (III and IV) have been synthesized and studied by X-ray diffraction. In structures I and II, the copper atoms coordinate a monodeprotonated molecule of the organic ligand, nitrate ions, and a water molecule. In crystals of I, the complexes are monomeric, whereas complexes II are linked via nitrate ions to form polymeric chains. In both structures the coordination polyhedron of the copper atom can be described as a distorted tetragonal bipyramid—(4 + 1 + 1) in I and (4 + 2) in II. These coordination polyherdra have different compositions. In structures III and IV, the metal atoms coordinate a monodeprotonated (2-[2-phenyl(pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazole molecule and chloride ions. In III the complex-forming ion has square-planar coordination geometry, whereas structure IV consists of centrosymmetric dimers with two bridging chlorine atoms. It was found that nitrato-(2-[2-(1-pyridine-2-ylethylidene)hydrazine]-1,3-benzothiazolo) aquacopper possesses antitumor activity.

  20. Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum; Etude de l`oxydation electrochimique directe et indirecte de l`hydrazine en milieu acide nitrique sur platine

    Energy Technology Data Exchange (ETDEWEB)

    Cames, B

    1997-12-31

    In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media ({<=} 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 {<=} E {<=} 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

  1. Electrocatalytic oxidation of diethylaminoethanethiol and hydrazine at single-walled carbon nanotubes modified with prussian blue nanoparticles

    CSIR Research Space (South Africa)

    Adekunle, AS

    2010-11-01

    Full Text Available good electrochemical stability in the analytical solution, showing limit of detection in the micromolar range and catalytic rate constant of 3.71×106 and 7.56×106 cm3 mol-1 s-1 for DEAET and hydrazine respectively. The adsorption properties...

  2. Homoaromatics as intermediates in the substitution reactions of 1,2,4,5-tetrazines with ammonia and hydrazine

    International Nuclear Information System (INIS)

    Counotte-Potman, A.D.

    1981-01-01

    This thesis describes some nucleophilic substitution reactions between the red 1,2,4,5-tetrazines and hydrazine-hydrate or ammonia. Special attention was paid to the occurrence of the Ssub(N) (ANRORC) mechanism in these substitution reactions. This mechanism comprises a sequence of reactions, involving the Addition of a Nucleopile to a heteroaromatic species, followed by a Ring-Opening and Ring Closure reaction to the substitution product. 3-Alkyl(aryl)-1,2,4,5-tetrazines were found to undergo a Chichibabin hydrazination into 6-hydrazino-3-alkyl(aryl)-1,2,4,5-tetrazines on treatment with hydrazine-hydrate. The first step in this reaction sequence was the formation of a homoaromatic sigma-adduct. Subsequently an open-chain intermediate was observed by NMR, on raising the temperature. Finally the hydrazino compound is formed by ring closure. This reaction sequence can be considered as an Ssub(N)(ANRORC) process. With 15 N-labelled hydrazine, only part of the label was found to be built in the 1,2,4,5-tetrazine ring of the 6-hydrazino compounds. This is the first example of a reaction in which both the hydrazino compound with the 15 N-label in the ring and with the 15 N-label in the exocyclic hydrazino group are formed according to the Ssub(N)(ANRORC) mechanism. (Auth.)

  3. Sol-gel process preparation and evaluation of the analytical performances of an hydrazine specific chemical sensor

    International Nuclear Information System (INIS)

    Gojon, C.

    1996-12-01

    The realisation of optical fibers active chemical collector to analyze hydrazine in line, in the spent fuel reprocessing process is the subject of this work. The p.dimethyl-amino-benzaldehyde has been chosen as reagent for its chemical and optical properties

  4. Linker Histone Phosphorylation Regulates Global Timing of Replication Origin Firing*S⃞

    Science.gov (United States)

    Thiriet, Christophe; Hayes, Jeffrey J.

    2009-01-01

    Despite the presence of linker histone in all eukaryotes, the primary function(s) of this histone have been difficult to clarify. Knock-out experiments indicate that H1s play a role in regulation of only a small subset of genes but are an essential component in mouse development. Here, we show that linker histone (H1) is involved in the global regulation of DNA replication in Physarum polycephalum. We find that genomic DNA of H1 knock-down cells is more rapidly replicated, an effect due at least in part to disruption of the native timing of replication fork firing. Immunoprecipitation experiments demonstrate that H1 is transiently lost from replicating chromatin via a process facilitated by phosphorylation. Our results suggest that linker histones generate a chromatin environment refractory to replication and that their transient removal via protein phosphorylation during S phase is a critical step in the epigenetic regulation of replication timing. PMID:19015270

  5. The centrosomal linker and microtubules provide dual levels of spatial coordination of centrosomes.

    Directory of Open Access Journals (Sweden)

    Marko Panic

    2015-05-01

    Full Text Available The centrosome is the principal microtubule organizing center in most animal cells. It consists of a pair of centrioles surrounded by pericentriolar material. The centrosome, like DNA, duplicates exactly once per cell cycle. During interphase duplicated centrosomes remain closely linked by a proteinaceous linker. This centrosomal linker is composed of rootletin filaments that are anchored to the centrioles via the protein C-Nap1. At the onset of mitosis the linker is dissolved by Nek2A kinase to support the formation of the bipolar mitotic spindle. The importance of the centrosomal linker for cell function during interphase awaits characterization. Here we assessed the phenotype of human RPE1 C-Nap1 knockout (KO cells. The absence of the linker led to a modest increase in the average centrosome separation from 1 to 2.5 μm. This small impact on the degree of separation is indicative of a second level of spatial organization of centrosomes. Microtubule depolymerisation or stabilization in C-Nap1 KO cells dramatically increased the inter-centrosomal separation (> 8 μm. Thus, microtubules position centrosomes relatively close to one another in the absence of linker function. C-Nap1 KO cells had a Golgi organization defect with a two-fold expansion of the area occupied by the Golgi. When the centrosomes of C-Nap1 KO cells showed considerable separation, two spatially distinct Golgi stacks could be observed. Furthermore, migration of C-Nap1 KO cells was slower than their wild type RPE1 counterparts. These data show that the spatial organization of centrosomes is modulated by a combination of centrosomal cohesion and microtubule forces. Furthermore a modest increase in centrosome separation has major impact on Golgi organization and cell migration.

  6. A New Achiral Linker Reagent for the Incorporation of Multiple Amino Groups Into Oligonucleotides

    DEFF Research Database (Denmark)

    1997-01-01

    The present invention relates to a new functionalized achiral linker reagent for incorporating multiple primary amino groups or reporter groups into oligonucleotides following the phosphoramidite methodology. It is possible to substitute any ribodeoxynucleotide, deoxynucleotide, or nucleotide......-oxyl-2,2,5,5-tetramethylpyrrolidine), TEMPO (N-oxyl-2,2,6,6-tetramethylpiperidine), dinitrophenyl, texas red, tetramethyl rhodamine, 7-nitrobenzo-2-oxa-1-diazole (NBD), or pyrene. The present invention also relates to a solid phase support, e.g. a Controlled Pore Glass (CPG), immobilized linker reagent...

  7. Linker-dependent Junction Formation Probability in Single-Molecule Junctions

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Pil Sun; Kim, Taekyeong [HankukUniversity of Foreign Studies, Yongin (Korea, Republic of)

    2015-01-15

    We compare the junction formation probabilities of single-molecule junctions with different linker molecules by using a scanning tunneling microscope-based break-junction technique. We found that the junction formation probability varies as SH > SMe > NH2 for the benzene backbone molecule with different types of anchoring groups, through quantitative statistical analysis. These results are attributed to different bonding forces according to the linker groups formed with Au atoms in the electrodes, which is consistent with previous works. Our work allows a better understanding of the contact chemistry in the metal.molecule junction for future molecular electronic devices.

  8. Electrocatalytic oxidation of hydrazine at overoxidized polypyrrole film modified glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Majidi, Mir Reza [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of); Jouyban, Abolghasem [Faculty of Pharmacy and Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz 51664 (Iran, Islamic Republic of); Asadpour-Zeynali, Karim [Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 51664 (Iran, Islamic Republic of)]. E-mail: asadpour@tabrizu.ac.ir

    2007-06-20

    Electrocatalytic oxidation of hydrazine (HZ) was studied on an overoxidized polypyrrole (OPPy) modified glassy carbon electrode using cyclic voltammetry and chronoamperometry techniques. The OPPy-modified glassy carbon electrode has very high catalytic ability for electrooxidation of HZ, which appeared as a reduced overpotential in a wide operational pH range of 5-10. The overall numbers of electrons involved in the catalytic oxidation of HZ, the number of electrons involved in the rate-determining and diffusion coefficient of HZ were estimated using cyclic voltammetry and chronoamperometry. It has been shown that using the OPPy-modified electrode, HZ can be determined by cyclic voltammetry and amperometry with limit of detection 36 and 3.7 {mu}M, respectively. The results of the analysis suggest that the proposed method promises accurate results and could be employed for the routine determination of HZ.

  9. Loss mechanisms in hydrazine-processed Cu2ZnSn(Se,S)4 solar cells

    Science.gov (United States)

    Gunawan, Oki; Todorov, Teodor K.; Mitzi, David B.

    2010-12-01

    We present a device characterization study for hydrazine-processed kesterite Cu2ZnSn(Se,S)4 (CZTSSe) solar cells with a focus on pinpointing the main loss mechanisms limiting device efficiency. Temperature-dependent study and time-resolved photoluminescence spectroscopy on these cells, in comparison to analogous studies on a reference Cu(In,Ga)(Se,S)2 (CIGS) cell, reveal strong recombination loss at the CZTSSe/CdS interface, very low minority-carrier lifetimes, and high series resistance that diverges at low temperature. These findings help identify the key areas for improvement of these CZTSSe cells in the quest for a high-performance indium- and tellurium-free solar cell.

  10. A novel approach for high precision rapid potentiometric titrations: application to hydrazine assay.

    Science.gov (United States)

    Sahoo, P; Malathi, N; Ananthanarayanan, R; Praveen, K; Murali, N

    2011-11-01

    We propose a high precision rapid personal computer (PC) based potentiometric titration technique using a specially designed mini-cell to carry out redox titrations for assay of chemicals in quality control laboratories attached to industrial, R&D, and nuclear establishments. Using this technique a few microlitre of sample (50-100 μl) in a total volume of ~2 ml solution can be titrated and the waste generated after titration is extremely low comparing to that obtained from the conventional titration technique. The entire titration including online data acquisition followed by immediate offline analysis of data to get information about concentration of unknown sample is completed within a couple of minutes (about 2 min). This facility has been created using a new class of sensors, viz., pulsating sensors developed in-house. The basic concept in designing such instrument and the salient features of the titration device are presented in this paper. The performance of the titration facility was examined by conducting some of the high resolution redox titrations using dilute solutions--hydrazine against KIO(3) in HCl medium, Fe(II) against Ce(IV) and uranium using Davies-Gray method. The precision of titrations using this innovative approach lies between 0.048% and 1.0% relative standard deviation in different redox titrations. With the evolution of this rapid PC based titrator it was possible to develop a simple but high precision potentiometric titration technique for quick determination of hydrazine in nuclear fuel dissolver solution in the context of reprocessing of spent nuclear fuel in fast breeder reactors. © 2011 American Institute of Physics

  11. A photolabile linker for the solid-phase synthesis of 4-substituted NH-1,2,3-triazoles

    DEFF Research Database (Denmark)

    Qvortrup, Katrine; Nielsen, Thomas Eiland

    2011-01-01

    A novel photolabile linker for solid-phase synthesis is presented. The linker displays an azido handle for copper-catalyzed azide–alkyne cycloaddition reactions with a variety of alkynes, remains intact under typical solid-phase reaction conditions, and enables a mild photolytic release of 4...

  12. Regulation of Cellular Dynamics and Chromosomal Binding Site Preference of Linker Histones H1.0 and H1.X.

    Science.gov (United States)

    Okuwaki, Mitsuru; Abe, Mayumi; Hisaoka, Miharu; Nagata, Kyosuke

    2016-11-01

    Linker histones play important roles in the genomic organization of mammalian cells. Of the linker histone variants, H1.X shows the most dynamic behavior in the nucleus. Recent research has suggested that the linker histone variants H1.X and H1.0 have different chromosomal binding site preferences. However, it remains unclear how the dynamics and binding site preferences of linker histones are determined. Here, we biochemically demonstrated that the DNA/nucleosome and histone chaperone binding activities of H1.X are significantly lower than those of other linker histones. This explains why H1.X moves more rapidly than other linker histones in vivo Domain swapping between H1.0 and H1.X suggests that the globular domain (GD) and C-terminal domain (CTD) of H1.X independently contribute to the dynamic behavior of H1.X. Our results also suggest that the N-terminal domain (NTD), GD, and CTD cooperatively determine the preferential binding sites, and the contribution of each domain for this determination is different depending on the target genes. We also found that linker histones accumulate in the nucleoli when the nucleosome binding activities of the GDs are weak. Our results contribute to understanding the molecular mechanisms of dynamic behaviors, binding site selection, and localization of linker histones. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  13. Onset of grain filling is associated with a change in properties of linker histone variants in maize kernels

    DEFF Research Database (Denmark)

    Kalamajka, R.; Finnie, Christine; Grasser, K.D.

    2010-01-01

    ) initiation of storage synthesis. Six linker histone gene products were identified by MALDI-TOF mass spectrometry. A marked shift of around 4 pH units was observed for the linker histone spot pattern after 2D-gel electrophoresis when comparing the proteins of 11 and 16 dap kernels. The shift from acidic...

  14. A Class of Rigid Linker-bearing Glucosides for Membrane Protein Structural Study

    DEFF Research Database (Denmark)

    Sadaf, Aiman; Mortensen, Jonas S; Capaldi, Stefano

    2016-01-01

    with a branched tail group and a triglucoside head group. These head and tail groups were connected via an amide or ether linkage by using a tris(hydroxylmethyl)aminomethane (TRIS) or neopentyl glycol (NPG) linker to produce TRIS-derived triglucosides (TDTs) and NPG-derived triglucosides (NDTs), respectively...

  15. Solid-phase synthesis of polyfunctional polylysine dendrons using aldehyde linkers

    DEFF Research Database (Denmark)

    Svenssen, Daniel K.; Mirsharghi, Sahar; Boas, Ulrik

    2014-01-01

    A straightforward method for the solid-phase synthesis of C-terminally modified polylysine dendrons has been developed by applying bisalkoxybenzaldehyde and trisalkoxybenzaldehyde linkers. The method has been used for the synthesis of polylysine dendrons with a variety of C-terminal ‘tail groups’...

  16. Identification of a minimal functional linker in human topoisomerase I by domain swapping with Cre recombinase

    DEFF Research Database (Denmark)

    Hougaard, Rikke Frøhlich; Juul, Sissel; Vinther, Maria

    2008-01-01

    . In this study we replace 86 amino acids including the linker domain of the cellular type IB topoisomerase, human topoisomerase I, with four, six, or eight amino acids from the corresponding short loop region in Cre recombinase. In vitro characterization of the resulting chimeras, denoted Cropos, reveals...

  17. SEVA Linkers: A Versatile and Automatable DNA Backbone Exchange Standard for Synthetic Biology

    DEFF Research Database (Denmark)

    Kim, Se Hyeuk; Cavaleiro, Mafalda; Rennig, Maja

    2016-01-01

    flexibility, and different researchers prefer and master different molecular technologies. Here, we describe a new, highly versatile and automatable standard “SEVA linkers” for vector exchange. SEVA linkers enable backbone swapping with 20 combinations of classical enzymatic restriction/ligation, Gibson...

  18. Rapid construction of mechanically- confined multi- cellular structures using dendrimeric intercellular linker.

    Science.gov (United States)

    Mo, Xuejun; Li, Qiushi; Yi Lui, Lena Wai; Zheng, Baixue; Kang, Chiang Huen; Nugraha, Bramasta; Yue, Zhilian; Jia, Rui Rui; Fu, Hong Xia; Choudhury, Deepak; Arooz, Talha; Yan, Jie; Lim, Chwee Teck; Shen, Shali; Hong Tan, Choon; Yu, Hanry

    2010-10-01

    Tissue constructs that mimic the in vivo cell-cell and cell-matrix interactions are especially useful for applications involving the cell- dense and matrix- poor internal organs. Rapid and precise arrangement of cells into functional tissue constructs remains a challenge in tissue engineering. We demonstrate rapid assembly of C3A cells into multi- cell structures using a dendrimeric intercellular linker. The linker is composed of oleyl- polyethylene glycol (PEG) derivatives conjugated to a 16 arms- polypropylenimine hexadecaamine (DAB) dendrimer. The positively charged multivalent dendrimer concentrates the linker onto the negatively charged cell surface to facilitate efficient insertion of the hydrophobic oleyl groups into the cellular membrane. Bringing linker- treated cells into close proximity to each other via mechanical means such as centrifugation and micromanipulation enables their rapid assembly into multi- cellular structures within minutes. The cells exhibit high levels of viability, proliferation, three- dimensional (3D) cell morphology and other functions in the constructs. We constructed defined multi- cellular structures such as rings, sheets or branching rods that can serve as potential tissue building blocks to be further assembled into complex 3D tissue constructs for biomedical applications. 2010 Elsevier Ltd. All rights reserved.

  19. Low Density Lipoprotein Receptor Class A Repeats Are O-Glycosylated in Linker Regions

    DEFF Research Database (Denmark)

    Pedersen, Nis Borbye; Wang, Shengjun; Narimatsu, Yoshiki

    2014-01-01

    , which in wild-type CHO cells is glycosylated with the typical sialylated core 1 structure. The glycosites in linker regions of LDLR class A repeats are conserved in LDLR from man to Xenopus and found in other homologous receptors. O-Glycosylation is controlled by a large family of polypeptide Gal...

  20. Nanostructured SnO{sub 2} encapsulated guar-gum hybrid nanocomposites for electrocatalytic determination of hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Malik, Priya [Department of Applied Chemistry & Polymer Technology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110042 (India); Srivastava, Manish [Department of Physics & Astrophysics, University of Delhi, Delhi 110007 (India); Verma, Ranjana [Solar Energy Material Laboratory, Department of Energy, Tezpur University, Tezpur, Assam 784 028 (India); Kumar, Manish [Department of Applied Chemistry & Polymer Technology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110042 (India); Kumar, D., E-mail: dkumar@dce.ac.in [Department of Applied Chemistry & Polymer Technology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110042 (India); Singh, Jay, E-mail: jay_singh143@yahoo.co.in [Department of Applied Chemistry & Polymer Technology, Delhi Technological University, Shahbad Daulatpur, Main Bawana Road, Delhi 110042 (India)

    2016-01-01

    The present article deals with synthesis of sol–gel derived tin dioxide (SnO{sub 2}) nanoparticles encapsulated in to guar gum (GG) biopolymer as the organic–inorganic hybrid materials for the determination of hydrazine. The organic–inorganic hybrid combines the perfunctory strength offered by the inorganic SnO{sub 2} nanoparticles with flexible binding sites provided by the organic biopolymer (GG) solution by the ultrasonication. The phase identification, crystalline size, surface morphology and optical properties of prepared SnO{sub 2} and SnO{sub 2}-GG nanocomposites has been investigated through FT-IR, XRD, SEM, AFM, TEM, UV–Vis, and PL techniques. The colloidal solution of SnO{sub 2} and GG is electrophoretically deposited (EPD) onto the indium tin-oxide (ITO) glass substrate and studied for the electrooxidation of hydrazine. Under the optimized experimental conditions, the linearity between the current response and the hydrazine concentration has been obtained in the range of 2–22 mM, with a low detection limit of 2.76 mM and a high sensitivity of 5.72 μA cm{sup −2}. Based on the linear increase in amperometric current, a sensitive hydrazine electrochemical sensor is constructed. The proposed SnO{sub 2}-GG/ITO electrode shows a good response time (35 s), reproducibility, and long-term stability. The obtained results suggest that SnO{sub 2}-GG nanocomposites electrode provides a favorable sensing platform for the electrochemical studies. In addition, the cyclic voltammetry (CV) studies are used to evaluate the kinetic parameters. - Graphical abstract: Synthesis of sol–gel derived tin dioxide (SnO{sub 2}) nanoparticles grafted in to gaur gum (GG) organic–inorganic hybrid nanocomposite for determination of hydrazine (HZ). Under optimized experimental conditions, SnO{sub 2}-GG/ITO electrode shows, linearity 2–22 mM, and detection limit 2.769 mM with high sensitivity of 5.72 μA cm{sup −2}. The results clearly suggest that SnO{sub 2}-GG

  1. Release of 3-methyladenine from linker and core DNA of chromatin by a purified DNA glycosylase

    International Nuclear Information System (INIS)

    Heller, E.P.; Goldthwait, D.A.

    1983-01-01

    Oligonucleosomes were isolated from [ 14 C]thymidine-labeled HeLa cells by digestion of the nuclei with micrococcal nuclease and were then alkylated with [ 3 H]methylnitrosourea. Nucleosome core particles were also prepared by further digestion of the oligonucleosomes. The distribution of 3 H-labeled methyl groups in the linker versus the core DNA was established by a determination of 3 H: 14 C ratios in oligonucleosome and core DNA. The ratios in the core DNA of 145 and 165 base pair DNA fragments were 5.2 and 5.4, respectively, while the ratio in the oligonucleosomal DNA was 8.2. Assuming an equal mixture (as determined) of 145 and 165 base pair fragments of DNA in the 185 base pair repeat, the relative concentration of 3 H methyl groups in the linker versus the core DNA was 4.2. Thus, 45% of the 3 H methyl groups were in the linker DNA, and 55% were in the core DNA. Some shielding of the DNA was evident during alkylation. The concentrations of alkyl groups on the linker and core DNA were 67 and 12% of that found on free DNA alkylated under comparable conditions. No evidence for preferential shielding of the major or minor groove was observed. The purified 3-methyladenine DNA glycosylase I of Escherichia coli released approximately 37% of the 3-methyladenine from the linker DNA and 13% from the core DNA. The limited enzymatic removal of 3-methyladenine in vitro compared to the efficient removal in vivo suggests that conformational changes of the oligonucleosome and core structure must occur for total repair

  2. SH2-catalytic domain linker heterogeneity influences allosteric coupling across the SFK family.

    Science.gov (United States)

    Register, A C; Leonard, Stephen E; Maly, Dustin J

    2014-11-11

    Src-family kinases (SFKs) make up a family of nine homologous multidomain tyrosine kinases whose misregulation is responsible for human disease (cancer, diabetes, inflammation, etc.). Despite overall sequence homology and identical domain architecture, differences in SH3 and SH2 regulatory domain accessibility and ability to allosterically autoinhibit the ATP-binding site have been observed for the prototypical SFKs Src and Hck. Biochemical and structural studies indicate that the SH2-catalytic domain (SH2-CD) linker, the intramolecular binding epitope for SFK SH3 domains, is responsible for allosterically coupling SH3 domain engagement to autoinhibition of the ATP-binding site through the conformation of the αC helix. As a relatively unconserved region between SFK family members, SH2-CD linker sequence variability across the SFK family is likely a source of nonredundant cellular functions between individual SFKs via its effect on the availability of SH3 and SH2 domains for intermolecular interactions and post-translational modification. Using a combination of SFKs engineered with enhanced or weakened regulatory domain intramolecular interactions and conformation-selective inhibitors that report αC helix conformation, this study explores how SH2-CD sequence heterogeneity affects allosteric coupling across the SFK family by examining Lyn, Fyn1, and Fyn2. Analyses of Fyn1 and Fyn2, isoforms that are identical but for a 50-residue sequence spanning the SH2-CD linker, demonstrate that SH2-CD linker sequence differences can have profound effects on allosteric coupling between otherwise identical kinases. Most notably, a dampened allosteric connection between the SH3 domain and αC helix leads to greater autoinhibitory phosphorylation by Csk, illustrating the complex effects of SH2-CD linker sequence on cellular function.

  3. The influence of ultrasound on the reduction of plutonium (4) by hydrazine and hydroxylamine in nitric acid and hydrochloric acid media

    International Nuclear Information System (INIS)

    Nikonov, M.V.; Shilov, V.P.

    1989-01-01

    Spectrophotometric method was used to study reduction of Pu(4) by hydrazine and hydroxylamine in HNO 3 and HCl solutions under the effect of ultrasonic waves at 18-20 deg C. It is shown that reaction of Pu(4) with hydrazine is accelerated in ultrasonic field approximately 10 times; ultrasound doesn't produce noticeable effect on behaviour of the actinoid in the case of hydroxylamine

  4. Molecular dissection of the interaction between the SH3 domain and the SH2-Kinase Linker region in PTK6.

    Science.gov (United States)

    Kim, Han Ie; Jung, Jinwon; Lee, Eun-Saem; Kim, Yong-Chul; Lee, Weontae; Lee, Seung-Taek

    2007-11-03

    PTK6 (also known as Brk) is an intracellular tyrosine kinase that contains SH3, SH2, and tyrosine kinase catalytic (Kinase) domains. The SH3 domain of PTK6 interacts with the N-terminal half of the linker (Linker) region between the SH2 and Kinase domains. Site-directed mutagenesis and surface plasmon resonance studies showed that a tryptophan residue (Trp44) in the SH3 domain and proline residues in the Linker region, in the order of Pro177, Pro175, and Pro179, contribute to the interaction. The three-dimensional modeled structure of the SH3-Linker complex was in agreement with the biochemical data. Disruption of the intramolecular interaction between the SH3 domain and the Linker region by mutation of Trp44, Pro175, Pro177, and Pro179 markedly increased the catalytic activity of PTK6 in HEK 293 cells. These results demonstrate that Trp44 in the SH3 domain and Pro177, Pro175, and Pro179 in the N-terminal half of the Linker region play important roles in the SH3-Linker interaction to maintain the protein in an inactive conformation along with the phosphorylated Tyr447-SH2 interaction.

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  6. Development of Bioorthogonally Degradable Linkers and Polymers Using alpha-Azidoethers

    Science.gov (United States)

    Rajagopalan, Chandrasekhar Ramasubramanian

    Degradable polymers have gained a lot of attention in recent years for applications in biotechnology and medicine. External control over polymer degradation can be obtained by incorporating functional groups that cleave in the presence of triggers that would normally be absent in biological environments, i.e. are bioorthogonal. This thesis explores the use of chemically cleavable alpha-azidoethers as a new method to obtain external control over the degradation behavior of polymers. My first goal is to illustrate the potential of alpha-azidoethers toward developing cleavable linkers. We have studied the relationship between alpha-azidoether structure and hydrolytic stability, to prepare linkers that withstand background hydrolytic cleavage until they are exposed to the cleaving trigger. The cleavage kinetics of the alpha-azidoether functional group was quantified. In addition to the conventionally used tris(2-carboxyethyl)phosphine (TCEP), dihydrolipoic acid (DHLA), a previously unexplored, biocompatible reducing agent, was also evaluated as a cleaving trigger. Based on these results, we have proposed design rules for utilizing alpha-azidoethers as cleavable linkers in applications that require bioorthogonal control over linker cleavage. Secondly, the alpha-azidoether cleavable linker chemistry was implemented into the development of polymeric materials. Two different types of polymers were developed. Polyamides incorporating alpha-azidoethers along the backbone were synthesized, and their physical properties and chemically triggered degradation behavior were characterized. The degradation timescale of these polymers can be tuned simply by manipulating the concentration of the externally applied chemical trigger. The alpha-azidoether functional group was then utilized to develop a unique triggered-release polymeric adhesive for potential applications in dental adhesive formulations. A methacrylamide-phosphonate adhesive monomer incorporating an alpha

  7. Electrochemical studies on the reduction of uranyl ions in nitric acid-hydrazine media at platinum electrode

    International Nuclear Information System (INIS)

    Mishra, Satyabrata; Sini, K.; Mallika, C.; Kamachi Mudali, U.; Jagadeeswara Rao, Ch.

    2015-01-01

    Production of uranous nitrate with good conversion efficiency is one of the major steps in the aqueous reprocessing of spent fuels of nuclear reactors, as U(IV) is used for the separation of Pu from U by the selective reduction of Pu(IV) into practically non-extractable Pu(III) in aqueous streams. Electro-reduction of uranyl ions has the advantage of not introducing corrosive chemicals into the process stream. High current efficiency with maximum conversion of U(VI) to U(IV) can be achieved in continuous as well as batch mode electro-reduction, if the process is voltage-controlled rather than current controlled. As potentiostatic studies reveal the mechanism of reduction of uranyl ions in potential controlled electrolysis, the reduction behavior of uranyl ions (UO 2 2+ ) in nitric acid and nitric acid-hydrazine media were investigated by Cyclic Voltammetric (CV) and Chronopotentiometric (CP) techniques using platinum working electrode at 298 K. Heterogeneous electron transfer rate constant (ks) for uranyl reduction was estimated at a very low concentration of nitric acid (0.05 M) using Klinger and Kochi equation. Values of the diffusion coefficients were determined as a function of acidity with and without hydrazine. Reduction of uranyl ions was found to be under kinetic as well as diffusion control when the concentration of nitric acid was 0.05 M and in the absence of hydrazine. However, as the acidity of the supporting electrolyte increased, the reduction was purely under kinetic control. (author)

  8. Increased hydrazine during partial nitritation process in upflow air-lift reactor fed with supernatant of anaerobic digester effluent

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jeongdong [University of Alberta, Alberta (Canada); Jung, Sokhee [Samsung SDS, Seoul (Korea, Republic of); Ahn, Young-Ho [Yeungnam University, Gyungsan (Korea, Republic of)

    2013-06-15

    The optimal balance of ammonium and nitrite is essential for successful operation of the subsequent anammox process. We conducted a partial nitritation experiment using an upflow air-lift reactor to provide operational parameters for achieving the optimal ratio of ammonium to nitrite, by feeding supernatant of anaerobic digester effluent, high-nitrogen containing rejection water. Semi-continuous operation results show that HRT should be set between 15 and 17 hours to achieve the optimum ration of 1.3 of NO{sub 2}-N/NH{sub 4}-N. In the UAR, nitritation was the dominant reaction due to high concentration of ammonia and low biodegradable organics. The influent contained low concentrations of hydroxylamine and hydrazine. However, hydrazine increased during partial nitritation by ⁓60-130% although there was no potential anammox activity in the reactor. The partial nitritation process successfully provided the ratio of nitrogen species for the anammox reaction, and relived the nitrite restraint on the anammox activity by increasing hydrazine concentration.

  9. Derivatization Ion Chromatography for the Determination of Monoethanolamine in Presence of Hydrazine in PHWR Steam-Water Circuits

    Directory of Open Access Journals (Sweden)

    Ayushi D.

    2011-01-01

    Full Text Available A simple, rapid and accurate method for the determination of monoethanolamine (MEA in PHWR steam-water circuits has been developed. MEA is added in the feed water to provide protection against corrosion while hydrazine is added to scavenge dissolved oxygen. The quantitative determination of MEA in presence of hydrazine was accomplished using derivatization ion chromatography with conductometric detection in nonsuppressed mode. A Metrosep cation 1-2 analytical column and a Metrosep cartridge were used for cation separation. A mixture of 4 mM tartaric acid, 20% acetone and 0.05 mM HNO3 was used as eluent. Acetone in the mobile phase leads to the formation of different derivatives with MEA and hydrazine. The interferences due Na+ and NH4 + were eliminated by adopting a simple pretreatment procedure employing OnGuard-H cartridge. The limit of detection limit of MEA was 0.1 μg mL−1 and the relative standard deviation was 2% for the overall method. The recovery of MEA added was in the range 95%–102%. The method was applied to the determination of MEA in steam generator water samples.

  10. cis-Apa: a practical linker for the microwave-assisted preparation of cyclic pseudopeptides via RCM cyclative cleavage.

    Science.gov (United States)

    Baron, Alice; Verdié, Pascal; Martinez, Jean; Lamaty, Frédéric

    2011-02-04

    A new linker cis-5-aminopent-3-enoic acid (cis-Apa) was prepared for the synthesis of cyclic pseudopeptides by cyclization-cleavage by using ring-closing methatesis (RCM). We developed a new synthetic pathway for the preparation of the cis-Apa linker that was tested in the cyclization-cleavage process of different RGD peptide sequences. Different macrocyclic peptidomimetics were prepared by using this integrated microwave-assisted method, showing that the readily available cis-Apa amino acid is well adapted as a linker in the cyclization-cleavage process.

  11. The H1 linker histones: multifunctional proteins beyond the nucleosomal core particle.

    Science.gov (United States)

    Hergeth, Sonja P; Schneider, Robert

    2015-11-01

    The linker histone H1 family members are a key component of chromatin and bind to the nucleosomal core particle around the DNA entry and exit sites. H1 can stabilize both nucleosome structure and higher-order chromatin architecture. In general, H1 molecules consist of a central globular domain with more flexible tail regions at both their N- and C-terminal ends. The existence of multiple H1 subtypes and a large variety of posttranslational modifications brings about a considerable degree of complexity and makes studying this protein family challenging. Here, we review recent progress in understanding the function of linker histones and their subtypes beyond their role as merely structural chromatin components. We summarize current findings on the role of H1 in heterochromatin formation, transcriptional regulation and embryogenesis with a focus on H1 subtypes and their specific modifications. © 2015 The Authors.

  12. Destabilization of the Outer and Inner Mitochondrial Membranes by Core and Linker Histones

    Science.gov (United States)

    Cascone, Annunziata; Bruelle, Celine; Lindholm, Dan; Bernardi, Paolo; Eriksson, Ove

    2012-01-01

    Background Extensive DNA damage leads to apoptosis. Histones play a central role in DNA damage sensing and may mediate signals of genotoxic damage to cytosolic effectors including mitochondria. Methodology/Principal Findings We have investigated the effects of histones on mitochondrial function and membrane integrity. We demonstrate that both linker histone H1 and core histones H2A, H2B, H3, and H4 bind strongly to isolated mitochondria. All histones caused a rapid and massive release of the pro-apoptotic intermembrane space proteins cytochrome c and Smac/Diablo, indicating that they permeabilize the outer mitochondrial membrane. In addition, linker histone H1, but not core histones, permeabilized the inner membrane with a collapse of the membrane potential, release of pyridine nucleotides, and mitochondrial fragmentation. Conclusions We conclude that histones destabilize the mitochondrial membranes, a mechanism that may convey genotoxic signals to mitochondria and promote apoptosis following DNA damage. PMID:22523586

  13. Linker histones: novel insights into structure-specific recognition of the nucleosome.

    Science.gov (United States)

    Cutter, Amber R; Hayes, Jeffrey J

    2017-04-01

    Linker histones (H1s) are a primary component of metazoan chromatin, fulfilling numerous functions, both in vitro and in vivo, including stabilizing the wrapping of DNA around the nucleosome, promoting folding and assembly of higher order chromatin structures, influencing nucleosome spacing on DNA, and regulating specific gene expression. However, many molecular details of how H1 binds to nucleosomes and recognizes unique structural features on the nucleosome surface remain undefined. Numerous, confounding studies are complicated not only by experimental limitations, but the use of different linker histone isoforms and nucleosome constructions. This review summarizes the decades of research that has resulted in several models of H1 association with nucleosomes, with a focus on recent advances that suggest multiple modes of H1 interaction in chromatin, while highlighting the remaining questions.

  14. Construction of Multivalent Homo- and Heterofunctional ABO Blood Group Glycoconjugates Using a Trifunctional Linker Strategy.

    Science.gov (United States)

    Daskhan, Gour Chand; Tran, Hanh-Thuc Ton; Meloncelli, Peter J; Lowary, Todd L; West, Lori J; Cairo, Christopher W

    2018-02-21

    The design and synthesis of multivalent ligands displaying complex oligosaccharides is necessary for the development of therapeutics, diagnostics, and research tools. Here, we report an efficient conjugation strategy to prepare complex glycoconjugates with 4 copies of 1 or 2 separate glycan epitopes, providing 4-8 carbohydrate residues on a tetravalent poly(ethylene glycol) scaffold. This strategy provides complex glycoconjugates that approach the size of glycoproteins (15-18 kDa) while remaining well-defined. The synthetic strategy makes use of three orthogonal functional groups, including a reactive N-hydroxysuccinimide (NHS)-ester moiety on the linker to install the first carbohydrate epitope via reaction with an amine. A masked amine functionality on the linker is revealed after the removal of a fluorenylmethyloxycarbonyl (Fmoc)-protecting group, allowing the attachment to the NHS-activated poly(ethylene glycol) (PEG) scaffold. An azide group in the linker was then used to incorporate the second carbohydrate epitope via catalyzed alkyne-azide cycloaddition. Using a known tetravalent PEG scaffold (PDI, 1.025), we prepared homofunctional glycoconjugates that display four copies of lactose and the A-type II or the B-type II human blood group antigens. Using our trifunctional linker, we expanded this strategy to produce heterofunctional conjugates with four copies of two separate glycan epitopes. These heterofunctional conjugates included Neu5Ac, 3'-sialyllactose, or 6'-sialyllactose as a second antigen. Using an alternative strategy, we generated heterofunctional conjugates with three copies of the glycan epitope and one fluorescent group (on average) using a sequential dual-amine coupling strategy. These conjugation strategies should be easily generalized for conjugation of other complex glycans. We demonstrate that the glycan epitopes of heterofunctional conjugates engage and cluster target B-cell receptors and CD22 receptors on B cells, supporting the

  15. Elastin-like Polypeptide Linkers for Single-Molecule Force Spectroscopy.

    Science.gov (United States)

    Ott, Wolfgang; Jobst, Markus A; Bauer, Magnus S; Durner, Ellis; Milles, Lukas F; Nash, Michael A; Gaub, Hermann E

    2017-06-27

    Single-molecule force spectroscopy (SMFS) is by now well established as a standard technique in biophysics and mechanobiology. In recent years, the technique has benefitted greatly from new approaches to bioconjugation of proteins to surfaces. Indeed, optimized immobilization strategies for biomolecules and refined purification schemes are being steadily adapted and improved, which in turn has enhanced data quality. In many previously reported SMFS studies, poly(ethylene glycol) (PEG) was used to anchor molecules of interest to surfaces and/or cantilever tips. The limitation, however, is that PEG exhibits a well-known trans-trans-gauche to all-trans transition, which results in marked deviation from standard polymer elasticity models such as the worm-like chain, particularly at elevated forces. As a result, the assignment of unfolding events to protein domains based on their corresponding amino acid chain lengths is significantly obscured. Here, we provide a solution to this problem by implementing unstructured elastin-like polypeptides as linkers to replace PEG. We investigate the suitability of tailored elastin-like polypeptides linkers and perform direct comparisons to PEG, focusing on attributes that are critical for single-molecule force experiments such as linker length, monodispersity, and bioorthogonal conjugation tags. Our results demonstrate that by avoiding the ambiguous elastic response of mixed PEG/peptide systems and instead building the molecular mechanical systems with only a single bond type with uniform elastic properties, we improve data quality and facilitate data analysis and interpretation in force spectroscopy experiments. The use of all-peptide linkers allows alternative approaches for precisely defining elastic properties of proteins linked to surfaces.

  16. Computational engineering of cellulase Cel9A-68 functional motions through mutations in its linker region.

    Science.gov (United States)

    Costa, M G S; Silva, Y F; Batista, P R

    2018-03-14

    Microbial cellulosic degradation by cellulases has become a complementary approach for biofuel production. However, its efficiency is hindered by the recalcitrance of cellulose fibres. In this context, computational protein design methods may offer an efficient way to obtain variants with improved enzymatic activity. Cel9A-68 is a cellulase from Thermobifida fusca that is still active at high temperatures. In a previous work, we described a collective bending motion, which governs the overall cellulase dynamics. This movement promotes the approximation of its CBM and CD structural domains (that are connected by a flexible linker). We have identified two residues (G460 and P461) located at the linker that act as a hinge point. Herein, we applied a new level of protein design, focusing on the modulation of this collective motion to obtain cellulase variants with enhanced functional dynamics. We probed whether specific linker mutations would affect Cel9A-68 dynamics through computational simulations. We assumed that P461G and G460+ (with an extra glycine) constructs would present enhanced interdomain motions, while the G460P mutant would be rigid. From our results, the P461G mutation resulted in a broader exploration of the conformational space, as confirmed by clustering and free energy analyses. The WT enzyme was the most rigid system. However, G460P and P460+ explored distinct conformational states described by opposite directions of low-frequency normal modes; they sampled preferentially closed and open conformations, respectively. Overall, we highlight two significant findings: (i) all mutants explored larger conformational spaces than the WT; (ii) the selection of distinct conformational populations was intimately associated with the mutation considered. Thus, the engineering of Cel9A-68 motions through linker mutations may constitute an efficient way to improve cellulase activity, facilitating the disruption of cellulose fibres.

  17. Hydrazine-based deposition route for device-quality CIGS films

    International Nuclear Information System (INIS)

    Mitzi, David B.; Yuan, Min; Liu, Wei; Kellock, Andrew J.; Chey, S. Jay; Gignac, Lynne; Schrott, Alex G.

    2009-01-01

    A simple solution-based approach for depositing CIGS (Cu-In-Ga-Se/S) absorber layers is discussed, with an emphasis on film characterization, interfacial properties and integration into photovoltaic devices. The process involves incorporating all metal and chalcogenide components into a single hydrazine-based solution, spin coating a precursor film, and heat treating in an inert atmosphere, to form the desired CIGS film with up to micron-scaled film thickness and grain size. PV devices (glass/Mo/CIGS/CdS/i-ZnO/ITO) employing the spin-coated CIGS and using processing temperatures below 500 deg. C have yielded power conversion efficiencies of up to 10% (AM 1.5 illumination), without the need for a post-CIGS-deposition treatment in a gaseous Se source or a cyanide-based bath etch. Short-duration low-temperature (T < 200 deg. C ) oxygen treatment of completed devices is shown to have a positive impact on the performance of initially underperforming cells, thereby enabling better performance in devices prepared at temperatures below 500 deg. C

  18. Hydrazine-based deposition route for device-quality CIGS films

    Energy Technology Data Exchange (ETDEWEB)

    Mitzi, David B. [IBM T. J. Watson Research Center, P. O. Box 218, Yorktown Heights, NY 10598 (United States)], E-mail: dmitzi@us.ibm.com; Yuan, Min; Liu, Wei [IBM T. J. Watson Research Center, P. O. Box 218, Yorktown Heights, NY 10598 (United States); Kellock, Andrew J [IBM Almaden Research Center, 650 Harry Rd, San Jose, CA 95120 (United States); Chey, S Jay; Gignac, Lynne; Schrott, Alex G [IBM T. J. Watson Research Center, P. O. Box 218, Yorktown Heights, NY 10598 (United States)

    2009-02-02

    A simple solution-based approach for depositing CIGS (Cu-In-Ga-Se/S) absorber layers is discussed, with an emphasis on film characterization, interfacial properties and integration into photovoltaic devices. The process involves incorporating all metal and chalcogenide components into a single hydrazine-based solution, spin coating a precursor film, and heat treating in an inert atmosphere, to form the desired CIGS film with up to micron-scaled film thickness and grain size. PV devices (glass/Mo/CIGS/CdS/i-ZnO/ITO) employing the spin-coated CIGS and using processing temperatures below 500 deg. C have yielded power conversion efficiencies of up to 10% (AM 1.5 illumination), without the need for a post-CIGS-deposition treatment in a gaseous Se source or a cyanide-based bath etch. Short-duration low-temperature (T < 200 deg. C ) oxygen treatment of completed devices is shown to have a positive impact on the performance of initially underperforming cells, thereby enabling better performance in devices prepared at temperatures below 500 deg. C.

  19. Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst

    Directory of Open Access Journals (Sweden)

    Hongbin Dai

    2017-02-01

    Full Text Available The synthesis of highly active and selective catalysts is the central issue in the development of hydrous hydrazine (N2H4·H2O as a viable hydrogen carrier. Herein, we report the synthesis of bimetallic Ni-Ir nanocatalyts supported on CeO2 using a one-pot coprecipitation method. A combination of XRD, HRTEM and XPS analyses indicate that the Ni-Ir/CeO2 catalyst is composed of tiny Ni-Ir alloy nanoparticles with an average size of around 4 nm and crystalline CeO2 matrix. The Ni-Ir/CeO2 catalyst exhibits high catalytic activity and excellent selectivity towards hydrogen generation from N2H4·H2O at mild temperatures. Furthermore, in contrast to previously reported Ni-Pt catalysts, the Ni-Ir/CeO2 catalyst shows an alleviated requirement on alkali promoter to achieve its optimal catalytic performance.

  20. Synthesis of nickel nanoparticles by hydrazine reduction: mechanistic study and continuous flow synthesis

    International Nuclear Information System (INIS)

    Eluri, Ravi; Paul, Brian

    2012-01-01

    The continuous synthesis of nickel nanoparticles (NiNPs) in a static microchannel T-mixer by the reduction of NiCl 2 ·6H 2 O in the presence of ethylene glycol without a stabilizing/capping agent was investigated. The nanoparticles were formed in accordance with the modified polyol process with hydrazine used as a reducing agent and NaOH as a catalyst for nanoparticle formation. The reaction mechanism for NiNP formation was investigated in batch with the help of Fourier transform infrared spectroscopy and X-ray diffraction (XRD) techniques. Parameters were found for reducing reaction times from 60 to 1 min. The effects of temperature (60–120 °C) and NaOH concentration (0.1 and 0.5 M) on batch-processed particle characteristics were also studied using XRD, transmission electron microscope and electron microprobe analysis. Average particle size was reduced from 9.2 ± 2.9 to 5.4 ± 0.9 nm at higher temperature and NaOH concentration. Adaptation of this chemistry to a static microchannel T-mixer for continuous synthesis resulted in smooth, spherical particles. Increases in the reaction temperature from 120 to 130 °C resulted in a narrow size distribution of 5.3 ± 1 nm and also resulted in magnetic properties of 5.1 emu/g (saturation magnetization), 1.1 emu/g (remanent magnetization), and 62 Oe (coercivity).

  1. 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.

  2. Efficient Naphthalenediimide-Based Hole Semiconducting Polymer with Vinylene Linkers between Donor and Acceptor Units

    KAUST Repository

    Zhang, Lei

    2016-11-04

    We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm(2) s(-1) with hole to electron mobility ratio of three (mu(h)/mu(e), similar to 3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.

  3. Efficient Naphthalenediimide-Based Hole Semiconducting Polymer with Vinylene Linkers between Donor and Acceptor Units

    KAUST Repository

    Zhang, Lei; Rose, Bradley Daniel; Liu, Yao; Nahid, Masrur M.; Gann, Eliot; Ly, Jack; Zhao, Wei; Rosa, Stephen J.; Russell, Thomas P.; Facchetti, Antonio; McNei, Christopher R.; Bredas, Jean-Luc; Briseno, Alejandro L.

    2016-01-01

    We demonstrate a new method to reverse the polarity and charge transport behavior of naphthalenediimide (NDI)-based copolymers by inserting a vinylene linker between the donor and acceptor units. The vinylene linkers minimize the intrinsic steric congestion between the NDI and thiophene moieties to prompt backbone planarity. The polymers with vinylene linkers exhibit electron n-channel transport characteristics under vacuum, similar to the benchmark polymer, P(NDI2OD-T2). To our surprise, when the polymers are measured in air, the dominant carrier type switches from n- to p-type and yield hole mobilities up to 0.45 cm(2) s(-1) with hole to electron mobility ratio of three (mu(h)/mu(e), similar to 3), which indicates that the hole density in the active layer can be significantly increased by exposure to air. This increase is consistent with the intrinsic more delocalized nature of the highest occupied molecular orbital of the charged vinylene polymer, as estimated by density functional theory (DFT) calculations, which facilitates hole transport within the polymer chains. This is the first demonstration of an efficient NDI-based hole semiconducting polymer, which will enable new developments in all-polymer solar cells, complementary circuits, and dopable polymers for use in thermoelectrics.

  4. 5-fold increase of hydrogen uptake in MOF74 through linker decorations

    Science.gov (United States)

    Thonhauser, T.; Zuluaga, S.; Harrison, D.; Welchman, E.; Arter, C.

    We present ab initio results for linker decorations in Mg-MOF74-i.e. attaching various metals  = Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker-creating new strong adsorption sites and thus maximizing small molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening we chose metals that bind favorably to the linker and further investigate adsorption of H2, CO2, and H2O for  = Li, Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the MOF unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a 5-fold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular-where the gravimetric hydrogen density increases from 1 . 63 mass% to 7 . 28 mass% and the volumetric density from 15.10 g H2 L-1 to 75.50 g H2 L-1. This work was supported by NSF Grant No. DMR-1145968.

  5. Fivefold increase of hydrogen uptake in MOF74 through linker decorations

    Science.gov (United States)

    Arter, C. A.; Zuluaga, S.; Harrison, D.; Welchman, E.; Thonhauser, T.

    2016-10-01

    We present ab initio results for linker decorations in Mg-MOF74, i.e., attaching various metals M =Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker, creating new strong adsorption sites and thus maximizing small-molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening, we chose metals that bind favorably to the linker and further investigated adsorption of H2,CO2, and H2O for M =Li , Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the metal-organic framework (MOF) unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a fivefold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular, where the gravimetric hydrogen density increases from 1.63 to 7.28 mass % and the volumetric density increases from 15.10 to 75.50 g H2L-1 .

  6. Saccharomyces cerevisiae Linker Histone—Hho1p Maintains Chromatin Loop Organization during Ageing

    Directory of Open Access Journals (Sweden)

    Katya Uzunova

    2013-01-01

    Full Text Available Intricate, dynamic, and absolutely unavoidable ageing affects cells and organisms through their entire lifetime. Driven by diverse mechanisms all leading to compromised cellular functions and finally to death, this process is a challenge for researchers. The molecular mechanisms, the general rules that it follows, and the complex interplay at a molecular and cellular level are yet little understood. Here, we present our results showing a connection between the linker histones, the higher-order chromatin structures, and the process of chronological lifespan of yeast cells. By deleting the gene for the linker histone in Saccharomyces cerevisiae we have created a model for studying the role of chromatin structures mainly at its most elusive and so far barely understood higher-order levels of compaction in the processes of yeast chronological lifespan. The mutant cells demonstrated controversial features showing slower growth than the wild type combined with better survival during the whole process. The analysis of the global chromatin organization during different time points demonstrated certain loss of the upper levels of chromatin compaction in the cells without linker histone. The results underlay the importance of this histone for the maintenance of the chromatin loop structures during ageing.

  7. Prototype development and test results of a continuous ambient air monitoring system for hydrazine at the 10 ppb level

    Science.gov (United States)

    Meneghelli, Barry; Parrish, Clyde; Barile, Ron; Lueck, Dale E.

    1995-01-01

    A Hydrazine Vapor Area Monitor (HVAM) system is currently being field tested as a detector for the presence of hydrazine in ambient air. The MDA/Polymetron Hydrazine Analyzer has been incorporated within the HVAM system as the core detector. This analyzer is a three-electrode liquid analyzer typically used in boiler feed water applications. The HVAM system incorporates a dual-phase sample collection/transport method which simultaneously pulls ambient air samples containing hydrazine and a very dilute sulfuric acid solution (0.0001 M) down a length of 1/4 inch outside diameter (OD) tubing from a remote site to the analyzer. The hydrazine-laden dilute acid stream is separated from the air and the pH is adjusted by addition of a dilute caustic solution to a pH greater than 10.2 prior to analysis. Both the dilute acid and caustic used by the HVAM are continuously generated during system operation on an "as needed" basis by mixing a metered amount of concentrated acid/base with dilution water. All of the waste water generated by the analyzer is purified for reuse by Barnstead ion-exchange cartridges so that the entire system minimizes the generation of waste materials. The pumping of all liquid streams and mixing of the caustic solution and dilution water with the incoming sample are done by a single pump motor fitted with the appropriate mix of peristaltic pump heads. The signal to noise (S/N) ratio of the analyzer has been enhanced by adding a stirrer in the MDA liquid cell to provide mixing normally generated by the high liquid flow rate designed by the manufacturer. An onboard microprocessor continuously monitors liquid levels, sample vacuum, and liquid leak sensors, as well as handles communications and other system functions (such as shut down should system malfunctions or errors occur). The overall system response of the HVAM can be automatically checked at regular intervals by measuring the analyzer response to a metered amount of calibration standard injected

  8. Mixed-linker zeolitic imidazolate framework mixed-matrix membranes for aggressive CO2 separation from natural gas

    KAUST Repository

    Thompson, Joshua A.; Vaughn, Justin T.; Brunelli, Nicholas A.; Koros, William J.; Jones, Christopher W.; Nair, Sankar

    2014-01-01

    Zeolitic imidazolate framework (ZIF) materials are a promising subclass of metal-organic frameworks (MOF) for gas separations. However, due to the deleterious effects of gate-opening phenomena associated with organic linker rotation near

  9. Charged residues in the H-NS linker drive DNA binding and gene silencing in single cells.

    Science.gov (United States)

    Gao, Yunfeng; Foo, Yong Hwee; Winardhi, Ricksen S; Tang, Qingnan; Yan, Jie; Kenney, Linda J

    2017-11-21

    Nucleoid-associated proteins (NAPs) facilitate chromosome organization in bacteria, but the precise mechanism remains elusive. H-NS is a NAP that also plays a major role in silencing pathogen genes. We used genetics, single-particle tracking in live cells, superresolution microscopy, atomic force microscopy, and molecular dynamics simulations to examine H-NS/DNA interactions in single cells. We discovered a role for the unstructured linker region connecting the N-terminal oligomerization and C-terminal DNA binding domains. In the present work we demonstrate that linker amino acids promote engagement with DNA. In the absence of linker contacts, H-NS binding is significantly reduced, although no change in chromosome compaction is observed. H-NS is not localized to two distinct foci; rather, it is scattered all around the nucleoid. The linker makes DNA contacts that are required for gene silencing, while chromosome compaction does not appear to be an important H-NS function.

  10. How to remain nonfolded and pliable: the linkers in modular α-amylases as a case study.

    Science.gov (United States)

    Feller, Georges; Dehareng, Dominique; Lage, Jean-Luc Da

    2011-07-01

    The primary structure of linkers in a new class of modular α-amylases constitutes a paradigm of the structural basis that allows a polypeptide to remain nonfolded, extended and pliable. Unfolding is mediated through a depletion of hydrophobic residues and an enrichment of hydrophilic residues, amongst which Ser and Thr are over-represented. An extended and flexible conformation is promoted by the sequential arrangement of Pro and Gly, which are the most abundant residues in these linkers. This is complemented by charge repulsion, charge clustering and disulfide-bridged loops. Molecular dynamics simulations suggest the existence of conformational transitions resulting from a transient and localized hydrophobic collapse, arising from the peculiar composition of the linkers. Accordingly, these linkers should not be regarded as fully disordered, but rather as possessing various discrete structural patterns allowing them to fulfill their biological function as a free energy reservoir for concerted motions between structured domains. © 2011 The Authors Journal compilation © 2011 FEBS.

  11. The unstructured linker arms of Mlh1-Pms1 are important for interactions with DNA during mismatch repair

    Science.gov (United States)

    Plys, Aaron J.; Rogacheva, Maria V.; Greene, Eric C.; Alani, Eric

    2012-01-01

    DNA mismatch repair (MMR) models have proposed that MSH proteins identify DNA polymerase errors while interacting with the DNA replication fork. MLH proteins (primarily Mlh1-Pms1 in baker’s yeast) then survey the genome for lesion-bound MSH proteins. The resulting MSH-MLH complex formed at a DNA lesion initiates downstream steps in repair. MLH proteins act as dimers and contain long (20 – 30 nanometers) unstructured arms that connect two terminal globular domains. These arms can vary between 100 to 300 amino acids in length, are highly divergent between organisms, and are resistant to amino acid substitutions. To test the roles of the linker arms in MMR, we engineered a protease cleavage site into the Mlh1 linker arm domain of baker’s yeast Mlh1-Pms1. Cleavage of the Mlh1 linker arm in vitro resulted in a defect in Mlh1-Pms1 DNA binding activity, and in vivo proteolytic cleavage resulted in a complete defect in MMR. We then generated a series of truncation mutants bearing Mlh1 and Pms1 linker arms of varying lengths. This work revealed that MMR is greatly compromised when portions of the Mlh1 linker are removed, whereas repair is less sensitive to truncation of the Pms1 linker arm. Purified complexes containing truncations in Mlh1 and Pms1 linker arms were analyzed and found to have differential defects in DNA binding that also correlated with the ability to form a ternary complex with Msh2-Msh6 and mismatch DNA. These observations are consistent with the unstructured linker domains of MLH proteins providing distinct interactions with DNA during MMR. PMID:22659005

  12. Mixed-linker zeolitic imidazolate framework mixed-matrix membranes for aggressive CO2 separation from natural gas

    KAUST Repository

    Thompson, Joshua A.

    2014-07-01

    Zeolitic imidazolate framework (ZIF) materials are a promising subclass of metal-organic frameworks (MOF) for gas separations. However, due to the deleterious effects of gate-opening phenomena associated with organic linker rotation near the limiting pore apertures of ZIFs, there have been few demonstrations of improved gas separation properties over pure polymer membranes when utilizing ZIF materials in composite membranes for CO2-based gas separations. Here, we report a study of composite ZIF/polymer membranes, containing mixed-linker ZIF materials with ZIF-8 crystal topologies but composed of different organic linker compositions. Characterization of the mixed-linker ZIFs shows that the mixed linker approach offers control over the porosity and pore size distribution of the materials, as determined from nitrogen physisorption and Horváth-Kawazoe analysis. Single gas permeation measurements on mixed-matrix membranes reveal that inclusion of mixed-linker ZIFs yields membranes with better ideal CO2/CH4 selectivity than membranes containing ZIF-8. This improvement is shown to likely occur from enhancement in the diffusion selectivity of the membranes associated with controlling the pore size distribution of the ZIF filler. Mixed-gas permeation experiments show that membranes with mixed-linker ZIFs display an effective plasticization resistance that is not typical of the pure polymeric matrix. Overall, we demonstrate that mixed-linker ZIFs can improve the gas separation properties in composite membranes and may be applicable to aggressive CO2 concentrations in natural gas feeds. © 2013 Elsevier Inc. All rights reserved.

  13. Rapid One-Pot Microwave Synthesis of Mixed-Linker Hybrid Zeolitic-Imidazolate Framework Membranes for Tunable Gas Separations.

    Science.gov (United States)

    Hillman, Febrian; Brito, Jordan; Jeong, Hae-Kwon

    2018-02-14

    The relatively slow and complex fabrication processes of polycrystalline metal-organic framework (MOF) membranes often times restrict their way to commercialization, despite their potential for molecular separation applications. Herein, we report a rapid one-pot microwave synthesis of mixed-linker hybrid zeolitic-imidazolate framework (ZIF) membranes consisting of 2-methylimidazolate (ZIF-8 linker) and benzimidazolate (ZIF-7 linker) linkers, termed ZIF-7-8 membranes. The fast-volumetric microwave heating in conjunction with a unique counter diffusion of metal and linker solutions enabled unprecedented rapid synthesis of well-intergrown ZIF-7-8 membranes in ∼90 s, the fastest MOF membrane preparation up to date. Furthermore, we were able to tune the molecular sieving properties of the ZIF-7-8 membranes by varying the benzimidazole-to-2-methylimidazole (bIm-to-mIm) linker ratio in the hybrid frameworks. The tuning of their molecular sieving properties led to the systematic change in the permeance and selectivity of various small gases. The unprecedented rapid synthesis of well-intergrown ZIF-7-8 membranes with tunable molecular sieving properties is an important step forward for the commercial gas separation applications of ZIF membranes.

  14. Effect of linkers on the αvβ3 integrin targeting efficiency of cyclic RGD-conjugates

    Science.gov (United States)

    Karmakar, Partha; Grabowska, Dorota; Sudlow, Gail; Ziabrev, Kostiantyn; Sanyal, Nibedita; Achilefu, Samuel

    2018-02-01

    Cyclic arginine-glycine-aspartic acid (cRGD) peptides are well known to target ανβ3 integrin expressed on cancer cells and neovasculature. Conjugation of these peptides with dyes, drugs, antibodies and other biomolecules through covalent linkers provides a facile way to deliver these products to tumor cells for targeted cancer therapy and diagnosis. Click chemistry and acid-amine couplings are widely used conjugation strategies. However, the effects of different linkers and the distance between the cRGD and the conjugates on the binding of cRGD ligand with ανβ3 has been underexplored. In this present study, we prepared cRGD-conjugates using different linkers and determined how they altered the tumor targeting efficiency in vitro and in vivo. The results demonstrate that different linkers significantly altered the pharmacokinetics of the cRGD conjugates and the tumor uptake kinetics. Unlike large antibodies, this preliminary finding shows that linkers used to attach drugs and fluorescent molecular probes to small peptides play a major role in the accuracy of tumor targeting and treatment outcomes. As a result, considerable attention should be paid to the nature of linkers used in the design of molecular probes and targeted therapeutics.

  15. ATPase Domain and Interdomain Linker Play a Key Role in Aggregation of Mitochondrial Hsp70 Chaperone Ssc1*

    Science.gov (United States)

    Blamowska, Marta; Sichting, Martin; Mapa, Koyeli; Mokranjac, Dejana; Neupert, Walter; Hell, Kai

    2010-01-01

    The co-chaperone Hep1 is required to prevent the aggregation of mitochondrial Hsp70 proteins. We have analyzed the interaction of Hep1 with mitochondrial Hsp70 (Ssc1) and the determinants in Ssc1 that make it prone to aggregation. The ATPase and peptide binding domain (PBD) of Hsp70 proteins are connected by a linker segment that mediates interdomain communication between the domains. We show here that the minimal Hep1 binding entity of Ssc1 consists of the ATPase domain and the interdomain linker. In the absence of Hep1, the ATPase domain with the interdomain linker had the tendency to aggregate, in contrast to the ATPase domain with the mutated linker segment or without linker, and in contrast to the PBD. The closest homolog of Ssc1, bacterial DnaK, and a Ssc1 chimera, in which a segment of the ATPase domain of Ssc1 was replaced by the corresponding segment from DnaK, did not aggregate in Δhep1 mitochondria. The propensity to aggregate appears to be a specific property of the mitochondrial Hsp70 proteins. The ATPase domain in combination with the interdomain linker is crucial for aggregation of Ssc1. In conclusion, our results suggest that interdomain communication makes Ssc1 prone to aggregation. Hep1 counteracts aggregation by binding to this aggregation-prone conformer. PMID:20007714

  16. ATPase domain and interdomain linker play a key role in aggregation of mitochondrial Hsp70 chaperone Ssc1.

    Science.gov (United States)

    Blamowska, Marta; Sichting, Martin; Mapa, Koyeli; Mokranjac, Dejana; Neupert, Walter; Hell, Kai

    2010-02-12

    The co-chaperone Hep1 is required to prevent the aggregation of mitochondrial Hsp70 proteins. We have analyzed the interaction of Hep1 with mitochondrial Hsp70 (Ssc1) and the determinants in Ssc1 that make it prone to aggregation. The ATPase and peptide binding domain (PBD) of Hsp70 proteins are connected by a linker segment that mediates interdomain communication between the domains. We show here that the minimal Hep1 binding entity of Ssc1 consists of the ATPase domain and the interdomain linker. In the absence of Hep1, the ATPase domain with the interdomain linker had the tendency to aggregate, in contrast to the ATPase domain with the mutated linker segment or without linker, and in contrast to the PBD. The closest homolog of Ssc1, bacterial DnaK, and a Ssc1 chimera, in which a segment of the ATPase domain of Ssc1 was replaced by the corresponding segment from DnaK, did not aggregate in Delta hep1 mitochondria. The propensity to aggregate appears to be a specific property of the mitochondrial Hsp70 proteins. The ATPase domain in combination with the interdomain linker is crucial for aggregation of Ssc1. In conclusion, our results suggest that interdomain communication makes Ssc1 prone to aggregation. Hep1 counteracts aggregation by binding to this aggregation-prone conformer.

  17. Chemical synthesis, characterization and electro-oxidation of hydrazine via a carbon paste electrode modified with poly (P-phenylendiamine/Al2O3) nanocomposite

    International Nuclear Information System (INIS)

    Emamgholizadeh, Abbas; Omrani, Abdollah; Rostami, Abbas Ali

    2012-01-01

    Highlights: ► A novel nanocomposite based on poly (P-phenylendiamine)/alumina was synthesized. ► It was observed that the nanocomposite increased the surface catalytic activity of CPE toward oxidation of hydrazine. ► The EIS measurements showed that the values of R ct decreases by the nanoalumina presence. - Abstract: In this article, the chemical synthesis and characterization of Al 2 O 3 nanoparticles dispersed into poly (P-phenylendiamine) (PpDP) was reported. The morphology, conductivity and structure of the nanocomposite was characterized by scanning electron microscopy (SEM), four probe testing and XRD experiment, respectively. Catalytic activity and stability for the oxidation of hydrazine were studied by using cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The results show that the nanocomposite significantly enhances the effective surface area and the catalytic activity of the CPE (carbon paste electrode) for oxidation of hydrazine. The results obtained confirmed that the dispersion of the Al 2 O 3 particles is connected with catalytic response to a higher activity. The nanotubular morphology of poly (P-phenylendiamine) helps in the effective dispersion of Al 2 O 3 particles facilitating the easier access of hydrazine to the catalytic sites. The poly (P-phenylendiamine) nanotubes modified with Al 2 O 3 nanoparticles cause a great increase in electroactivity and the electro-catalytic properties of CPE for hydrazine oxidation.

  18. Preparation of three-dimensional porous Cu film supported on Cu foam and its electrocatalytic performance for hydrazine electrooxidation in alkaline medium

    International Nuclear Information System (INIS)

    Liu, Ran; Ye, Ke; Gao, Yinyi; Long, Ziyao; Cheng, Kui; Zhang, Wenping; Wang, Guiling; Cao, Dianxue

    2016-01-01

    Highlights: • A binder-free Cu/Cu foam electrode is prepared by an electrochemical method. • The electrode owns a novel three-dimensional porous structure. • The electrode exhibits superior catalytic activity for hydrazine electrooxidation. - Abstract: A three-dimensional porous copper film is directly deposited on Cu foam by an electrodeposition method using hydrogen bubbles as dynamic template (denoted as Cu/Cu foam). Its electrocatalytic activity toward hydrazine electrooxidation is tested by linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Compared with Cu foam, hydrazine electrooxidation on the Cu/Cu foam electrode shows that the onset oxidation potential displays a ~100 mV negative shift, the current density at −0.6 V raises about 14 times, the apparent activation energy and the charge transfer resistance reduce significantly. The increasing electrocatalytic performance for hydrazine electrooxidation is mainly caused by the highly porous structure of the Cu/Cu foam electrode which can provide a large surface area and make electrolyte access the electrocatalyst surfaces more easily. Hydrazine electrooxidation on the Cu/Cu foam electrode proceeds through a near 4-electron process.

  19. Hydrazine reduction of metal ions to porous submicro-structures of Ag, Pd, Cu, Ni, and Bi

    Energy Technology Data Exchange (ETDEWEB)

    Wang Yue; Shi Yongfang; Chen Yubiao [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Wu Liming, E-mail: liming_wu@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2012-07-15

    Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. Phase purity, morphology, and specific surface area have been characterized. The reactions probably undergo three different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. The reductant hydrazine also plays an important role to the formation of the porous submicro-structure. The reaction temperature influences the size of the constituent particles and the overall architecture of the submicro-structure so as to influence the surface area value. The as-prepared porous metals have shown the second largest surface area ever reported, which are smaller than those made by the reduction of NaBH{sub 4}, but larger than those made by hard or soft template methods. - Graphical abstract: Porous submicro-structures of Ag, Pd, Cu, Ni, and Bi with high surface area have been prepared by the reduction of hydrazine in the glycerol-ethanol solution at room temperature or 120-180 Degree-Sign C. The reactions undergo different mechanisms: simple reduction for Ag and Pd, coordination-then-reduction for Cu and Ni, and hydrolysis-then-reduction for Bi. Highlights: Black-Right-Pointing-Pointer Syntheses of porous Ag, Pd, Cu, Ni, and Bi with high surface area. Black-Right-Pointing-Pointer Ag and Pd undergo simple reduction. Black-Right-Pointing-Pointer Cu and Ni undergo coordination-then-reduction. Black-Right-Pointing-Pointer Bi undergoes hydrolysis-then-reduction. Black-Right-Pointing-Pointer The as-prepared metals have shown the second largest surface area ever reported.

  20. Study of the relationship between chemical structure and antimicrobial activity in a series of hydrazine-based coordination compounds.

    Science.gov (United States)

    Dobrova, B N; Dimoglo, A S; Chumakov, Y M

    2000-08-01

    The dependence of antimicrobial activity on the structure of compounds is studied in a series of compounds based on hydrazine coordinated with ions of Cu(II), Ni(II) and Pd(II). The study has been carried out by means of the original electron-topological method developed earlier. A molecular fragment has been found that is only characteristic of biologically active compounds. Its spatial and electron parameters have been used for the quantitative assessment of the activity in view. The results obtained can be used for the antimicrobial activity prediction in a series of compounds with similar structures.

  1. Reaction of 1-bromo-3-chloropropane with tellurium and dimethyl telluride in the system of hydrazine hydrate-alkali

    International Nuclear Information System (INIS)

    Russavskaya, N.V.; Levanova, E.P.; Sukhomazova, Eh.N.; Grabel'nykh, V.A.; Elaev, A.V.; Klyba, L.V.; Zhanchipova, E.R.; Albanov, A.I.; Korotaeva, I.M.; Toryashinova, D.S.D.; Korchevin, N.A.

    2006-01-01

    A synthesis of oligomeric substance of thiocol type, the poly(trimethyleneditelluride), from 1-bromo-3-chloropropane and elemental tellurium is performed using a hydrazine hydrate-alkali system. Reductive splitting of the tellurocol followed by alkylation with methyl iodide give rise to preparation of bis(methyltelluro)propane, which was synthesized also from dimethyl telluride and 1,3-dihalopropanes using the N 2 H 4 ·H 2 O/KOH system. The reaction products were characterized by elementary analysis, NMR, and IR spectra. Mass spectra of the synthesized low molecular weight organotellurium compounds are considered [ru

  2. Hydrazine-Free Solution-Deposited CuIn(S,Se)2 Solar Cells by Spray Deposition of Metal Chalcogenides.

    Science.gov (United States)

    Arnou, Panagiota; van Hest, Maikel F A M; Cooper, Carl S; Malkov, Andrei V; Walls, John M; Bowers, Jake W

    2016-05-18

    Solution processing of semiconductors, such as CuInSe2 and its alloys (CIGS), can significantly reduce the manufacturing costs of thin film solar cells. Despite the recent success of solution deposition approaches for CIGS, toxic reagents such as hydrazine are usually involved, which introduce health and safety concerns. Here, we present a simple and safer methodology for the preparation of high-quality CuIn(S, Se)2 absorbers from metal sulfide solutions in a diamine/dithiol mixture. The solutions are sprayed in air, using a chromatography atomizer, followed by a postdeposition selenization step. Two different selenization methods are explored resulting in power conversion efficiencies of up to 8%.

  3. The hard start phenomena in hypergolic engines. Volume 4: The chemistry of hydrazine fuels and nitrogen tetroxide propellant systems

    Science.gov (United States)

    Miron, Y.; Perlee, H. E.

    1974-01-01

    The various chemical reactions that occur and that could possibly occur in the RCS engines utilizing hydrazine-type fuel/nitrogen tetroxide propellant systems, prior to ignition (preignition), during combustion, and after combustion (postcombustion), and endeavors to relate the hard-start phenomenon to some of these reactions are discussed. The discussion is based on studies utilizing a variety of experimental techniques and apparatus as well as current theories of chemical reactions and reaction kinetics. The chemical reactions were studied in low pressure gas flow reactors, low temperature homogeneous- and heterogeneous-phase reactors, simulated two-dimensional (2-D) engines, and scaled and full size engines.

  4. [Construction of cTnC-linker-TnI (P) Genes, Expression of Fusion Protein and Preparation of Lyophilized Protein].

    Science.gov (United States)

    Song, Xiaoli; Liu, Xiaoyun; Cai, Lei; Wu, Jianwei; Wang, Jihua

    2015-12-01

    In order to construct and express human cardiac troponin C-linker-troponin I(P) [ cTnC-linker-TnI(P)] fusion protein, detect its activity and prepare lyophilized protein, we searched the CDs of human cTnC and cTnI from GenBank, synthesized cTnC and cTnI(30-110aa) into cloning vector by a short DNA sequence coding for 15 neutral amino acid residues. pCold I-cTnC-linker-TnI(P) was constructed and transformed into E. coli BL21(DE3). Then, cTnC-linker-TnI(P) fusion protein was induced by isopropyl-β-D-thiogalactopyranoside (IPTG). Soluable expression of cTnC-linker-TnI(P) in prokaryotic system was successfully obtained. The fusion protein was purified by Ni²⁺ Sepharose 6 Fast Flow affinity chromatography with over 95% purity and prepared into lyophilized protein. The activity of purified cTnC-linker-TnI(P) and its lyophilized protein were detected by Wondfo Finecare™ cTnI Test. Lyophilized protein of cTnC-linker-TnI(P) was stable for 10 or more days at 37 °C and 4 or more months at 25 °C and 4 °C. The expression system established in this research is feasible and efficient. Lyophilized protein is stable enough to be provided as biological raw materials for further research.

  5. Dynamics of Linker Residues Modulate the Nucleic Acid Binding Properties of the HIV-1 Nucleocapsid Protein Zinc Fingers

    Science.gov (United States)

    Zargarian, Loussiné; Tisné, Carine; Barraud, Pierre; Xu, Xiaoqian; Morellet, Nelly; René, Brigitte; Mély, Yves; Fossé, Philippe; Mauffret, Olivier

    2014-01-01

    The HIV-1 nucleocapsid protein (NC) is a small basic protein containing two zinc fingers (ZF) separated by a short linker. It is involved in several steps of the replication cycle and acts as a nucleic acid chaperone protein in facilitating nucleic acid strand transfers occurring during reverse transcription. Recent analysis of three-dimensional structures of NC-nucleic acids complexes established a new property: the unpaired guanines targeted by NC are more often inserted in the C-terminal zinc finger (ZF2) than in the N-terminal zinc finger (ZF1). Although previous NMR dynamic studies were performed with NC, the dynamic behavior of the linker residues connecting the two ZF domains remains unclear. This prompted us to investigate the dynamic behavior of the linker residues. Here, we collected 15N NMR relaxation data and used for the first time data at several fields to probe the protein dynamics. The analysis at two fields allows us to detect a slow motion occurring between the two domains around a hinge located in the linker at the G35 position. However, the amplitude of motion appears limited in our conditions. In addition, we showed that the neighboring linker residues R29, A30, P31, R32, K33 displayed restricted motion and numerous contacts with residues of ZF1. Our results are fully consistent with a model in which the ZF1-linker contacts prevent the ZF1 domain to interact with unpaired guanines, whereas the ZF2 domain is more accessible and competent to interact with unpaired guanines. In contrast, ZF1 with its large hydrophobic plateau is able to destabilize the double-stranded regions adjacent to the guanines bound by ZF2. The linker residues and the internal dynamics of NC regulate therefore the different functions of the two zinc fingers that are required for an optimal chaperone activity. PMID:25029439

  6. A Novel MS-Cleavable Azo Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS)

    Science.gov (United States)

    Iacobucci, Claudio; Hage, Christoph; Schäfer, Mathias; Sinz, Andrea

    2017-10-01

    The chemical cross-linking/mass spectrometry (MS) approach is a growing research field in structural proteomics that allows gaining insights into protein conformations. It relies on creating distance constraints between cross-linked amino acid side chains that can further be used to derive protein structures. Currently, the most urgent task for designing novel cross-linking principles is an unambiguous and automated assignment of the created cross-linked products. Here, we introduce the homobifunctional, amine-reactive, and water soluble cross-linker azobisimidoester (ABI) as a prototype of a novel class of cross-linkers. The ABI-linker possesses an innovative modular scaffold combining the benefits of collisional activation lability with open shell chemistry. This MS-cleavable cross-linker can be efficiently operated via free radical initiated peptide sequencing (FRIPS) in positive ionization mode. Our proof-of-principle study challenges the gas phase behavior of the ABI-linker for the three amino acids, lysine, leucine, and isoleucine, as well as the model peptide thymopentin. The isomeric amino acids leucine and isoleucine could be discriminated by their characteristic side chain fragments. Collisional activation experiments were conducted via positive electrospray ionization (ESI) on two Orbitrap mass spectrometers. The ABI-mediated formation of odd electron product ions in MS/MS and MS3 experiments was evaluated and compared with a previously described azo-based cross-linker. All cross-linked products were amenable to automated analysis by the MeroX software, underlining the future potential of the ABI-linker for structural proteomics studies. [Figure not available: see fulltext.

  7. Preparation and in vivo evaluation of linkers for 211At labeling of humanized anti-Tac

    International Nuclear Information System (INIS)

    Yordanov, A.T.; Garmestani, K.; Zhang, M.; Zhang, Z.; Yao, Z.; Phillips, K.E.; Herring, B.; Horak, E.; Beitzel, M.P.; Schwarz, U.P.; Gansow, O.A.; Plascjak, P.S.; Eckelman, W.C.; Waldmann, T.A.; Brechbiel, M.W.

    2001-01-01

    The syntheses, radiolabeling, antibody conjugation, and in vivo evaluation of new linkers for 211 At labeling of humanized anti-Tac (Hu-anti-Tac), an antibody to the α-chain of the IL-2 receptor (IL-2Rα) shown to be a useful target for radioimmunotherapy are described. Synthesis of the organometallic linker precursors is accomplished by reaction of the corresponding bromo- or iodoaryl esters with bis(tributyltin) in the presence of a palladium catalyst. Subsequent conversion to the corresponding N-succinimidyl ester and labeling with 211 At of two new linkers, N-succinimidyl 4-[ 211 At]astato-3-methylbenzoate and N-succinimidyl N-(4-[ 211 At]astatophenethyl)succinamate (SAPS), together with the previously reported N-succinimidyl 4-[ 211 At]astatobenzoate and N-succinimidyl 3-[ 211 At]astato-4-methylbenzoate, are each conjugated to Hu-anti-Tac. The plasma survival times of these conjugates are compared to those of directly iodinated ( 125 I) Hu-anti-Tac. The N-succinimidyl N-(4-[ 211 At]astatophenethyl)succinamate compound (SAPS) emerged from this assay as the most viable candidate for 211 At-labeling of Hu-anti-Tac. SAPS, along with the directly analogous radio-iodinated reagent, N-succinimidyl N-(4-[ 125 I]astatophenethyl)succinamate (SIPS), are evaluated in a biodistribution study along with directly iodinated ( 125 I) Hu-anti-Tac. Blood clearance and biological accretion results indicate that SAPS is a viable candidate for further evaluation for radioimmunotherapy of cancer

  8. Simultaneous quantitation of hydrazine and acetylhydrazine in human plasma by high performance liquid chromatography-tandem mass spectrometry after derivatization with p-tolualdehyde.

    Science.gov (United States)

    Song, Lu; Gao, Dan; Li, Shangfu; Wang, Yanwei; Liu, Hongxia; Jiang, Yuyang

    2017-09-15

    A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was developed for simultaneous quantitative analysis of hydrazine and acetylhydrazine in human plasma based on the strategy of p-tolualdehyde derivatization. The derivatization reactions were easily realized by ultrasonic manipulation for 40min. Good separation of the derivatization products was achieved using a C 18 column by gradient elution. The optimized mass transition ion-pairs (m/z) monitored for the two hydrazine derivatives were m/z 237.1≫>119.9 and m/z 176.9≫>117.8, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for hydrazine were 0.002 and 0.005ngmL -1 separately. And they were 0.03 and 0.05ngmL -1 for acetylhydrazine, respectively. The linear range was 0.005-50ngmL -1 for hydrazine and 0.05-500ngmL -1 for acetylhydrazine with R 2 greater than 0.999. The recovery range was determined to be 95.38-108.12% with the relative standard deviation (RSD) in the range of 1.24-14.89%. The method was successfully applied to detect 30 clinical plasma samples of pulmonary tuberculosis patients treated with isoniazid. The concentrations were from 0.04-1.99ngmL -1 for hydrazine and 0.06-142.43ngmL -1 for acetylhydrazine. The results indicated that our developed method had the potential for the detection of hydrazine toxicology in complex biological samples. Furthermore, the method has an important significance to clinical treatment with drugs. Copyright © 2017. Published by Elsevier B.V.

  9. Accurate distance determination of nucleic acids via Förster resonance energy transfer: implications of dye linker length and rigidity.

    Science.gov (United States)

    Sindbert, Simon; Kalinin, Stanislav; Nguyen, Hien; Kienzler, Andrea; Clima, Lilia; Bannwarth, Willi; Appel, Bettina; Müller, Sabine; Seidel, Claus A M

    2011-03-02

    In Förster resonance energy transfer (FRET) experiments, the donor (D) and acceptor (A) fluorophores are usually attached to the macromolecule of interest via long flexible linkers of up to 15 Å in length. This causes significant uncertainties in quantitative distance measurements and prevents experiments with short distances between the attachment points of the dyes due to possible dye-dye interactions. We present two approaches to overcome the above problems as demonstrated by FRET measurements for a series of dsDNA and dsRNA internally labeled with Alexa488 and Cy5 as D and A dye, respectively. First, we characterize the influence of linker length and flexibility on FRET for different dye linker types (long, intermediate, short) by analyzing fluorescence lifetime and anisotropy decays. For long linkers, we describe a straightforward procedure that allows for very high accuracy of FRET-based structure determination through proper consideration of the position distribution of the dye and of linker dynamics. The position distribution can be quickly calculated with geometric accessible volume (AV) simulations, provided that the local structure of RNA or DNA in the proximity of the dye is known and that the dye diffuses freely in the sterically allowed space. The AV approach provides results similar to molecular dynamics simulations (MD) and is fully consistent with experimental FRET data. In a benchmark study for ds A-RNA, an rmsd value of 1.3 Å is achieved. Considering the case of undefined dye environments or very short DA distances, we introduce short linkers with a propargyl or alkenyl unit for internal labeling of nucleic acids to minimize position uncertainties. Studies by ensemble time correlated single photon counting and single-molecule detection show that the nature of the linker strongly affects the radius of the dye's accessible volume (6-16 Å). For short propargyl linkers, heterogeneous dye environments are observed on the millisecond time scale. A

  10. Bioinformatic Analysis Reveals Conservation of Intrinsic Disorder in the Linker Sequences of Prokaryotic Dual-family Immunophilin Chaperones.

    Science.gov (United States)

    Barik, Sailen

    2018-01-01

    The two classical immunophilin families, found essentially in all living cells, are: cyclophilin (CYN) and FK506-binding protein (FKBP). We previously reported a novel class of immunophilins that are natural chimera of these two, which we named dual-family immunophilin (DFI). The DFIs were found in either of two conformations: CYN-linker-FKBP (CFBP) or FKBP-3TPR-CYN (FCBP). While the 3TPR domain can serve as a flexible linker between the FKBP and CYN modules in the FCBP-type DFI, the linker sequences in the CFBP-type DFIs are relatively short, diverse in sequence, and contain no discernible motif or signature. Here, I present several lines of computational evidence that, regardless of their primary structure, these CFBP linkers are intrinsically disordered. This report provides the first molecular foundation for the model that the CFBP linker acts as an unstructured, flexible loop, allowing the two flanking chaperone modules function independently while linked in cis , likely to assist in the folding of multisubunit client complexes.

  11. Synthesis, characterization and anti-bacterial activity of divalent transition metal complexes of hydrazine and trimesic acid

    Directory of Open Access Journals (Sweden)

    K. Kumar

    2018-01-01

    Full Text Available Transition metal complexes of trimesic acid and hydrazine mixed-ligands with a general formula M(Htma(N2H42, where, M = Mn, Co, Ni, Cu and Zn; H3tma = trimesic acid, have been prepared and characterized by elemental, structural, spectral and thermal analyses. For the complexes, the carboxylate νasym and νsym stretchings are observed at about 1626 and 1367 cm−1 respectively, with Δν between them of ∼260 cm−1, showing the unidentate coordination of each carboxylate group. The hydrazine moieties are present as bridging bidentates. Electronic and EPR spectral studies suggest an octahedral geometry for the complexes. All these complexes show three steps of decomposition in TGA/DTA. SEM images of CuO and MnO residues obtained from the complexes show nano-sized clusters suggesting that the complexes may be used as precursors for nano-CuO and nano-MnO preparation. The antimicrobial activities of the prepared complexes, against four bacteria have been evaluated.

  12. Study of Supported Nickel Catalysts Prepared by Aqueous Hydrazine Method. Hydrogenating Properties and Hydrogen Storage: Support Effect. Silver Additive Effect

    International Nuclear Information System (INIS)

    Wojcieszak, R.

    2006-06-01

    We have studied Ni or NiAg nano-particles obtained by the reduction of nickel salts (acetate or nitrate) by hydrazine and deposited by simple or EDTA-double impregnation on various supports (γ-Al 2 O 3 , amorphous or crystallized SiO 2 , Nb 2 O 5 , CeO 2 and carbon). Prepared catalysts were characterized by different methods (XRD, XPS, low temperature adsorption and desorption of N 2 , FTIR and FTIR-Pyridine, TEM, STEM, EDS, H 2 -TPR, H 2 -adsorption, H 2 -TPD, isopropanol decomposition) and tested in the gas phase hydrogenation of benzene or as carbon materials in the hydrogen storage at room temperature and high pressure. The catalysts prepared exhibited better dispersion and activity than classical catalysts. TOF's of NiAg/SiO 2 or Ni/carbon catalysts were similar to Pt catalysts in benzene hydrogenation. Differences in support acidity or preparation method and presence of Ag as metal additive play a crucial role in the chemical reduction of Ni by hydrazine and in the final properties of the materials. Ni/carbon catalysts could store significant amounts of hydrogen at room temperature and high pressure (0.53%/30 bars), probably through the hydrogen spillover effect. (author)

  13. Preparation and characterization of AuNPs/CNTs-ErGO electrochemical sensors for highly sensitive detection of hydrazine.

    Science.gov (United States)

    Zhao, Zhenting; Sun, Yongjiao; Li, Pengwei; Zhang, Wendong; Lian, Kun; Hu, Jie; Chen, Yong

    2016-09-01

    A highly sensitive electrochemical sensor of hydrazine has been fabricated by Au nanoparticles (AuNPs) coating of carbon nanotubes-electrochemical reduced graphene oxide composite film (CNTs-ErGO) on glassy carbon electrode (GCE). Cyclic voltammetry and potential amperometry have been used to investigate the electrochemical properties of the fabricated sensors for hydrazine detection. The performances of the sensors were optimized by varying the CNTs to ErGO ratio and the quantity of Au nanoparticles. The results show that under optimal conditions, a sensitivity of 9.73μAμM(-1)cm(-2), a short response time of 3s, and a low detection limit of 0.065μM could be achieved with a linear concentration response range from 0.3μM to 319μM. The enhanced electrochemical performances could be attributed to the synergistic effect between AuNPs and CNTs-ErGO film and the outstanding catalytic effect of the Au nanoparticles. Finally, the sensor was successfully used to analyse the tap water, showing high potential for practical applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. A first-principles study on adsorption behaviors of pristine and Li-decorated graphene sheets toward hydrazine molecules

    Science.gov (United States)

    Zeng, Huadong; Cheng, Xinlu; Wang, Wei

    2018-03-01

    The adsorption behaviors and properties of hydrazine (N2H4) molecules on pristine and Li-decorated graphene sheets were investigated by means of first-principles based on density functional theory. We systematically analyzed the optimal geometry, average binding energy, charge transfer, charge density difference and density of states of N2H4 molecules adsorbed on pristine and Li-decorated graphene sheets. It is found that the interaction between single N2H4 molecule and pristine graphene is weak physisorption with the low binding energy of -0.026 eV, suggesting that the pristine graphene sheet is insensitive to the presence of N2H4 molecule. However, it is markedly enhanced after lithium decoration with the high binding energy of -1.004 eV, verifying that the Li-decorated graphene sheet is significantly sensitive to detect N2H4 molecule. Meanwhile, the effects of the concentrations of N2H4 molecules on two different substrates were studied detailedly. For pristine graphene substrate, the average binding energy augments apparently with increasing the number of N2H4 molecules, which is mainly attributed to the van der Waals interactions and hydrogen bonds among N2H4 clusters. Li-decorated graphene sheet has still a strong affinity to N2H4 molecules despite the corresponding average binding energy emerges a contrary tendency. Overall, Li-decorated graphene sheet could be considered as a potential gas sensor in field of hydrazine molecules.

  15. Hybrid Zeolitic Imidazolate Frameworks: Controlling Framework Porosity and Functionality by Mixed-Linker Synthesis

    KAUST Repository

    Thompson, Joshua A.

    2012-05-22

    Zeolitic imidazolate frameworks (ZIFs) are a subclass of nanoporous metal-organic frameworks (MOFs) that exhibit zeolite-like structural topologies and have interesting molecular recognition properties, such as molecular sieving and gate-opening effects associated with their pore apertures. The synthesis and characterization of hybrid ZIFs with mixed linkers in the framework are described in this work, producing materials with properties distinctly different from the parent frameworks (ZIF-8, ZIF-90, and ZIF-7). NMR spectroscopy is used to assess the relative amounts of the different linkers included in the frameworks, whereas nitrogen physisorption shows the evolution of the effective pore size distribution in materials resulting from the framework hybridization. X-ray diffraction shows these hybrid materials to be crystalline. In the case of ZIF-8-90 hybrids, the cubic space group of the parent frameworks is continuously maintained, whereas in the case of the ZIF-7-8 hybrids there is a transition from a cubic to a rhombohedral space group. Nitrogen physisorption data reveal that the hybrid materials exhibit substantial changes in gate-opening phenomena, either occurring at continuously tunable partial pressures of nitrogen (ZIF-8-90 hybrids) or loss of gate-opening effects to yield more rigid frameworks (ZIF-7-8 hybrids). With this synthetic approach, significant alterations in MOF properties may be realized to suit a desired separation or catalytic process. © 2012 American Chemical Society.

  16. Effective generation of transgenic pigs and mice by linker based sperm-mediated gene transfer.

    Directory of Open Access Journals (Sweden)

    Shih Ping Yao

    2002-04-01

    Full Text Available Abstract Background Transgenic animals have become valuable tools for both research and applied purposes. The current method of gene transfer, microinjection, which is widely used in transgenic mouse production, has only had limited success in producing transgenic animals of larger or higher species. Here, we report a linker based sperm-mediated gene transfer method (LB-SMGT that greatly improves the production efficiency of large transgenic animals. Results The linker protein, a monoclonal antibody (mAb C, is reactive to a surface antigen on sperm of all tested species including pig, mouse, chicken, cow, goat, sheep, and human. mAb C is a basic protein that binds to DNA through ionic interaction allowing exogenous DNA to be linked specifically to sperm. After fertilization of the egg, the DNA is shown to be successfully integrated into the genome of viable pig and mouse offspring with germ-line transfer to the F1 generation at a highly efficient rate: 37.5% of pigs and 33% of mice. The integration is demonstrated again by FISH analysis and F2 transmission in pigs. Furthermore, expression of the transgene is demonstrated in 61% (35/57 of transgenic pigs (F0 generation. Conclusions Our data suggests that LB-SMGT could be used to generate transgenic animals efficiently in many different species.

  17. Ab initio study of hydrogen adsorption on benzenoid linkers in metal-organic framework materials

    International Nuclear Information System (INIS)

    Gao Yi; Zeng, X C

    2007-01-01

    We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal-organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We find that the hybrid B3LYP (Becke three-parameter Lee-Yang-Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular linkers. Both local-density approximation (LDA) and generalized gradient approximation (GGA) DFT methods are inaccurate in predicting the values of hydrogen binding energies, but can give a qualitatively correct prediction of the hydrogen binding. When compared to the more accurate binding-energy results based on the ab initio Moeller-Plesset second-order perturbation (MP2) method, the LDA results may be viewed as an upper limit while the GGA results may be viewed as a lower limit. Since the MP2 calculation is impractical for realistic metal-organic framework systems, the combined LDA and GGA calculations provide a cost-effective way to assess the hydrogen binding capability of these systems

  18. G-CSF receptor-binding cyclic peptides designed with artificial amino-acid linkers

    International Nuclear Information System (INIS)

    Shibata, Kenji; Maruyama-Takahashi, Kumiko; Yamasaki, Motoo; Hirayama, Noriaki

    2006-01-01

    Designing small molecules that mimic the receptor-binding local surface structure of large proteins such as cytokines or growth factors is fascinating and challenging. In this study, we designed cyclic peptides that reproduce the receptor-binding loop structures of G-CSF. We found it is important to select a suitable linker to join two or more discontinuous sequences and both termini of the peptide corresponding to the receptor-binding loop. Structural simulations based on the crystallographic structure of KW-2228, a stable and potent analog of human G-CSF, led us to choose 4-aminobenzoic acid (Abz) as a part of the linker. A combination of 4-Abz with β-alanine or glycine, and disulfide bridges between cysteins or homocysteins, gave a structure suitable for receptor binding. In this structure, the side-chains of several amino acids important for the interactions with the receptor are protruding from one side of the peptide ring. This artificial peptide showed G-CSF antagonistic activity in a cell proliferation assay

  19. A Switchable Linker-Based Immunoassay for Ultrasensitive Visible Detection of Salmonella in Tomatoes.

    Science.gov (United States)

    Hahn, Jungwoo; Kim, Eunghee; You, Young Sang; Gunasekaran, Sundaram; Lim, Seokwon; Choi, Young Jin

    2017-10-01

    On-site detection for sensitive identification of foodborne pathogens on fresh produce with minimal use of specialized instrumentation is crucial to the food industry. A switchable linker (SL)-based immunoassay was designed for ultrasensitive on-site detection of Salmonella in tomato samples. The assay is based on large-scale aggregation of gold nanoparticles (GNPs), induced by a quantitative relationship among the biotinylated Salmonella polyclonal antibody (b-Ab) used as the SL, the functionalized GNPs, and Salmonella. Important factors such as the concentration of SLs, time required for large-scale aggregation, and selectivity of b-Ab were optimized to minimize the detection time (within 45 min with gentle agitation) and achieve the lowest limit of detection (LOD; 10 CFU/g in tomato samples) possible. This SL-based immunoassay with its relatively low LOD and short detection time may meet the need for rapid, simple, on-site analysis of pathogens in fresh produce. The novel switchable linker-based immunoassay is a rapid, specific, and sensitive method that has potential applications for routine diagnostics of Salmonella in tomato products. These advantages make it a practical approach for general use in the processing industry to detect Salmonella rapidly and to implement appropriate regulatory procedures. Furthermore, it could be applied to other fresh products including cantaloupe, strawberry, and cucumbers. © 2017 Institute of Food Technologists®.

  20. The First MS-Cleavable, Photo-Thiol-Reactive Cross-Linker for Protein Structural Studies

    Science.gov (United States)

    Iacobucci, Claudio; Piotrowski, Christine; Rehkamp, Anne; Ihling, Christian H.; Sinz, Andrea

    2018-04-01

    Cleavable cross-linkers are gaining increasing importance for chemical cross-linking/mass spectrometry (MS) as they permit a reliable and automated data analysis in structural studies of proteins and protein assemblies. Here, we introduce 1,3-diallylurea (DAU) as the first CID-MS/MS-cleavable, photo-thiol-reactive cross-linker. DAU is a commercially available, inexpensive reagent that efficiently undergoes an anti-Markovnikov hydrothiolation with cysteine residues in the presence of a radical initiator upon UV-A irradiation. Radical cysteine cross-linking proceeds via an orthogonal "click reaction" and yields stable alkyl sulfide products. DAU reacts at physiological pH and cross-linking reactions with peptides, and proteins can be performed at temperatures as low as 4 °C. The central urea bond is efficiently cleaved upon collisional activation during tandem MS experiments generating characteristic product ions. This improves the reliability of automated cross-link identification. Different radical initiators have been screened for the cross-linking reaction of DAU using the thiol-containing compounds cysteine and glutathione. Our concept has also been exemplified for the biologically relevant proteins bMunc13-2 and retinal guanylyl cyclase-activating protein-2. [Figure not available: see fulltext.

  1. Structural basis for activation of ZAP-70 by phosphorylation of the SH2-kinase linker.

    Science.gov (United States)

    Yan, Qingrong; Barros, Tiago; Visperas, Patrick R; Deindl, Sebastian; Kadlecek, Theresa A; Weiss, Arthur; Kuriyan, John

    2013-06-01

    Serial activation of the tyrosine kinases Lck and ZAP-70 initiates signaling downstream of the T cell receptor. We previously reported the structure of an autoinhibited ZAP-70 variant in which two regulatory tyrosine residues (315 and 319) in the SH2-kinase linker were replaced by phenylalanine. We now present a crystal structure of ZAP-70 in which Tyr 315 and Tyr 319 are not mutated, leading to the recognition of a five-residue sequence register error in the SH2-kinase linker of the original crystallographic model. The revised model identifies distinct roles for these two tyrosines. As seen in a recently reported structure of the related tyrosine kinase Syk, Tyr 315 of ZAP-70 is part of a hydrophobic interface between the regulatory apparatus and the kinase domain, and the integrity of this interface would be lost upon engagement of doubly phosphorylated peptides by the SH2 domains. Tyr 319 is not necessarily dislodged by SH2 engagement, which activates ZAP-70 only ∼5-fold in vitro. In contrast, phosphorylation by Lck activates ZAP-70 ∼100-fold. This difference is due to the ability of Tyr 319 to suppress ZAP-70 activity even when the SH2 domains are dislodged from the kinase domain, providing stringent control of ZAP-70 activity downstream of Lck.

  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. Synthesis, DNA Binding, and Anticancer Properties of Bis-Naphthalimide Derivatives with Lysine-Modified Polyamine Linkers

    Directory of Open Access Journals (Sweden)

    Yu Huang

    2018-01-01

    Full Text Available A series of bis-naphthalimide derivatives with different diamine linkers were designed and synthesized. All of the synthesized bis-naphthalimide derivatives were characterized by NMR and HRMS spectra. The binding ability between the compounds and CT DNA was evaluated by using UV–Vis titration experiments. The bis-naphthalimide compound with an ethylenediamine linker showed the largest binding constant with CT DNA. Hence, it was used as the model compound to study the DNA binding selectivity by UV–Vis titration aiming at different DNA duplexes. As a result, this compound showed binding preference to AT-rich duplexes. The DNA binding modes of the compounds were also measured by viscosity titration. The cytotoxicity of the compounds was evaluated by MTT assay. Compounds with 1,6-diaminohexane or 1,4-phenylenedimethanamine linkers showed higher cytotoxicity compared with other bis-naphthalimide derivatives.

  4. Mutations in Biosynthetic Enzymes for the Protein Linker Region of Chondroitin/Dermatan/Heparan Sulfate Cause Skeletal and Skin Dysplasias

    Directory of Open Access Journals (Sweden)

    Shuji Mizumoto

    2015-01-01

    Full Text Available Glycosaminoglycans, including chondroitin, dermatan, and heparan sulfate, have various roles in a wide range of biological events such as cell signaling, cell proliferation, tissue morphogenesis, and interactions with various growth factors. Their polysaccharides covalently attach to the serine residues on specific core proteins through the common linker region tetrasaccharide, -xylose-galactose-galactose-glucuronic acid, which is produced through the stepwise addition of respective monosaccharides by four distinct glycosyltransferases. Mutations in the human genes encoding the glycosyltransferases responsible for the biosynthesis of the linker region tetrasaccharide cause a number of genetic disorders, called glycosaminoglycan linkeropathies, including Desbuquois dysplasia type 2, spondyloepimetaphyseal dysplasia, Ehlers-Danlos syndrome, and Larsen syndrome. This review focused on recent studies on genetic diseases caused by defects in the biosynthesis of the common linker region tetrasaccharide.

  5. Linker length dependent binding of a focal adhesion kinase derived peptide to the Src SH3-SH2 domains.

    Science.gov (United States)

    Lindfors, Hanna E; Venkata, Bharat Somireddy; Drijfhout, Jan W; Ubbink, Marcellus

    2011-02-18

    The interaction between a peptide encompassing the SH3 and SH2 binding motifs of focal adhesion kinase (FAK) and the Src SH3-SH2 domains has been investigated with NMR spectroscopy and calorimetry. The binding to both motifs is anti-cooperative. Reduction of the long linker connecting the motifs does not lead to cooperativity. Short linkers that do not allow simultaneous intramolecular binding of the peptide to both motifs cause peptide-mediated dimerisation, even with a linker of only three amino acids. The role of the SH3 binding motif is discussed in view of the independent nature of the SH interactions. Copyright © 2011 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  6. The S4-S5 linker acts as a signal integrator for HERG K+ channel activation and deactivation gating.

    Directory of Open Access Journals (Sweden)

    Chai Ann Ng

    Full Text Available Human ether-à-go-go-related gene (hERG K(+ channels have unusual gating kinetics. Characterised by slow activation/deactivation but rapid inactivation/recovery from inactivation, the unique gating kinetics underlie the central role hERG channels play in cardiac repolarisation. The slow activation and deactivation kinetics are regulated in part by the S4-S5 linker, which couples movement of the voltage sensor domain to opening of the activation gate at the distal end of the inner helix of the pore domain. It has also been suggested that cytosolic domains may interact with the S4-S5 linker to regulate activation and deactivation kinetics. Here, we show that the solution structure of a peptide corresponding to the S4-S5 linker of hERG contains an amphipathic helix. The effects of mutations at the majority of residues in the S4-S5 linker of hERG were consistent with the previously identified role in coupling voltage sensor movement to the activation gate. However, mutations to Ser543, Tyr545, Gly546 and Ala548 had more complex phenotypes indicating that these residues are involved in additional interactions. We propose a model in which the S4-S5 linker, in addition to coupling VSD movement to the activation gate, also contributes to interactions that stabilise the closed state and a separate set of interactions that stabilise the open state. The S4-S5 linker therefore acts as a signal integrator and plays a crucial role in the slow deactivation kinetics of the channel.

  7. Preparation of value-added metal-organic frameworks (MOFs) using waste PET bottles as source of acid linker

    CSIR Research Space (South Africa)

    Dyosiba, Xoliswa

    2016-12-01

    Full Text Available of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker Xoliswa Dyosiba, Jianwei Ren, Nicholas M. Musyoka, Henrietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango PII: S2214-9937(16)30053-7 DOI: doi:10.1016/j..., Hen- rietta W. Langmi, Mkhulu Mathe, Maurice S. Onyango, Preparation of Value-added Metal-organic Frameworks (MOFs) Using Waste PET Bottles as Source of Acid Linker, Sustainable Materials and Technologies (2016), doi:10.1016/j.susmat.2016...

  8. A Linker for the Solid-Phase Synthesis of Hydroxamic Acids and Identification of HDAC6 Inhibitors

    DEFF Research Database (Denmark)

    Bang, Claus Gunnar; Jensen, Jakob Feldthusen; Cohrt, Anders Emil O'Hanlon

    2017-01-01

    We herein present broadly useful, readily available and nonintegral hydroxylamine linkers for the routine solid-phase synthesis of hydroxamic acids. The developed protocols enable the efficient synthesis and release of a wide range of hydroxamic acids from various resins, relying on high control...... and flexibility with respect to reagents and synthetic processes. A trityl-based hydroxylamine linker was used to synthesize a library of peptide hydroxamic acids. The inhibitory effects of the compounds were examined for seven HDAC enzyme subtypes using a chemiluminescence-based assay....

  9. Novel cross-linkers for PDMS networks for controlled and well distributed grafting of functionalities by click chemistry

    DEFF Research Database (Denmark)

    Bahrt, Frederikke; Dimitrov, Ivaylo; Daugaard, Anders Egede

    2013-01-01

    by 35%. The contact angle of PDMS films was increased from 108° to 116° by the introduction of a small poly(pentafluorostyrene) chain. Finally, 17α-ethynyl-1,3,5(10)-estratriene-3,17β-diol and 1-ethynyl-3,5- bis(trifluoromethyl)benzene were incorporated as examples of other functional groups. © 2013......-linkers have been utilized to prepare novel polydimethylsiloxane (PDMS) networks. All functional cross-linkers were successfully incorporated into the networks and were demonstrated to be well distributed within the PDMS films. This was substantiated by fluorescence microscopy of a film prepared with the 4...

  10. A QSAR/QSTR Study on the Environmental Health Impact by the Rocket Fuel 1,1-Dimethyl Hydrazine and its Transformation Products

    Directory of Open Access Journals (Sweden)

    Lars Carlsen

    2008-01-01

    Full Text Available QSAR/QSTR modelling constitutes an attractive approach to preliminary assessment of the impact on environmental health by a primary pollutant and the suite of transformation products that may be persistent in and toxic to the environment. The present paper studies the impact on environmental health by residuals of the rocket fuel 1,1-dimethyl hydrazine (heptyl and its transformation products. The transformation products, comprising a variety of nitrogen containing compounds are suggested all to possess a significant migration potential. In all cases the compounds were found being rapidly biodegradable. However, unexpected low microbial activity may cause significant changes. None of the studied compounds appear to be bioaccumulating. Apart from substances with an intact hydrazine structure or hydrazone structure the transformation products in general display rather low environmental toxicities. Thus, it is concluded that apparently further attention should be given to tri- and tetramethyl hydrazine and 1-formyl 2,2-dimethyl hydrazine as well as to the hydrazones of formaldehyde and acetaldehyde as these five compounds may contribute to the overall environmental toxicity of residual rocket fuel and its transformation products.

  11. Preferential 5-Methylcytosine Oxidation in the Linker Region of Reconstituted Positioned Nucleosomes by Tet1 Protein.

    Science.gov (United States)

    Kizaki, Seiichiro; Zou, Tingting; Li, Yue; Han, Yong-Woon; Suzuki, Yuki; Harada, Yoshie; Sugiyama, Hiroshi

    2016-11-07

    Tet (ten-eleven translocation) family proteins oxidize 5-methylcytosine (mC) to 5-hydroxymethylcytosine (hmC), 5-formylcytosine (fC), and 5-carboxycytosine (caC), and are suggested to be involved in the active DNA demethylation pathway. In this study, we reconstituted positioned mononucleosomes using CpG-methylated 382 bp DNA containing the Widom 601 sequence and recombinant histone octamer, and subjected the nucleosome to treatment with Tet1 protein. The sites of oxidized methylcytosine were identified by bisulfite sequencing. We found that, for the oxidation reaction, Tet1 protein prefers mCs located in the linker region of the nucleosome compared with those located in the core region. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Efficient loading of primary alcohols onto a solid phase using a trityl bromide linker

    DEFF Research Database (Denmark)

    Crestey, François; Ottesen, Lars Korsgaard; Jaroszewski, Jerzy Witold

    2008-01-01

    The Letter describes an improved, rapid and mild strategy for the loading of primary alcohols onto a polystyrene trityl resin via a highly reactive trityl bromide linker. This protocol facilitates an efficient resin loading even of acid-sensitive or heat-labile alcohols, which otherwise require...... expensive or non-commercial resin types. Secondary alcohols were only attached in moderate to low yields, while attempts to load a tertiary alcohol expectedly failed. Importantly, selective attachment of diols via a primary alcohol group in the presence of more hindered alcohol groups proved possible....... The effects of activation time and reagent excess as well as alcohol structure were investigated. This improved method provides a convenient access to O-linked resin-bound N-Fmoc-protected amino alcohols that may be employed in SPS of peptides with C-terminal alcohol functionalities. In the case...

  13. Temperature-triggered release of a liquid cross-linker micro-encapsulated in a glassy polymer for low temperature curing

    NARCIS (Netherlands)

    Senatore, D.; Cate, ten A.T.; Laven, J.; Benthem, van R.A.T.M.; With, de G.

    2013-01-01

    In order to prevent a liquid epoxy cross-linker from premature, Arrhenius-law predicted, reaction with an acid-functional polyester resin, the liquid cross-linker has been physically separated from the resin by encapsulation while release is only possible by a temperature-controlled trigger. The

  14. Synthesis of Selective Butyrylcholinesterase Inhibitors Coupled between α-Lipoic Acid and Polyphenols by Using 2-(Piperazin-1-yl)ethanol Linker

    Energy Technology Data Exchange (ETDEWEB)

    Yeun, Go Heun; Lee, Seung Hwan; LIm, Yong Bae; Lee, Hye Sook; Lee, Bong Ho; Park, Jeong Ho [Hanbat National Univ., Daejeon (Korea, Republic of); Won, Mooho [Kangwon National Univ., Chuncheon (Korea, Republic of)

    2013-04-15

    In the previous paper (Bull. Korean Chem. Soc., 2011, 32, 2997), the hybrid molecules between α-lipoic acid (ALA) and polyphenols (PPs) connected with neutral 2-(2-aminoethoxy)ethanol linker (linker-1) showed new biological activity such as butyrylcholinesterase (BuChE) inhibition. In order to increase the binding affinity of the hybrid compounds to cholinesterase (ChE), the neutral 2-(2-aminoethoxy)ethanol (linker 1) was switched to the cationic 2-(piperazin-1-yl)ethanol linker (linker 2). The IC{sub 50} values of the linker-2 hybrid molecules for BuChE inhibition were lower than those of linker-1 hybrid molecules (except 9-2) and they also had the same great selectivity for BuChE over AChE (> 800 fold) as linker-1 hybrid molecules. ALA-acetyl caffeic acid (10-2, ALA-AcCA) was shown as an effective inhibitor of BuChE (IC{sub 50} = 0.44 ± 0.24 μM). A kinetic study using 7-2 showed that it is the same mixed type inhibition as 7-1. Its inhibition constant (Ki) to BuChE is 4.3 ± 0.09 μM.

  15. Synthesis of Selective Butyrylcholinesterase Inhibitors Coupled between α-Lipoic Acid and Polyphenols by Using 2-(Piperazin-1-yl)ethanol Linker

    International Nuclear Information System (INIS)

    Yeun, Go Heun; Lee, Seung Hwan; LIm, Yong Bae; Lee, Hye Sook; Lee, Bong Ho; Park, Jeong Ho; Won, Mooho

    2013-01-01

    In the previous paper (Bull. Korean Chem. Soc., 2011, 32, 2997), the hybrid molecules between α-lipoic acid (ALA) and polyphenols (PPs) connected with neutral 2-(2-aminoethoxy)ethanol linker (linker-1) showed new biological activity such as butyrylcholinesterase (BuChE) inhibition. In order to increase the binding affinity of the hybrid compounds to cholinesterase (ChE), the neutral 2-(2-aminoethoxy)ethanol (linker 1) was switched to the cationic 2-(piperazin-1-yl)ethanol linker (linker 2). The IC 50 values of the linker-2 hybrid molecules for BuChE inhibition were lower than those of linker-1 hybrid molecules (except 9-2) and they also had the same great selectivity for BuChE over AChE (> 800 fold) as linker-1 hybrid molecules. ALA-acetyl caffeic acid (10-2, ALA-AcCA) was shown as an effective inhibitor of BuChE (IC 50 = 0.44 ± 0.24 μM). A kinetic study using 7-2 showed that it is the same mixed type inhibition as 7-1. Its inhibition constant (Ki) to BuChE is 4.3 ± 0.09 μM

  16. Modulations of DNA Contacts by Linker Histones and Post-translational Modifications Determine the Mobility and Modifiability of Nucleosomal H3 Tails.

    Science.gov (United States)

    Stützer, Alexandra; Liokatis, Stamatios; Kiesel, Anja; Schwarzer, Dirk; Sprangers, Remco; Söding, Johannes; Selenko, Philipp; Fischle, Wolfgang

    2016-01-21

    Post-translational histone modifications and linker histone incorporation regulate chromatin structure and genome activity. How these systems interface on a molecular level is unclear. Using biochemistry and NMR spectroscopy, we deduced mechanistic insights into the modification behavior of N-terminal histone H3 tails in different nucleosomal contexts. We find that linker histones generally inhibit modifications of different H3 sites and reduce H3 tail dynamics in nucleosomes. These effects are caused by modulations of electrostatic interactions of H3 tails with linker DNA and largely depend on the C-terminal domains of linker histones. In agreement, linker histone occupancy and H3 tail modifications segregate on a genome-wide level. Charge-modulating modifications such as phosphorylation and acetylation weaken transient H3 tail-linker DNA interactions, increase H3 tail dynamics, and, concomitantly, enhance general modifiability. We propose that alterations of H3 tail-linker DNA interactions by linker histones and charge-modulating modifications execute basal control mechanisms of chromatin function. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Eviction of linker histone H1 by NAP-family histone chaperones enhances activated transcription.

    Science.gov (United States)

    Zhang, Qian; Giebler, Holli A; Isaacson, Marisa K; Nyborg, Jennifer K

    2015-01-01

    In the Metazoan nucleus, core histones assemble the genomic DNA to form nucleosome arrays, which are further compacted into dense chromatin structures by the linker histone H1. The extraordinary density of chromatin creates an obstacle for accessing the genetic information. Regulation of chromatin dynamics is therefore critical to cellular homeostasis, and histone chaperones serve as prominent players in these processes. In the current study, we examined the role of specific histone chaperones in negotiating the inherently repressive chromatin structure during transcriptional activation. Using a model promoter, we demonstrate that the human nucleosome assembly protein family members hNap1 and SET/Taf1β stimulate transcription in vitro during pre-initiation complex formation, prior to elongation. This stimulatory effect is dependent upon the presence of activators, p300, and Acetyl-CoA. We show that transcription from our chromatin template is strongly repressed by H1, and that both histone chaperones enhance RNA synthesis by overcoming H1-induced repression. Importantly, both hNap1 and SET/Taf1β directly bind H1, and function to enhance transcription by evicting the linker histone from chromatin reconstituted with H1. In vivo studies demonstrate that SET/Taf1β, but not hNap1, strongly stimulates activated transcription from the chromosomally-integrated model promoter, consistent with the observation that SET/Taf1β is nuclear, whereas hNap1 is primarily cytoplasmic. Together, these observations indicate that SET/Taf1β may serve as a critical regulator of H1 dynamics and gene activation in vivo. These studies uncover a novel function for SET that mechanistically couples transcriptional derepression with H1 dynamics. Furthermore, they underscore the significance of chaperone-dependent H1 displacement as an essential early step in the transition of a promoter from a dense chromatin state into one that is permissive to transcription factor binding and robust

  18. Cytoskeletal Linker Protein Dystonin Is Not Critical to Terminal Oligodendrocyte Differentiation or CNS Myelination.

    Directory of Open Access Journals (Sweden)

    Samantha F Kornfeld

    Full Text Available Oligodendrocyte differentiation and central nervous system myelination require massive reorganization of the oligodendrocyte cytoskeleton. Loss of specific actin- and tubulin-organizing factors can lead to impaired morphological and/or molecular differentiation of oligodendrocytes, resulting in a subsequent loss of myelination. Dystonin is a cytoskeletal linker protein with both actin- and tubulin-binding domains. Loss of function of this protein results in a sensory neuropathy called Hereditary Sensory Autonomic Neuropathy VI in humans and dystonia musculorum in mice. This disease presents with severe ataxia, dystonic muscle and is ultimately fatal early in life. While loss of the neuronal isoforms of dystonin primarily leads to sensory neuron degeneration, it has also been shown that peripheral myelination is compromised due to intrinsic Schwann cell differentiation abnormalities. The role of this cytoskeletal linker in oligodendrocytes, however, remains unclear. We sought to determine the effects of the loss of neuronal dystonin on oligodendrocyte differentiation and central myelination. To address this, primary oligodendrocytes were isolated from a severe model of dystonia musculorum, Dstdt-27J, and assessed for morphological and molecular differentiation capacity. No defects could be discerned in the differentiation of Dstdt-27J oligodendrocytes relative to oligodendrocytes from wild-type littermates. Survival was also compared between Dstdt-27J and wild-type oligodendrocytes, revealing no significant difference. Using a recently developed migration assay, we further analysed the ability of primary oligodendrocyte progenitor cell motility, and found that Dstdt-27J oligodendrocyte progenitor cells were able to migrate normally. Finally, in vivo analysis of oligodendrocyte myelination was done in phenotype-stage optic nerve, cerebral cortex and spinal cord. The density of myelinated axons and g-ratios of Dstdt-27J optic nerves was normal, as

  19. Synthesis of two new alkyne-bearing linkers used for the preparation of siRNA for labeling by click chemistry with fluorine-18

    International Nuclear Information System (INIS)

    Flagothier, Jessica; Kaisin, Geoffroy; Mercier, Frederic; Thonon, David; Teller, Nathalie; Wouters, Johan; Luxen, André

    2012-01-01

    Oligonucleotides (ONs) and more particularly siRNAs are promising drugs but their pharmacokinetics and biodistribution are widely unknown. Positron Emission Tomography (PET) using fluorine-18 is a suitable technique to quantify these biological processes. Click chemistry (Huisgen cycloaddition) is the current method for labeling siRNA. In order to study the influence of a linker bearing by [ 18 F] labeled ONs, on the in vivo pharmacokinetic and metabolism, we have developed two modified ONs by two new linkers. Here we report the synthesis of two alkyne-bearing linkers, the incorporation onto a ONs and the conjugation by click chemistry with a [ 18 F] prosthetic group. - Highlights: ► Synthesis of two new alkyne linkers. ► Functionalization at the 3′-end siRNA by alkyne linker derived of proline. ► Click chemistry between alkyne modified siRNA and [ 18 F] prosthetic group.

  20. One-pot preparation of mRNA/cDNA display by a novel and versatile puromycin-linker DNA.

    Science.gov (United States)

    Mochizuki, Yuki; Biyani, Manish; Tsuji-Ueno, Sachika; Suzuki, Miho; Nishigaki, Koichi; Husimi, Yuzuru; Nemoto, Naoto

    2011-09-12

    A rapid, easy, and robust preparation method for mRNA/cDNA display using a newly designed puromycin-linker DNA is presented. The new linker is structurally simple, easy to synthesize, and cost-effective for use in "in vitro peptide and protein selection". An introduction of RNase T1 nuclease site to the new linker facilitates the easy recovery of mRNA/cDNA displayed protein by an improvement of the efficiency of ligating the linker to mRNAs and efficient release of mRNA/cDNA displayed protein from the solid-phase (magnetic bead). For application demonstration, affinity selections were successfully performed. Furthermore, we introduced a "one-pot" preparation protocol to perform mRNA display easy. Unlike conventional approaches that require tedious and downstream multistep process including purification, this protocol will make the mRNA/cDNA display methods more practical and convenient and also facilitate the development of next-generation, high-throughput mRNA/cDNA display systems amenable to automation.

  1. Mechanistic Evaluation of Motion in Redox-Driven Rotaxanes Reveals Longer Linkers Hasten Forward Escape's and Hinder Backward Translations

    DEFF Research Database (Denmark)

    Andersen, S. S.; Share, A. I.; Poulsen, B. L.

    2014-01-01

    temperatures to provide activation enthalpies (Delta H-double dagger) and entropies (Delta S-double dagger). Longer glycol linkers led to modest increases in the forward escape (t(1/2) = 60 to 69 s); though not because of a diffusive walk. The reduced rate of motion backward depended on folded structures...

  2. The interdomain flexible linker of the polypeptide GalNAc transferases dictates their long-range glycosylation preferences

    DEFF Research Database (Denmark)

    Rivas, Matilde De Las; Lira-Navarrete, Erandi; Daniel, Earnest James Paul

    2017-01-01

    The polypeptide GalNAc-transferases (GalNAc-Ts), that initiate mucin-type O-glycosylation, consist of a catalytic and a lectin domain connected by a flexible linker. In addition to recognizing polypeptide sequence, the GalNAc-Ts exhibit unique long-range N- A nd/or C-terminal prior glycosylation ...

  3. Synthesis and catalytic evaluation in the Heck reaction of deposited palladium catalysts immobilized via amide linkers and their molecular analogues

    Czech Academy of Sciences Publication Activity Database

    Semler, M.; Čejka, Jiří; Štěpnička, P.

    2014-01-01

    Roč. 227, MAY 2014 (2014), s. 207-214 ISSN 0920-5861 R&D Projects: GA ČR GA104/09/0561; GA ČR(CZ) GA13-08944S Institutional support: RVO:61388955 Keywords : deposited catalysts * palladium * amide linkers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.893, year: 2014

  4. Differential solvation of intrinsically disordered linkers drives the formation of spatially organized droplets in ternary systems of linear multivalent proteins

    Science.gov (United States)

    Harmon, Tyler S.; Holehouse, Alex S.; Pappu, Rohit V.

    2018-04-01

    Intracellular biomolecular condensates are membraneless organelles that encompass large numbers of multivalent protein and nucleic acid molecules. The bodies assemble via a combination of liquid–liquid phase separation and gelation. A majority of condensates included multiple components and show multilayered organization as opposed to being well-mixed unitary liquids. Here, we put forward a simple thermodynamic framework to describe the emergence of spatially organized droplets in multicomponent systems comprising of linear multivalent polymers also known as associative polymers. These polymers, which mimic proteins and/or RNA have the architecture of domains or motifs known as stickers that are interspersed by flexible spacers known as linkers. Using a minimalist numerical model for a four-component system, we have identified features of linear multivalent molecules that are necessary and sufficient for generating spatially organized droplets. We show that differences in sequence-specific effective solvation volumes of disordered linkers between interaction domains enable the formation of spatially organized droplets. Molecules with linkers that are preferentially solvated are driven to the interface with the bulk solvent, whereas molecules that have linkers with negligible effective solvation volumes form cores in the core–shell architectures that emerge in the minimalist four-component systems. Our modeling has relevance for understanding the physical determinants of spatially organized membraneless organelles.

  5. Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network

    Science.gov (United States)

    Bin Imran, Abu; Esaki, Kenta; Gotoh, Hiroaki; Seki, Takahiro; Ito, Kohzo; Sakai, Yasuhiro; Takeoka, Yukikazu

    2014-01-01

    Stimuli-sensitive hydrogels changing their volumes and shapes in response to various stimulations have potential applications in multiple fields. However, these hydrogels have not yet been commercialized due to some problems that need to be overcome. One of the most significant problems is that conventional stimuli-sensitive hydrogels are usually brittle. Here we prepare extremely stretchable thermosensitive hydrogels with good toughness by using polyrotaxane derivatives composed of α-cyclodextrin and polyethylene glycol as cross-linkers and introducing ionic groups into the polymer network. The ionic groups help the polyrotaxane cross-linkers to become well extended in the polymer network. The resulting hydrogels are surprisingly stretchable and tough because the cross-linked α-cyclodextrin molecules can move along the polyethylene glycol chains. In addition, the polyrotaxane cross-linkers can be used with a variety of vinyl monomers; the mechanical properties of the wide variety of polymer gels can be improved by using these cross-linkers. PMID:25296246

  6. High-resolution two-dimensional liquid chromatography analysis of key linker drug intermediate used in antibody drug conjugates.

    Science.gov (United States)

    Venkatramani, C J; Huang, Shu Rong; Al-Sayah, Mohammad; Patel, Ila; Wigman, Larry

    2017-10-27

    In this manuscript, the application of high-resolution sampling (HRS) two-dimensional liquid chromatography (2D-LC) in the detailed analysis of key linker drug intermediate is presented. Using HRS, selected regions of the primary column eluent were transferred to a secondary column with fidelity enabling qualitative and quantitative analysis of linker drugs. The primary column purity of linker drug intermediate ranged from 88.9% to 94.5% and the secondary column purity ranged from 99.6% to 99.9%, showing lot-to-lot variability, significant differences between the three lots, and substantiating the synthetic and analytical challenges of ADCs. Over 15 impurities co-eluting with the linker drug intermediate in the primary dimension were resolved in the secondary dimension. The concentrations of most of these impurities were over three orders of magnitude lower than the linker drug. Effective peak focusing and high-speed secondary column analysis resulted in sharp peaks in the secondary dimension, improving the signal-to-noise ratios. The sensitivity of 2D-LC separation was over five fold better than conventional HPLC separation. The limit of quantitation (LOQ) was less than 0.01%. Many peaks originating from primary dimension were resolved into multiple components in the complementary secondary dimension, demonstrating the complexity of these samples. The 2D-LC was highly reproducible, showing good precision between runs with%RSD of peak areas less than 0.1 for the main component. The absolute difference in the peak areas of impurities less than 0.1% were within ±0.01% and for impurities in the range of 0.1%-0.3%, the absolute difference were ±0.02%, which are comparable to 1D-LC. The overall purity of the linker drug intermediate was determined from the product of primary and secondary column purity (HPLC Purity=%peak area of main component in the primary dimension×%peak area of main component in the secondary dimension). Additionally, the 2D-LC separation enables

  7. Pivotal role of extended linker 2 in the activation of Gα by G protein-coupled receptor.

    Science.gov (United States)

    Huang, Jianyun; Sun, Yutong; Zhang, J Jillian; Huang, Xin-Yun

    2015-01-02

    G protein-coupled receptors (GPCRs) relay extracellular signals mainly to heterotrimeric G-proteins (Gαβγ) and they are the most successful drug targets. The mechanisms of G-protein activation by GPCRs are not well understood. Previous studies have revealed a signal relay route from a GPCR via the C-terminal α5-helix of Gα to the guanine nucleotide-binding pocket. Recent structural and biophysical studies uncover a role for the opening or rotating of the α-helical domain of Gα during the activation of Gα by a GPCR. Here we show that β-adrenergic receptors activate eight Gαs mutant proteins (from a screen of 66 Gαs mutants) that are unable to bind Gβγ subunits in cells. Five of these eight mutants are in the αF/Linker 2/β2 hinge region (extended Linker 2) that connects the Ras-like GTPase domain and the α-helical domain of Gαs. This extended Linker 2 is the target site of a natural product inhibitor of Gq. Our data show that the extended Linker 2 is critical for Gα activation by GPCRs. We propose that a GPCR via its intracellular loop 2 directly interacts with the β2/β3 loop of Gα to communicate to Linker 2, resulting in the opening and closing of the α-helical domain and the release of GDP during G-protein activation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  8. Evaluation of ¹¹¹in-labelled exendin-4 derivatives containing different meprin β-specific cleavable linkers.

    Directory of Open Access Journals (Sweden)

    Andreas Jodal

    Full Text Available Cleavable linkers, which are specifically cleaved by defined conditions or enzymes, are powerful tools that can be used for various purposes. Amongst other things, they have been successfully used to deliver toxic payloads as prodrugs into target tissues. In this work novel linker sequences targeting meprin β, a metalloprotease expressed in the kidney brush-border membrane, were designed and included in the sequence of three radiolabelled exendin-4 derivatives. As radiolabelled exendin-4 derivatives strongly accumulate in the kidneys, we hypothesised that specific cleavage of the radiolabelled moiety at the kidney brush-border membrane would allow easier excretion of the activity into the urine and therefore improve the pharmacological properties of the peptide.The insertion of a cleavable linker did not negatively influence the in vitro properties of the peptides. They showed a good affinity to the GLP-1 receptor expressed in CHL cells, a high internalisation and sufficiently high stability in fresh human blood plasma. In vitro digestion with recombinant meprin β rapidly metabolised the corresponding linker sequences. After 60 min the majority of the corresponding peptides were digested and at the same time the anticipated fragments were formed. The peptides were also quickly metabolised in CD1 nu/nu mouse kidney homogenates. Immunofluorescence staining of meprin β in kidney sections confirmed the expression of the protease in the kidney brush-border membrane. Biodistribution in GLP-1 receptor positive tumour-xenograft bearing mice revealed high specific uptake of the 111In-labelled tracers in receptor positive tissue. Accumulation in the kidneys, however, was still high and comparable to the lead compound 111In-Ex4NOD40.In conclusion, we show that the concept of cleavable linkers specific for meprin β is feasible, as the peptides are rapidly cleaved by the enzyme while retaining their biological properties.

  9. Prescreening of Nicotine Hapten Linkers in Vitro To Select Hapten-Conjugate Vaccine Candidates for Pharmacokinetic Evaluation in Vivo.

    Science.gov (United States)

    Arutla, Viswanath; Leal, Joseph; Liu, Xiaowei; Sokalingam, Sriram; Raleigh, Michael; Adaralegbe, Adejimi; Liu, Li; Pentel, Paul R; Hecht, Sidney M; Chang, Yung

    2017-05-08

    Since the demonstration of nicotine vaccines as a possible therapeutic intervention for the effects of tobacco smoke, extensive effort has been made to enhance nicotine specific immunity. Linker modifications of nicotine haptens have been a focal point for improving the immunogenicity of nicotine, in which the evaluation of these modifications usually relies on in vivo animal models, such as mice, rats or nonhuman primates. Here, we present two in vitro screening strategies to estimate and predict the immunogenic potential of our newly designed nicotine haptens. One utilizes a competition enzyme-linked immunoabsorbent assay (ELISA) to profile the interactions of nicotine haptens or hapten-protein conjugates with nicotine specific antibodies, both polyclonal and monoclonal. Another relies on computational modeling of the interactions between haptens and amino acid residues near the conjugation site of the carrier protein to infer linker-carrier protein conjugation effect on antinicotine antibody response. Using these two in vitro methods, we ranked the haptens with different linkers for their potential as viable vaccine candidates. The ELISA-based hapten ranking was in an agreement with the results obtained by in vivo nicotine pharmacokinetic analysis. A correlation was found between the average binding affinity (IC 50 ) of the haptens to an anti-Nic monoclonal antibody and the average brain nicotine concentration in the immunized mice. The computational modeling of hapten and carrier protein interactions helps exclude conjugates with strong linker-carrier conjugation effects and low in vivo efficacy. The simplicity of these in vitro screening strategies should facilitate the selection and development of more effective nicotine conjugate vaccines. In addition, these data highlight a previously under-appreciated contribution of linkers and hapten-protein conjugations to conjugate vaccine immunogenicity by virtue of their inclusion in the epitope that binds and

  10. Modification of Titanium Substrates with Chimeric Peptides Comprising Antimicrobial and Titanium-Binding Motifs Connected by Linkers To Inhibit Biofilm Formation.

    Science.gov (United States)

    Liu, Zihao; Ma, Shiqing; Duan, Shun; Xuliang, Deng; Sun, Yingchun; Zhang, Xi; Xu, Xinhua; Guan, Binbin; Wang, Chao; Hu, Meilin; Qi, Xingying; Zhang, Xu; Gao, Ping

    2016-03-02

    Bacterial adhesion and biofilm formation are the primary causes of implant-associated infection, which is difficult to eliminate and may induce failure in dental implants. Chimeric peptides with both binding and antimicrobial motifs may provide a promising alternative to inhibit biofilm formation on titanium surfaces. In this study, chimeric peptides were designed by connecting an antimicrobial motif (JH8194: KRLFRRWQWRMKKY) with a binding motif (minTBP-1: RKLPDA) directly or via flexible/rigid linkers to modify Ti surfaces. We evaluated the binding behavior of peptides using quartz crystal microbalance (QCM) and atomic force microscopy (AFM) techniques and investigated the effect of the modification of titanium surfaces with these peptides on the bioactivity of Streptococcus gordonii (S. gordonii) and Streptococcus sanguis (S. sanguis). Compared with the flexible linker (GGGGS), the rigid linker (PAPAP) significantly increased the adsorption of the chimeric peptide on titanium surfaces (p chimeric peptide with the rigid linker exhibited more effective antimicrobial ability than the peptide with the flexible linker. This finding was ascribed to the ability of the rigid linker to separate functional domains and reduce their interference to the maximum extent. Consequently, the performance of chimeric peptides with specific titanium-binding motifs and antimicrobial motifs against bacteria can be optimized by the proper selection of linkers. This rational design of chimeric peptides provides a promising alternative to inhibit the formation of biofilms on titanium surfaces with the potential to prevent peri-implantitis and peri-implant mucositis.

  11. Multivalent cyclic RGD ligands: influence of linker lengths on receptor binding

    Energy Technology Data Exchange (ETDEWEB)

    Kubas, Holger; Schaefer, Martin; Bauder-Wuest, Ulrike; Eder, Matthias; Oltmanns, Doerte [Department of Radiopharmaceutical Chemistry, German Cancer Research Center, Im Neuenheimer Feld 280, 69120 Heidelberg (Germany); Haberkorn, Uwe; Mier, Walter [Department of Nuclear Medicine, University Hospital Heidelberg, Im Neuenheimer Feld 400, 69120 Heidelberg (Germany); Eisenhut, Michael, E-mail: m.eisenhut@dkfz.d [Department of Radiopharmaceutical Chemistry, German Cancer Research Center, Im Neuenheimer Feld 280, 69120 Heidelberg (Germany)

    2010-11-15

    Peptides involving the RGD motive (arginine-glycine-aspartic acid) recognize members of the integrin receptor family. Since the receptors are located mainly on the surface of endothelial cells, structural modifications including multimers of c(RGDfE) were recently found to improve the binding avidity for {alpha}{sub v{beta}3} integrin significantly. The multivalent RGD peptides exhibited rather loose linkages partly including oligo(ethylene glycol) spacers (EG{sub n}) with different chain lengths. Therefore, the dependence of multivalent RGD systems with and without EG{sub n} linkers were investigated on their binding properties to cultured {alpha}{sub v{beta}3} integrin-expressing U87MG cells. Methods: We synthesized a series of di-, tri- and tetravalent rigid scaffolds (terephthalic acid, trimesic acid and adamantane-1,3,5,7-tetracarboxylic acid) conjugated to c(RGDyK) ligands, which were linked contiguously or separated by the oligo(ethylene glycol) spacers. The inhibition constants of these c(RGDyK) derivatives were determined by competition assays with {sup 125}I-labeled echistatin. Results: While c(RGDyK) function is a relative weak competitor against [{sup 125}I]echistatin (K{sub i}, 329{+-}18 nM) for {alpha}{sub v{beta}3} integrin-expressing U87MG cells, RGD dimers improved the competition potency considerably (K{sub i}, 64{+-}23 nM). This effect was even more pronounced with the RGD trimers (K{sub i}, 40{+-}7 nM) and tetramers (K{sub i}, 26{+-}9 nM). The introduction of EG{sub n} spacers and the increase of linker lengths proved to be detrimental since more competitors were needed to compete with [{sup 125}I]echistatin. The EG{sub 6} group, for example, reduced the inhibition constants by 29% (dimer), 57% (trimer) and 97% (tetramer). Conclusion: The binding experiments performed with the three forms of multivalent RGD ligands indicate the weakening of competitive potency against [{sup 125}I]echistatin with the introduction of EG{sub n} spacers. This effect

  12. Effects of hydrazine on the solvothermal synthesis of Cu2ZnSnSe4 and Cu2CdSnSe4 nanocrystals for particle-based deposition of films

    International Nuclear Information System (INIS)

    Chiang, Ming-Hung; Fu, Yaw-Shyan; Shih, Cheng-Hung; Kuo, Chun-Cheng; Guo, Tzung-Fang; Lin, Wen-Tai

    2013-01-01

    The effects of hydrazine on the synthesis of Cu 2 ZnSnSe 4 (CZTSe) and Cu 2 CdSnSe 4 (CCTSe) nanocrystals in an autoclave as a function of temperature and time were explored. On heating at 190 °C for 24-72 h, pure CZTSe and CCTSe nanocrystals could readily grow in the hydrazine-added solution, while in the hydrazine-free solution the intermediate phases such as ZnSe, Cu 2 Se, and Cu 2 SnSe 3 , and Cu 2 SnSe 3 and CdSe associated with the CZTSe and CCTSe nanocrystals grew, respectively. This result reveals that hydrazine can speed up the synthesis of pure CZTSe and CCTSe nanocrystals via a solvothermal process. The mechanisms for the hydrazine-enhanced growth of CZTSe and CCTSe nanocrystals were discussed. The pure CZTSe and CCTSe nanocrystals were subsequently fabricated to the smooth films by spin coating without further annealing in selenium atmosphere. This processing may be beneficial to the fabrication of the absorber layer for solar cells and thermoelectric devices. - Highlights: • Hydrazine enhances the growth of pure Cu 2 ZnSnSe 4 and Cu 2 CdSnSe 4 nanocrystals. • The nanocrystals can be fabricated to films by spin coating without annealing. • This solvothermal processing is promising for the fabrication of thin film devices

  13. Effects of hydrazine on the solvothermal synthesis of Cu{sub 2}ZnSnSe{sub 4} and Cu{sub 2}CdSnSe{sub 4} nanocrystals for particle-based deposition of films

    Energy Technology Data Exchange (ETDEWEB)

    Chiang, Ming-Hung [Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan 701 (China); Fu, Yaw-Shyan, E-mail: ysfu@mail.nutn.edu.tw [Department of Greenergy, National University of Tainan, Tainan, Taiwan 700 (China); Shih, Cheng-Hung; Kuo, Chun-Cheng [Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan 701 (China); Guo, Tzung-Fang [Department of Photonics, Advanced Optoelectronic Technology Center, National Cheng Kung University, Tainan, Taiwan 701 (China); Lin, Wen-Tai, E-mail: wtlin@mail.ncku.edu.tw [Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan 701 (China)

    2013-10-01

    The effects of hydrazine on the synthesis of Cu{sub 2}ZnSnSe{sub 4} (CZTSe) and Cu{sub 2}CdSnSe{sub 4} (CCTSe) nanocrystals in an autoclave as a function of temperature and time were explored. On heating at 190 °C for 24-72 h, pure CZTSe and CCTSe nanocrystals could readily grow in the hydrazine-added solution, while in the hydrazine-free solution the intermediate phases such as ZnSe, Cu{sub 2}Se, and Cu{sub 2}SnSe{sub 3}, and Cu{sub 2}SnSe{sub 3} and CdSe associated with the CZTSe and CCTSe nanocrystals grew, respectively. This result reveals that hydrazine can speed up the synthesis of pure CZTSe and CCTSe nanocrystals via a solvothermal process. The mechanisms for the hydrazine-enhanced growth of CZTSe and CCTSe nanocrystals were discussed. The pure CZTSe and CCTSe nanocrystals were subsequently fabricated to the smooth films by spin coating without further annealing in selenium atmosphere. This processing may be beneficial to the fabrication of the absorber layer for solar cells and thermoelectric devices. - Highlights: • Hydrazine enhances the growth of pure Cu{sub 2}ZnSnSe{sub 4} and Cu{sub 2}CdSnSe{sub 4} nanocrystals. • The nanocrystals can be fabricated to films by spin coating without annealing. • This solvothermal processing is promising for the fabrication of thin film devices.

  14. Contributions of nonextracting Pu reductants (ferrous sulphamate and hydroxylamine nitrate) and holding reductant (hydrazine nitrate) to the aqueous density in U-Pu partitioning system

    International Nuclear Information System (INIS)

    Shekhar Kumar; Rajnish Kumar; Koganti, S.B.

    2005-08-01

    As nonextracting Pu reductants and holding reductants contribute to the density of aqueous phase sub-system considerably, to account their contributions in aqueous phase in solvent extraction simulation code is essential. In this regard, in-house generated precise density data on aqueous ferrous sulphamate solutions as well as aqueous density data, reported in the literature, for HAN, hydrazine nitrate and HAN-HNO 3 systems were analyzed and density equation earlier proposed by authors was extended to it. It was observed that the equation earlier proposed by the authors were simple and were easy to extend for multicomponent system. The contributions of ferrous sulphamate, HAN and hydrazine nitrate to the aqueous density were quantified. It was also observed that the classical value of contribution for nonextractible solute to the aqueous density was quite different from the results reported in this work. (author)

  15. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin

    2015-11-02

    The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

  16. Cobalt nanoparticles as sacrificial templates for the electrodeposition of palladium nanomaterials in an ionic liquid, and its application to electrochemical sensing of hydrazine

    International Nuclear Information System (INIS)

    He, Y.; Zheng, J.; Sheng, Q.

    2012-01-01

    We report on the electrodeposition of palladium nanomaterials in choline chloride-based ionic liquid ethaline. A glassy carbon electrode (GCE) was modified with cobalt nanoparticles (acting as sacrificial templates) and a GCE modified with palladium nanoparticles (PdNPs) were fabricated and used to study the electrocatalytic oxidation of hydrazine (N 2 H 4 ). Scanning electron microscopy revealed that the PdNP modified GCE has a uniform morphology. Zero current potentiometry was used for in-situ probing the changes in interfacial potential of the oxidation of hydrazine. An amperometric study showed that the PdNP modified GCE possesses excellent electrocatalytic activity towards N 2 H 4 . The modified electrode displays a fast response ( -1 ) -1 cm -2 ) and broad linearity in the range from 0.1 to 800 μmol L -1 with a detection limit of 0.03 μmol L -1 (S/N = 3). (author)

  17. Surface modification of g-C3N4 by hydrazine: Simple way for noble-metal free hydrogen evolution catalysts

    KAUST Repository

    Chen, Yin; Lin, Bin; Wang, Hong; Yang, Yong; Zhu, Haibo; Yu, Weili; Basset, Jean-Marie

    2015-01-01

    The graphitic carbon nitride (g-C3N4) usually is thought to be an inert material and it’s difficult to have the surface terminated NH2 groups functionalized. By modifying the g-C3N4 surface with hydrazine, the diazanyl group was successfully introduced onto the g-C3N4 surface, which allows the introduction with many other function groups. Here we illustrated that by reaction of surface hydrazine group modified g-C3N4 with CS2 under basic condition, a water electrolysis active group C(=S)SNi can be implanted on the g-C3N4 surface, and leads to a noble metal free hydrogen evolution catalyst. This catalyst has 40% hydrogen evolution efficiency compare to the 3 wt% Pt photo precipitated g-C3N4, with only less than 0.2 wt% nickel.

  18. Synthesis, Characterization, and Biological Evaluation of certain 6-methyl-2(3H)-benzo-1, 3-thiazolyl-1'-ethylidene-2-(o, p- Substituted Acetophenones) Hydrazine Analogs.

    Science.gov (United States)

    Alang, G; Kaur, G; Kaur, R; Singh, A; Tiwari, R

    2010-10-01

    In the present study, five new derivatives (GG4 to GG8) of benzothiazoles were synthesized and evaluated against Staphylococcus aureus (MTCC 737), Pseudomonas aeruginosa (MTCC 424), Escherichia coli (MTCC 1687), and yeast-like fungi Candida tropicalis. p-Toluidine on treatment with ammonium thiocynate formed 2-benzothiazolamines (II), which on reaction with hydrazine hydrate formed a hydrazino derivative (III). Compounds GG4 to GG8 were synthesized by reacting the hydrazine derivative with different acetophenones. All the synthesized compounds were identified by IR and (1)H-NMR, and antimicrobial activity was performed on the synthesized compounds. Presence of NO(2), Br, OCH(3), and Cl groups to the substituted benzothiazole enhanced the antibacterial and antifungal activities.

  19. Update of the water chemistry effect on the flow-accelerated corrosion rate of carbon steel: influence of hydrazine, boric acid, ammonia, morpholine and ethanolamine

    International Nuclear Information System (INIS)

    Pavageau, E.-M.; De Bouvier, O.; Trevin, S.; Bretelle, J.-L.; Dejoux, L.

    2007-01-01

    The influence of the water chemistry on Flow-Accelerated Corrosion (FAC) affecting carbon steel components has been studied for many years and is relatively well known and taken into account by the models. Nonetheless, experimental studies were conducted in the last few years at EDF on the CIROCO loop in order to check the influence of the water chemistry parameters (hydrazine, boric acid, ammonia, morpholine and ethanolamine) on the FAC rate of carbon steel in one phase flow conditions. The hydrazine impact on the FAC rate was shown to be minor in EDF's chemistry recommendation range, compared to other parameters' effects such as the pH effect. The presence of boric acid in the nominal secondary circuit conditions was negligible. Finally, as expected, the nature of the chemical conditioning (ammonia, morpholine or ethanolamine) did not modify the FAC rate, the influencing chemical variable being the at-temperature pH in one-phase flow conditions. (author)

  20. Inverse Effects on Gating and Modulation Caused by a Mutation in the M2-M3 Linker of the GABAA Receptor γ SubunitS⃞

    OpenAIRE

    O'Shea, Sean M.; Williams, Carrie A.; Jenkins, Andrew

    2009-01-01

    M2-M3 linkers are receptor subunit domains known to be critical for the normal function of cysteine-loop ligand-gated ion channels. Previous studies of α and β subunits of type “A” GABA receptors suggest that these linkers couple extracellular elements involved in GABA binding to the transmembrane segments that control the opening of the ion channel. To study the importance of the γ subunit M2-M3 linker, we examined the macroscopic and single-channel effects of an engi...

  1. A Class of Rigid Linker-bearing Glucosides for Membrane Protein Structural Study.

    Science.gov (United States)

    Sadaf, Aiman; Mortensen, Jonas S; Capaldi, Stefano; Tikhonova, Elena; Hariharan, Parameswaran; de Castro Ribeiro, Orquidea; Loland, Claus J; Guan, Lan; Byrne, Bernadette; Chae, Pil Seok

    2016-03-01

    Membrane proteins are amphipathic bio-macromolecules incompatible with the polar environments of aqueous media. Conventional detergents encapsulate the hydrophobic surfaces of membrane proteins allowing them to exist in aqueous solution. Membrane proteins stabilized by detergent micelles are used for structural and functional analysis. Despite the availability of a large number of detergents, only a few agents are sufficiently effective at maintaining the integrity of membrane proteins to allow successful crystallization. In the present study, we describe a novel class of synthetic amphiphiles with a branched tail group and a triglucoside head group. These head and tail groups were connected via an amide or ether linkage by using a tris(hydroxylmethyl)aminomethane (TRIS) or neopentyl glycol (NPG) linker to produce TRIS-derived triglucosides (TDTs) and NPG-derived triglucosides (NDTs), respectively. Members of this class conferred enhanced stability on target membrane proteins compared to conventional detergents. Because of straightforward synthesis of the novel agents and their favourable effects on a range of membrane proteins, these agents should be of wide applicability to membrane protein science.

  2. Gold nanoparticles deposited on linker-free silicon substrate and embedded in aluminum Schottky contact.

    Science.gov (United States)

    Gorji, Mohammad Saleh; Razak, Khairunisak Abdul; Cheong, Kuan Yew

    2013-10-15

    Given the enormous importance of Au nanoparticles (NPs) deposition on Si substrates as the precursor for various applications, we present an alternative approach to deposit Au NPs on linker-free n- and p-type Si substrates. It is demonstrated that, all conditions being similar, there is a significant difference between densities of the deposited NPs on both substrates. The Zeta-potential and polarity of charges surrounding the hydroxylamine reduced seeded growth Au NPs, are determined by a Zetasizer. To investigate the surface properties of Si substrates, contact angle measurement is performed. Field-emission scanning electron microscope is then utilized to distinguish the NPs density on the substrates. Finally, Al/Si Schottky barrier diodes with embedded Au NPs are fabricated, and their structural and electrical characteristics are further evaluated using an energy-filtered transmission electron microscope and current-voltage measurements, respectively. The results reveal that the density of NPs is significantly higher on n-type Si substrate and consequently has more pronounced effects on the electrical characteristics of the diode. It is concluded that protonation of Si-OH group on Si surface in low pH is responsible for the immobilization of Au NPs, which eventually contributes to the lowering of barrier height and enhances the electrical characteristics. Copyright © 2013 Elsevier Inc. All rights reserved.

  3. Preparation and in vivo evaluation of novel linkers for 211At labeling of proteins

    International Nuclear Information System (INIS)

    Talanov, Vladimir S.; Yordanov, Alexander T.; Garmestani, Kayhan; Milenic, Diane E.; Arora, Hans C.; Plascjak, Paul S.; Eckelman, William C.; Waldmann, Thomas A.; Brechbiel, Martin W.

    2004-01-01

    The syntheses, radiolabeling, antibody conjugation and in vivo evaluation of new linkers for 211 At labeling of monoclonal antibodies are described. Syntheses of the N-succinimidyl esters and labeling with 211 At to form succinimidyl 4-methoxymethyl-3-[ 211 At]astatobenzoate (9) and succinimidyl 4-methylthiomethyl-3-[ 211 At]astatobenzoate (11) from the corresponding bromo-aryl esters is reported. Previously reported succinimidyl N-{4-[ 211 At]astatophenethyl}succinamate (SAPS) is employed as a standard of in vivo stability. Each agent is conjugated with Herceptin in parallel with their respective 125 I analogue, succinimidyl 4-methoxymethyl-3-[ 125 I]iodobenzoate (10), succinimidyl 4-methylthiomethyl-3-[ 125 I]iodobenzoate (12) and succinimidyl N-{4-[ 125 I]iodophenethyl}succinamate (SIPS), respectively, for comparative assessment in LS-174T xenograft-bearing mice. With 9 and 11, inclusion of an electron pair donor in the ortho position does not appear to provide in vivo stability comparable to SAPS. Variables in radiolabeling chemistry of these three agents with 211 At are notable. Sequential elimination of acetic acid and oxidizing agent, N-chlorosuccinimide (NCS), from the 211 At radiolabeling protocol for forming SAPS improves yield, product purity and consistency. NCS appears to be critical for the radiolabeling of 6 with 211 At. Formation of 11, however, is found to require the absence of NCS. Elimination of acetic acid is found to have no effect on radiolabeling efficiency or yield for either of these reactions

  4. Effect of the Linker in Terephthalate-Functionalized Conducting Redox Polymers

    International Nuclear Information System (INIS)

    Yang, Li; Huang, Xiao; Gogoll, Adolf; Strømme, Maria; Sjödin, Martin

    2016-01-01

    The combination of high capacity redox active pendent groups and conducting polymers, realized in conducting redox polymers (CRPs), provides materials with high charge storage capacity that are electronically conducting which makes CRPs attractive for electrical energy storage applications. In this report, six polythiophene and poly(3,4-ethylenedioxythiophene)(PEDOT)-based CRPs with a diethyl terephthalate unit covalently bound to the polymer chain by various linkers have been synthesized and characterized electrochemically. The effects of the choice of polymer backbone and of the nature of the link on the electrochemistry, and in particular the cycling stability of these polymers, are discussed. All CRPs show both the doping of the polymer backbone as well as the redox behavior of the pendent groups and the redox potential of the pendent groups in the CRPs is close to that of corresponding monomer, indicating insignificant interaction between the pendant and the polymer backbone. While all CRPs show various degrees of charge decay upon electrochemical redox conversion, the PEDOT-based CRPs show significantly improved stability compared to the polythiophene counterparts. Moreover, we show that by the right choice of link the cycling stability of diethyl terephthalate substituted PEDOT-based CRPs can be significantly improved.

  5. Missing Linker Defects in a Homochiral Metal-Organic Framework: Tuning the Chiral Separation Capacity.

    Science.gov (United States)

    Slater, Benjamin; Wang, Zeru; Jiang, Shanxue; Hill, Matthew R; Ladewig, Bradley P

    2017-12-20

    Efficient chiral separation remains a very challenging task due to the identical physical and chemical properties of the enantiomers of a molecule. Enantiomers only behave differently from each other in the presence of other chiral species. Homochiral metal-organic frameworks (MOFs) have received much attention for their promising enantioseparation properties. However, there are still challenges to overcome in this field such as high enantiomeric separation. Structural defects play an important role in the properties of MOFs and can significantly change the pore architecture. In this work, we introduced missing linker defects into a homochiral metal-organic framework [Zn 2 (bdc)(l-lac)(dmf)] (ZnBLD; bdc = 1,4-benzenedicarboxylic acid, l-lac = l-lactic acid, dmf = N,N'-dimethylformamide) and observed an increase in enantiomeric excess for 1-phenylethanol of 35% with the defective frameworks. We adjusted the concentration of monocarboxylic acid ligand l-lactic acid by varying the ratio of Zn 2+ to ligand from 0.5 to 0.85 mmol. Additionally, a defective framework was synthesized with propanoic acid as modulator. In order to elucidate the correlation between defects and enantiomeric excess, five characterization techniques (FTIR, TGA, 1 H NMR, ICP, and PXRD) were employed. Full width at half-maximum analysis (fwhm) was performed on the powder X-ray diffraction traces and showed that the higher concentration of monocarboxylic acid MOFs were isostructural but suffered from increased fwhm values.

  6. Enhanced Charge Separation Efficiency in Pyridine-Anchored Phthalocyanine-Sensitized Solar Cells by Linker Elongation.

    Science.gov (United States)

    Ikeuchi, Takuro; Agrawal, Saurabh; Ezoe, Masayuki; Mori, Shogo; Kimura, Mutsumi

    2015-11-01

    A series of zinc phthalocyanine sensitizers (PcS22-24) having a pyridine anchoring group are designed and synthesized to investigate the structural dependence on performance in dye-sensitized solar cells. The pyridine-anchor zinc phthalocyanine sensitizer PcS23 shows 79 % incident-photon to current-conversion efficiency (IPCE) and 6.1 % energy conversion efficiency, which are comparable with similar phthalocyanine dyes having a carboxylic acid anchoring group. Based on DFT calculations, the high IPCE is attributed with the mixture of an excited-state molecular orbital of the sensitizer and the orbitals of TiO2 . Between pyridine and carboxylic acid anchor dyes, opposite trends are observed in the linker-length dependence of the IPCE. The red-absorbing PcS23 is applied for co-sensitization with a carboxyl-anchor organic dye D131 that has a complementary spectral response. The site-selective adsorption of PcS23 and D131 on the TiO2 surface results in a panchromatic photocurrent response for the whole visible-light region of sun light. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

    Science.gov (United States)

    Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

    2015-06-01

    In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

  8. Nucleosome–nucleosome interactions via histone tails and linker DNA regulate nuclear rigidity

    Science.gov (United States)

    Shimamoto, Yuta; Tamura, Sachiko; Masumoto, Hiroshi; Maeshima, Kazuhiro

    2017-01-01

    Cells, as well as the nuclei inside them, experience significant mechanical stress in diverse biological processes, including contraction, migration, and adhesion. The structural stability of nuclei must therefore be maintained in order to protect genome integrity. Despite extensive knowledge on nuclear architecture and components, however, the underlying physical and molecular mechanisms remain largely unknown. We address this by subjecting isolated human cell nuclei to microneedle-based quantitative micromanipulation with a series of biochemical perturbations of the chromatin. We find that the mechanical rigidity of nuclei depends on the continuity of the nucleosomal fiber and interactions between nucleosomes. Disrupting these chromatin features by varying cation concentration, acetylating histone tails, or digesting linker DNA results in loss of nuclear rigidity. In contrast, the levels of key chromatin assembly factors, including cohesin, condensin II, and CTCF, and a major nuclear envelope protein, lamin, are unaffected. Together with in situ evidence using living cells and a simple mechanical model, our findings reveal a chromatin-based regulation of the nuclear mechanical response and provide insight into the significance of local and global chromatin structures, such as those associated with interdigitated or melted nucleosomal fibers. PMID:28428255

  9. Role of H1 linker histones in mammalian development and stem cell differentiation.

    Science.gov (United States)

    Pan, Chenyi; Fan, Yuhong

    2016-03-01

    H1 linker histones are key chromatin architectural proteins facilitating the formation of higher order chromatin structures. The H1 family constitutes the most heterogeneous group of histone proteins, with eleven non-allelic H1 variants in mammals. H1 variants differ in their biochemical properties and exhibit significant sequence divergence from one another, yet most of them are highly conserved during evolution from mouse to human. H1 variants are differentially regulated during development and their cellular compositions undergo dramatic changes in embryogenesis, gametogenesis, tissue maturation and cellular differentiation. As a group, H1 histones are essential for mouse development and proper stem cell differentiation. Here we summarize our current knowledge on the expression and functions of H1 variants in mammalian development and stem cell differentiation. Their diversity, sequence conservation, complex expression and distinct functions suggest that H1s mediate chromatin reprogramming and contribute to the large variations and complexity of chromatin structure and gene expression in the mammalian genome. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. The gamma-ray induced chemisorption of oxygen on perovskite type catalysts: determination by reduction with hydrazine sulphate/hydroxylamine hydrochloride

    International Nuclear Information System (INIS)

    Srinivas, B.; Rao, V.R.S.; Kuriacose, J.C.

    1986-01-01

    Chemisorbed oxygen can be determined quantitatively by the measurement of gaseous N 2 /N 2 O liberated by treatment with hydrazine sulfate/hydroxylamine hydrochloride. The amount of chemisorbed oxygen depends on the degree of dispersion during irradiation and also on the γ-dose. The chemisorption is enhanced in the presence of moisture. The partial reduction of the transition metal ion favours the formation of chemisorbed oxygen. (author)

  11. Simple assembly of polysubstituted pyrazoles and isoxazoles via ring closure-ring opening domino reaction of 3-acyl-4,5-dihydrofurans with hydrazines and hydroxylamine.

    Science.gov (United States)

    Chagarovskiy, Alexey O; Budynina, Ekaterina M; Ivanova, Olga A; Rybakov, Victor B; Trushkov, Igor V; Melnikov, Mikhail Ya

    2016-03-14

    A convenient general approach to 2-(pyrazol-4-yl)- and 2-(isoxazol-4-yl)ethanols based on the Brønsted acid-initiated reaction of 3-acyl-4,5-dihydrofurans with hydrazines or hydroxylamine was developed. Further transformation of the alcohol moiety in 2-(pyrazolyl)ethanols affording 2-(pyrazolyl)ethylamine as potent bioactive compounds as well as pyrazole-substituted derivatives of antitumor alkaloid crispine A was elaborated.

  12. Dual-purpose linker for alpha helix stabilization and imaging agent conjugation to glucagon-like peptide-1 receptor ligands.

    Science.gov (United States)

    Zhang, Liang; Navaratna, Tejas; Liao, Jianshan; Thurber, Greg M

    2015-02-18

    Peptides display many characteristics of efficient imaging agents such as rapid targeting, fast background clearance, and low non-specific cellular uptake. However, poor stability, low affinity, and loss of binding after labeling often preclude their use in vivo. Using glucagon-like peptide-1 receptor (GLP-1R) ligands exendin and GLP-1 as a model system, we designed a novel α-helix-stabilizing linker to simultaneously address these limitations. The stabilized and labeled peptides showed an increase in helicity, improved protease resistance, negligible loss or an improvement in binding affinity, and excellent in vivo targeting. The ease of incorporating azidohomoalanine in peptides and efficient reaction with the dialkyne linker enable this technique to potentially be used as a general method for labeling α helices. This strategy should be useful for imaging beta cells in diabetes research and in developing and testing other peptide targeting agents.

  13. Optimizing the relaxivity of GdIII complexes appended to InP/ZnS quantum dots by linker tuning.

    Science.gov (United States)

    Stasiuk, Graeme J; Tamang, Sudarsan; Imbert, Daniel; Gateau, Christelle; Reiss, Peter; Fries, Pascal; Mazzanti, Marinella

    2013-06-21

    Three bimodal MRI/optical nanosized contrast agents with high per-nanoparticle relaxivity (up to 2523 mM(-1) s(-1) at 35 MHz and 932 mM(-1) s(-1) at 200 MHz) have been prepared connecting up to 115 tris-aqua Gd(III) complexes to fluorescent non-toxic InP/ZnS quantum dots. The structure of the linker has an important effect on the relaxivity of the final multimeric contrast agent.

  14. A Small Number of Residues Can Determine if Linker Histones Are Bound On or Off Dyad in the Chromatosome.

    Science.gov (United States)

    Zhou, Bing-Rui; Feng, Hanqiao; Ghirlando, Rodolfo; Li, Shipeng; Schwieters, Charles D; Bai, Yawen

    2016-10-09

    Linker histones bind to the nucleosome and regulate the structure and function of chromatin. We have previously shown that the globular domains of chicken H5 and Drosophila H1 linker histones bind to the nucleosome with on- or off-dyad modes, respectively. To explore the determinant for the distinct binding modes, we investigated the binding of a mutant globular domain of H5 to the nucleosome. This mutant, termed GH5_pMut, includes substitutions of five globular domain residues of H5 with the corresponding residues in the globular domain of Drosophila H1. The residues at these five positions play important roles in nucleosome binding by either H5 or Drosophila H1. NMR and spin-labeling experiments showed that GH5_pMut bound to the nucleosome off the dyad. We further found that the nucleosome array condensed by either the GH5_pMut or the globular domain of Drosophila H1 displayed a similar sedimentation coefficient, whereas the same nucleosome array condensed by the wild-type globular domain of H5 showed a much larger sedimentation coefficient. Moreover, NMR and spin-labeling results from the study of the nucleosome in complex with the full-length human linker histone H1.0, whose globular domain shares high sequence conservation with the corresponding globular domain of H5, are consistent with an on-dyad binding mode. Taken together, our results suggest that a small number of residues in the globular domain of a linker histone can control its binding location on the nucleosome and higher-order chromatin structure. Copyright © 2016. Published by Elsevier Ltd.

  15. Design of Tail-Clamp Peptide Nucleic Acid Tethered with Azobenzene Linker for Sequence-Specific Detection of Homopurine DNA

    Directory of Open Access Journals (Sweden)

    Shinjiro Sawada

    2017-10-01

    Full Text Available DNA carries genetic information in its sequence of bases. Synthetic oligonucleotides that can sequence-specifically recognize a target gene sequence are a useful tool for regulating gene expression or detecting target genes. Among the many synthetic oligonucleotides, tail-clamp peptide nucleic acid (TC-PNA offers advantages since it has two homopyrimidine PNA strands connected via a flexible ethylene glycol-type linker that can recognize complementary homopurine sequences via Watson-Crick and Hoogsteen base pairings and form thermally-stable PNA/PNA/DNA triplex structures. Here, we synthesized a series of TC-PNAs that can possess different lengths of azobenzene-containing linkers and studied their binding behaviours to homopurine single-stranded DNA. Introduction of azobenzene at the N-terminus amine of PNA increased the thermal stability of PNA-DNA duplexes. Further extension of the homopyrimidine PNA strand at the N-terminus of PNA-AZO further increased the binding stability of the PNA/DNA/PNA triplex to the target homopurine sequence; however, it induced TC-PNA/DNA/TC-PNA complex formation. Among these TC-PNAs, 9W5H-C4-AZO consisting of nine Watson-Crick bases and five Hoogsteen bases tethered with a beta-alanine conjugated azobenzene linker gave a stable 1:1 TC-PNA/ssDNA complex and exhibited good mismatch recognition. Our design for TC-PNA-AZO can be utilized for detecting homopurine sequences in various genes.

  16. Identification of Epithelial-Mesenchymal Transition-related Target Genes Induced by the Mutation of Smad3 Linker Phosphorylation

    Science.gov (United States)

    Park, Sujin; Yang, Kyung-Min; Park, Yuna; Hong, Eunji; Hong, Chang Pyo; Park, Jinah; Pang, Kyoungwha; Lee, Jihee; Park, Bora; Lee, Siyoung; An, Haein; Kwak, Mi-Kyung; Kim, Junil; Kang, Jin Muk; Kim, Pyunggang; Xiao, Yang; Nie, Guangjun; Ooshima, Akira

    2018-01-01

    Background Smad3 linker phosphorylation plays essential roles in tumor progression and metastasis. We have previously reported that the mutation of Smad3 linker phosphorylation sites (Smad3-Erk/Pro-directed kinase site mutant constructs [EPSM]) markedly reduced the tumor progression while increasing the lung metastasis in breast cancer. Methods We performed high-throughput RNA-Sequencing of the human prostate cancer cell lines infected with adenoviral Smad3-EPSM to identify the genes regulated by Smad3-EPSM. Results In this study, we identified genes which are differentially regulated in the presence of Smad3-EPSM. We first confirmed that Smad3-EPSM strongly enhanced a capability of cell motility and invasiveness as well as the expression of epithelial-mesenchymal transition marker genes, CDH2, SNAI1, and ZEB1 in response to TGF-β1 in human pancreatic and prostate cancer cell lines. We identified GADD45B, CTGF, and JUNB genes in the expression profiles associated with cell motility and invasiveness induced by the Smad3-EPSM. Conclusions These results suggested that inhibition of Smad3 linker phosphorylation may enhance cell motility and invasiveness by inducing expression of GADD45B, CTGF, and JUNB genes in various cancers. PMID:29629343

  17. Butane-1,2,3,4-tetraol-based amphiphilic stereoisomers for membrane protein study: importance of chirality in the linker region

    DEFF Research Database (Denmark)

    Das, Manabendra; Du, Yang; Mortensen, Jonas S.

    2017-01-01

    of the targeted membrane proteins depending on the chirality of the linker region. These findings indicate an important role for detergent stereochemistry in membrane protein stabilization. In addition, we generally observed enhanced detergent efficacy with increasing alkyl chain length, reinforcing...

  18. Key study on the potential of hydrazine bisborane for solid- and liquid-state chemical hydrogen storage.

    Science.gov (United States)

    Pylypko, Sergii; Petit, Eddy; Yot, Pascal G; Salles, Fabrice; Cretin, Marc; Miele, Philippe; Demirci, Umit B

    2015-05-04

    Hydrazine bisborane N2H4(BH3)2 (HBB; 16.8 wt %) recently re-emerged as a potential hydrogen storage material. However, such potential is controversial: HBB was seen as a hazardous compound up to 2010, but now it would be suitable for hydrogen storage. In this context, we focused on fundamentals of HBB because they are missing in the literature and should help to shed light on its effective potential while taking into consideration any risk. Experimental/computational methods were used to get a complete characterization data sheet, including, e.g., XRD, NMR, FTIR, Raman, TGA, and DSC. From the reported results and discussion, it is concluded that HBB has potential in the field of chemical hydrogen storage given that both thermolytic and hydrolytic dehydrogenations were analyzed. In solid-state chemical hydrogen storage, it cannot be used in the pristine state (risk of explosion during dehydrogenation) but can be used for the synthesis of derivatives with improved dehydrogenation properties. In liquid-state chemical hydrogen storage, it can be studied for room-temperature dehydrogenation, but this requires the development of an active and selective metal-based catalyst. HBB is a thus a candidate for chemical hydrogen storage.

  19. Removal of Lead from Water Using Calcium Alginate Beads Doped with Hydrazine Sulphate-Activated Red Mud as Adsorbent

    Directory of Open Access Journals (Sweden)

    A. Naga Babu

    2017-01-01

    Full Text Available Calcium alginate beads doped with hydrazine sulphate-treated red mud are investigated as adsorbent for extracting lead ions from water using batch methods of extraction. Different extraction conditions are optimised for maximum lead extraction. Substantial amount of lead is removed, and the adsorption ability is found to be 138.6 mg/g. Surface characterization using FTIR, EDX, and FESEM confirms that lead is “onto” the surface of the adsorbent. Thermodynamic parameters, adsorption isotherms, and kinetics of adsorption are analysed. Adsorption is “physisorption” in nature and spontaneous. The adsorbent developed can be regenerated using 0.1 M HCl. Thus regenerated adsorbent can be used as the adsorbent for further removal of lead at least 10 times, and this enables the complete removal of lead from water by repetitive use of the regenerated adsorbent. The beads facilitate the easy filtration. The methodology developed is successfully applied for removing lead from industrial waste waters.

  20. Hydrazine-Assisted Formation of Indium Phosphide (InP)-Based Nanowires and Core-Shell Composites.

    Science.gov (United States)

    Patzke, Greta R; Kontic, Roman; Shiolashvili, Zeinab; Makhatadze, Nino; Jishiashvili, David

    2012-12-27

    Indium phosphide nanowires (InP NWs) are accessible at 440 °C from a novel vapor phase deposition approach from crystalline InP sources in hydrazine atmospheres containing 3 mol % H₂O. Uniform zinc blende (ZB) InP NWs with diameters around 20 nm and lengths up to several tens of micrometers are preferably deposited on Si substrates. InP particle sizes further increase with the deposition temperature. The straightforward protocol was extended on the one-step formation of new core-shell InP-Ga NWs from mixed InP/Ga source materials. Composite nanocables with diameters below 20 nm and shells of amorphous gallium oxide are obtained at low deposition temperatures around 350 °C. Furthermore, InP/Zn sources afford InP NWs with amorphous Zn/P/O-coatings at slightly higher temperatures (400 °C) from analogous setups. At 450 °C, the smooth outer layer of InP-Zn NWs is transformed into bead-shaped coatings. The novel combinations of the key semiconductor InP with isotropic insulator shell materials open up interesting application perspectives in nanoelectronics.

  1. Hydrazine functionalized probes for chromogenic and fluorescent ratiometric sensing of pH and F-: experimental and DFT studies.

    Science.gov (United States)

    Roy Chowdhury, Additi; Mondal, Amita; Roy, Biswajit Gopal; K, Jagadeesh C Bose; Mukhopadhyay, Sudit; Banerjee, Priyabrata

    2017-11-08

    Two novel hydrazine based sensors, BPPIH (N 1 ,N 3 -bis(perfluorophenyl)isophthalohydrazide) and BPBIH (N 1' ,N 3' -bis(perfluorobenzylidene)isophthalohydrazide), are presented here. BPPIH is found to be a highly sensitive pH sensor in the pH range 5.0 to 10.0 in a DMSO-water solvent mixture with a pK a value of 9.22. Interesting optical responses have been observed for BPPIH in the above mentioned pH range. BPBIH on the other hand turns out to be a less effective pH sensor in the above mentioned pH range. The increase in fluorescence intensity at a lower pH for BPPIH was explained by using density functional theory. The ability of BPPIH to monitor the pH changes inside cancer cells is a useful application of the sensor as a functional material. In addition fluoride (F - ) selectivity studies of these two chemosensors have been performed and show that between them, BPBIH shows greater selectivity towards F - . The interaction energy calculated from the DFT-D3 supports the experimental findings. The pH sensor (BPPIH) can be further interfaced with suitable circuitry interfaced with desired programming for ease of access and enhancement of practical applications.

  2. Corrosion of carbon steel and low-alloy steel in diluted seawater containing hydrazine under gamma-rays irradiation

    International Nuclear Information System (INIS)

    Nakano, Junichi; Yamamoto, Masahiro; Tsukada, Takashi

    2014-01-01

    Seawater was injected into reactor cores of Units 1, 2, and 3 in the Fukushima Daiichi nuclear power station as an urgent coolant. It is considered that the injected seawater causes corrosion of steels of the reactor pressure vessel and primary containment vessel. To investigate the effects of gamma-rays irradiation on weight loss in carbon steel and low-alloy steel, corrosion tests were performed in diluted seawater at 50°C under gamma-rays irradiation. Specimens were irradiated with dose rates of 4.4 kGy/h and 0.2 kGy/h. To evaluate the effects of hydrazine (N 2 H 4 ) on the reduction of oxygen and hydrogen peroxide, N 2 H 4 was added to the diluted seawater. In the diluted seawater without N 2 H 4 , weight loss in the steels irradiated with 0.2 kGy/h was similar to that in the unirradiated steels, and weight loss in the steels irradiated with 4.4 kGy/h increased to approximate 1.7 times of those in the unirradiated steels. Weight loss in the steels irradiated in the diluted seawater containing N 2 H 4 was similar to that in the diluted seawater without N 2 H 4 . When N 2 was introduced into the gas phase in the flasks during gamma-rays irradiation, weight loss in the steels decreased. (author)

  3. Effect of dissolved oxygen, hydrazine and pH outside the crevice on the galvanic corrosion of support plate alloys

    International Nuclear Information System (INIS)

    McKubre, M.C.H.

    1985-01-01

    A study has been performed of the initial corrosion of support structure alloys in crevices of various geometries, when galvanically coupled to alloy 600. Corrosion rates were monitored continuously by measuring the galvanic current flowing in each couple, transduced by a zero impedance ammeter. Experiments were performed in a single-pass flowing electrolyte system, with AVT water pumped through alloy 600 tubing past the orifice of each crevice. Fourteen crevices were studied simultaneously in two parallel flow arms containing seven specimens each. The steady state AVT water pH/hydrazine/oxygen concentrations were controlled by microcomputer, allowing the effect of secondary water chemistry on the corrosion rate to be studied easily. Control of the crevice electrolyte composition was achieved by separately pumping electrolyte, at a low rate, directly into the crevices of the seven specimens in the lower flow arm. In addition, a high pressure syringe was used to introduce chemicals directly into the secondary or crevice electrolyte flow streams, in order to rapidly evaluate the influence of potential corrodent or corrosion control agents on the galvanic corrosion rates. Specimens were studied in the five basic geometries

  4. Mutations in B3GALT6, which Encodes a Glycosaminoglycan Linker Region Enzyme, Cause a Spectrum of Skeletal and Connective Tissue Disorders

    OpenAIRE

    Nakajima, Masahiro; Mizumoto, Shuji; Miyake, Noriko; Kogawa, Ryo; Iida, Aritoshi; Ito, Hironori; Kitoh, Hiroshi; Hirayama, Aya; Mitsubuchi, Hiroshi; Miyazaki, Osamu; Kosaki, Rika; Horikawa, Reiko; Lai, Angeline; Mendoza-Londono, Roberto; Dupuis, Lucie

    2013-01-01

    Proteoglycans (PGs) are a major component of the extracellular matrix in many tissues and function as structural and regulatory molecules. PGs are composed of core proteins and glycosaminoglycan (GAG) side chains. The biosynthesis of GAGs starts with the linker region that consists of four sugar residues and is followed by repeating disaccharide units. By exome sequencing, we found that B3GALT6 encoding an enzyme involved in the biosynthesis of the GAG linker region is responsible for a sever...

  5. Engineering of a novel Ca2+-regulated kinesin molecular motor using a calmodulin dimer linker

    International Nuclear Information System (INIS)

    Shishido, Hideki; Maruta, Shinsaku

    2012-01-01

    Highlights: ► Engineered kinesin–M13 and calmodulin involving single cysteine were prepared. ► CaM mutant was cross-linked to dimer by bifunctional thiol reactive reagent. ► Kinesin–M13 was dimerized via CaM dimer in the presence of calcium. ► Function of the engineered kinesin was regulated by a Ca 2+ -calmodulin dimer linker. -- Abstract: The kinesin–microtubule system holds great promise as a molecular shuttle device within biochips. However, one current barrier is that such shuttles do not have “on–off” control of their movement. Here we report the development of a novel molecular motor powered by an accelerator and brake system, using a kinesin monomer and a calmodulin (CaM) dimer. The kinesin monomer, K355, was fused with a CaM target peptide (M13 peptide) at the C-terminal part of the neck region (K355–M13). We also prepared CaM dimers using CaM mutants (Q3C), (R86C), or (A147C) and crosslinkers that react with cysteine residues. Following induction of K355–M13 dimerization with CaM dimers, we measured K355–M13 motility and found that it can be reversibly regulated in a Ca 2+ -dependent manner. We also found that velocities of K355–M13 varied depending on the type and crosslink position of the CaM dimer used; crosslink length also had a moderate effect on motility. These results suggest Ca 2+ -dependent dimerization of K355–M13 could be used as a novel molecular shuttle, equipped with an accelerator and brake system, for biochip applications.

  6. Preparation and in vivo evaluation of a novel stabilized linker for 211At labeling of protein

    International Nuclear Information System (INIS)

    Talanov, Vladimir S.; Garmestani, Kayhan; Regino, Celeste A.S.; Milenic, Diane E.; Plascjak, Paul S.; Waldmann, Thomas A.; Brechbiel, Martin W.

    2006-01-01

    Significant improvement of in vivo stability of 211 At-labeled radioimmunoconjugates achieved upon employment of a recently reported new linker, succinimidyl N-2-(4-[ 211 At]astatophenethyl)succinamate (SAPS), prompted additional studies of its chemistry. The 211 At radiolabeling of succinimidyl N-2-(4-tributylstannylphenethyl)succinamate (1) was noted to decline after storage at -15 o C for greater than 6 months. Compound 1 was found to degrade via a ring closure reaction with the formation of N-2-(4-tributylstannylphenethyl)succinimide (3), and a modified procedure for the preparation of 1 was developed. The N-methyl structural analog of 1, succinimidyl N-2-(4-tributylstannylphenethyl)-N-methyl succinamate (SPEMS), was synthesized to investigate the possibility of improving the stability of reagent-protein linkage chemistry. Radiolabeling of SPEMS with 211 At generates succinimidyl N-2-(4-[ 211 At]astatophenethyl)-N-methyl succinamate (Methyl-SAPS), with yields being consistent for greater than 1 year. Radiolabelings of 1 and SPEMS with 125 I generated succinimidyl N-2-(4-[ 125 I]iodophenethyl)succinamate (SIPS) and succinimidyl N-2-(4-[ 125 I]iodophenethyl)-N-methyl succinamate (Methyl-SIPS), respectively, and showed no decline in yields. Methyl-SAPS, SAPS, Methyl-SIPS and SIPS were conjugated to Herceptin for a comparative assessment in LS-174T xenograft-bearing mice. The conjugates of Herceptin with Methyl-SAPS or Methyl-SIPS demonstrated immunoreactivity equivalent to if not superior to the SAPS and SIPS paired analogs. The in vivo studies also revealed that the N-methyl modification resulted in a superior statinated product

  7. X-ray-enhanced cancer cell migration requires the linker of nucleoskeleton and cytoskeleton complex.

    Science.gov (United States)

    Imaizumi, Hiromasa; Sato, Katsutoshi; Nishihara, Asuka; Minami, Kazumasa; Koizumi, Masahiko; Matsuura, Nariaki; Hieda, Miki

    2018-04-01

    The linker of nucleoskeleton and cytoskeleton (LINC) complex is a multifunctional protein complex that is involved in various processes at the nuclear envelope, including nuclear migration, mechanotransduction, chromatin tethering and DNA damage response. We recently showed that a nuclear envelope protein, Sad1 and UNC84 domain protein 1 (SUN1), a component of the LINC complex, has a critical function in cell migration. Although ionizing radiation activates cell migration and invasion in vivo and in vitro, the underlying molecular mechanism remains unknown. Here, we examined the involvement of the LINC complex in radiation-enhanced cell migration and invasion. A sublethal dose of X-ray radiation promoted human breast cancer MDA-MB-231 cell migration and invasion, whereas carbon ion beam radiation suppressed these processes in a dose-dependent manner. Depletion of SUN1 and SUN2 significantly suppressed X-ray-enhanced cell migration and invasion. Moreover, depletion or overexpression of each SUN1 splicing variant revealed that SUN1_888 containing 888 amino acids of SUN1 but not SUN1_916 was required for X-ray-enhanced migration and invasion. In addition, the results suggested that X-ray irradiation affected the expression level of SUN1 splicing variants and a SUN protein binding partner, nesprins. Taken together, our findings supported that the LINC complex contributed to photon-enhanced cell migration and invasion. © 2018 The Authors. Cancer Science published by John Wiley & Sons Australia, Ltd on behalf of Japanese Cancer Association.

  8. Distribution of linker histone variants during plant cell differentiation in the developmental zones of the maize root, dedifferentiation in callus culture after auxin treatment

    Directory of Open Access Journals (Sweden)

    ANASTASIOS ALATZAS

    2008-01-01

    Full Text Available Although several linker histone variants have been studied in both animal and plant organisms, little is known about their distribution during processes that involve alterations in chromatin function, such as differentiation, dedifferentiation and hormone treatment. In this study, we identified linker histone variants by using specific anti-histone Hl antibodies. Each variant's ratio to total Hl in the three developmental zones of maize (Zea mays L. root and in callus cultures derived from them was estimated in order to define possible alterations either during plant cell differentiation or during their dedifferentiation. We also evaluated linker histone variants' ratios in the developmental zones of maize roots treated with auxin in order to examine the effects of exogenous applied auxin to linker histone variant distribution. Finally, immunohistochemical detection was used to identify the root tissues containing each variant and correlate them with the physiological status of the plant cells. According to the results presented in this study, linker histone variants' ratios are altered in the developmental zones of maize root, while they are similar to the meristematic zone in samples from callus cultures and to the differentiation zone in samples from roots treated with auxin. We propose that the alterations in linker histone variants' ratios are correlated with plant cell differentiation and dedifferentiation.

  9. Substitution of the Lys linker with the β-Ala linker dramatically decreased the renal uptake of 99mTc-labeled Arg-X-Asp-conjugated and X-Ala-Asp-conjugated α-melanocyte stimulating hormone peptides.

    Science.gov (United States)

    Flook, Adam M; Yang, Jianquan; Miao, Yubin

    2014-11-13

    The purpose of this study was to examine whether the substitution of the Lys linker with the β-Ala could reduce the renal uptake of (99m)Tc-labeled Arg-X-Asp-conjugated and X-Ala-Asp-conjugated α-melanocyte stimulating hormone (α-MSH) peptides. RSD-β-Ala-(Arg(11))CCMSH (1) {c[Arg-Ser-Asp-dTyr-Asp]-β-Ala-Cys-Cys-Glu-His-dPhe-Arg-Trp-Cys-Arg-Pro-Val-NH2}, RTD-β-Ala-(Arg(11))CCMSH (2), RVD-β-Ala-(Arg(11))CCMSH (3), RAD-β-Ala-(Arg(11))CCMSH (4), NAD-β-Ala-(Arg(11))CCMSH (5), and EAD-β-Ala-(Arg(11))CCMSH (6) peptides were synthesized and evaluated for their melanocortin 1 (MC1) receptor binding affinities in B16/F1 melanoma cells. The biodistribution of their (99m)Tc-conjugates were determined in B16/F1 melanoma-bearing C57 mice. The substitution of the Lys linker with β-Ala linker dramatically reduced the renal uptake of all six (99m)Tc-peptides. (99m)Tc-4 exhibited the highest melanoma uptake (15.66 ± 6.19% ID/g) and the lowest kidney uptake (20.18 ± 3.86% ID/g) among these (99m)Tc-peptides at 2 h postinjection. The B16/F1 melanoma lesions could be clearly visualized by single photon emission computed tomography (SPECT)/CT using (99m)Tc-4 as an imaging probe.

  10. Fabrication of electrospun HPGL scaffolds via glycidyl methacrylate cross-linker: Morphology, mechanical and biological properties

    Energy Technology Data Exchange (ETDEWEB)

    Baratéla, Fernando José Costa; Zazuco Higa, Olga [Biotechnology Center, Institute of Energy and Nuclear Research (IPEN), Av. Professor Lineu Prestes 2242, 05508-000 São Paulo, SP (Brazil); Duarte dos Passos, Esdras [PostGraduate Program in Materials for Engineering, Federal University of Itajubá (UNIFEI), Av. BPS 1303, 37500-903 Itajubá, MG (Brazil); Alencar de Queiroz, Alvaro Antonio, E-mail: alencar@unifei.edu.br [Physics and Chemistry Institute (IFQ), Federal University of Itajubá (UNIFEI), Av. BPS 1303, 37500-903 Itajubá, MG (Brazil); High Voltage Laboratory (LAT-EFEI), Federal University of Itajubá (UNIFEI), Av. BPS 1303, 37500-903 Itajubá, MG (Brazil)

    2017-04-01

    Electrospinning is a suitable method to produce scaffolds composed of nanoscale to microscale fibers, which are comparable to the extracellular matrix (ECM). Hyperbranched polyglycerol (HPGL) is a highly biocompatible polyether polyol potentially useful for the design of fibrous scaffolds mimicking the ECM architecture. However, scaffolds developed from HPGL have poor mechanical properties and morphological stability in the aqueous environments required for tissue engineering applications. This work reports the production of stable electrospun HPGL scaffolds (EHPGLS) using glycidyl methacrylate (GMA) as cross-linker to enhance the water stability and mechanical property of electrospun HPGL. The diameter and morphology of the produced EHPGLS were analyzed by scanning electron microscopy (SEM). It was observed that electrical fields in the range of 0.2 kV·cm{sup −1} to 1.0 kV·cm{sup −1} decrease the average fiber diameter of EHPGLS. The increase in porosity of EHPGLS with GMA concentration indicates the in situ formation of a heterogeneous structure resultant from the phase separation during crosslinking of HPGL by GMA. EHPGLS containing 20% (w/w) GMA concentration possessed highest tensile strength (295.4 ± 11.32 kPa), which is approximately 58 times higher than that of non-crosslinked EHPGLS (5.1 ± 2.12 kPa). The MTS cell viability results showed that the EHPGLS have no significant cytotoxicity effect on Chinese hamster ovary (CHO-K1) cells. Scanning electron microscopy (SEM) indicates that the cultured BALB/3T3 fibroblasts cells were able to keep contact each other's, thus forming a homogeneous monolayer on the internal surface of the EHPGLS. - Highlights: • A hyperbranched polyglycerol (HPGL) scaffold with elastic modulus of 295.4 ± 11.32 kPa was developed for soft tissue repair. • HPGL scaffold was prepared by electrospinning method. • The porosity of HPGL scaffolds can be tuned by selecting the degree of GMA in HPGL. • Electrospun HPGL

  11. Integrity of the Linker of Nucleoskeleton and Cytoskeleton Is Required for Efficient Herpesvirus Nuclear Egress.

    Science.gov (United States)

    Klupp, Barbara G; Hellberg, Teresa; Granzow, Harald; Franzke, Kati; Dominguez Gonzalez, Beatriz; Goodchild, Rose E; Mettenleiter, Thomas C

    2017-10-01

    Herpesvirus capsids assemble in the nucleus, while final virion maturation proceeds in the cytoplasm. This requires that newly formed nucleocapsids cross the nuclear envelope (NE), which occurs by budding at the inner nuclear membrane (INM), release of the primary enveloped virion into the perinuclear space (PNS), and subsequent rapid fusion with the outer nuclear membrane (ONM). During this process, the NE remains intact, even at late stages of infection. In addition, the spacing between the INM and ONM is maintained, as is that between the primary virion envelope and nuclear membranes. The linker of nucleoskeleton and cytoskeleton (LINC) complex consists of INM proteins with a luminal SUN (Sad1/UNC-84 homology) domain connected to ONM proteins with a KASH (Klarsicht, ANC-1, SYNE homology) domain and is thought to be responsible for spacing the nuclear membranes. To investigate the role of the LINC complex during herpesvirus infection, we generated cell lines constitutively expressing dominant negative (dn) forms of SUN1 and SUN2. Ultrastructural analyses revealed a significant expansion of the PNS and the contiguous intracytoplasmic lumen, most likely representing endoplasmic reticulum (ER), especially in cells expressing dn-SUN2. After infection, primary virions accumulated in these expanded luminal regions, also very distant from the nucleus. The importance of the LINC complex was also confirmed by reduced progeny virus titers in cells expressing dn-SUN2. These data show that the intact LINC complex is required for efficient nuclear egress of herpesviruses, likely acting to promote fusion of primary enveloped virions with the ONM. IMPORTANCE While the viral factors for primary envelopment of nucleocapsids at the inner nuclear membrane are known to the point of high-resolution structures, the roles of cellular components and regulators remain enigmatic. Furthermore, the machinery responsible for fusion with the outer nuclear membrane is unsolved. We show here

  12. Hydrazine-based synergistic Ti(III)/N doping of surfactant-templated TiO{sub 2} thin films for enhanced visible light photocatalysis

    Energy Technology Data Exchange (ETDEWEB)

    Islam, Syed Z.; Rankin, Stephen E., E-mail: srankin@engr.uky.edu

    2016-10-01

    This study reports the preparation of titanium (Ti{sup 3+}) and nitrogen co-doped cubic ordered mesoporous TiO{sub 2} thin films using N{sub 2}H{sub 4} treatment. The resulting co-doped TiO{sub 2} (Ti{sup 3+}-N-TiO{sub 2}) thin films show significant enhancements in visible light absorption and photocatalytic activity. Cubic ordered mesoporous TiO{sub 2} thin films were prepared via a sol-gel method with Pluronic F127 as the pore template. After brief calcination, the TiO{sub 2} films were dipped into hydrazine hydrate which acts both as a nitrogen source and as a reducing agent, followed by heating at low temperature (90 °C). The hydrazine treatment period was varied from 5 to 20 h to obtain different degrees of reduction and nitrogen doping. X-ray photoelectron spectroscopy (XPS) analyses and UV–vis absorbance spectra of Ti{sup 3+}-N-TiO{sub 2} films indicate that the incorporated N atoms and Ti{sup 3+} reduce the band gap of TiO{sub 2} and thus enhance the absorption of visible light. The corresponding visible light photocatalytic activity of Ti{sup 3+}-N-TiO{sub 2} films was determined from the photocatalytic degradation of methylene blue under visible light illumination (at 455 nm). The Ti{sup 3+}-N-TiO{sub 2} films prepared with 10 h of treatment show the optimum photocatalytic activity, with a pseudo-first order rate coefficient of 0.12 h{sup −1}, which is 3 times greater than that of undoped TiO{sub 2} films. Calcination temperature and time were varied prior to hydrazine treatment to confirm that a brief calcination at low temperature (10 min at 350 °C) gave the best photochemical activity. In photoelectrochemical water oxidation using a 455 nm LED, the Ti{sup 3+}-N-TiO{sub 2} films prepared with 10 h of N{sub 2}H{sub 4} treatment show about 4 times the photocurrent compared to undoped TiO{sub 2} films. The present study suggests that hydrazine induced doping is a promising approach to enable synergistic incorporation of N and Ti{sup 3+} into the

  13. Structural Polymorphism of the Actin-Espin System: A Prototypical System of Filaments and Linkers in Stereocilia

    International Nuclear Information System (INIS)

    Purdy, Kirstin R.; Wong, Gerard C. L.; Bartles, James R.

    2007-01-01

    We examine the interaction between cytoskeletal F-actin and espin 3A, a prototypical actin bundling protein found in sensory cell microvilli, including ear cell stereocilia. Espin induces twist distortions in F-actin as well as facilitates bundle formation. Mutations in one of the two F-actin binding sites of espin, which have been implicated in deafness, can tune espin-actin interactions and radically transform the system's phase behavior. These results are compared to recent theoretical work on the general phase behavior linker-rod systems

  14. The First Extracellular Linker Is Important for Several Aspects of the Gating Mechanism of Human TRPA1 Channel

    Czech Academy of Sciences Publication Activity Database

    Maršáková, Lenka; Barvík, I.; Zíma, V.; Zímová, Lucie; Vlachová, Viktorie

    2017-01-01

    Roč. 10, Jan 31 (2017), č. článku 16. ISSN 1662-5099 R&D Projects: GA ČR(CZ) GA15-15839S; GA ČR(CZ) GBP304/12/G069; GA MŠk(CZ) EE2.3.30.0025 Institutional support: RVO:67985823 Keywords : TRP channel * S1-S2 linker * allyl isothiocynate * sensor module Subject RIV: FH - Neurology OBOR OECD: Neuroscience s (including psychophysiology Impact factor: 5.076, year: 2016

  15. Micropatterning of biomolecules on a glass substrate in fused silica microchannels by using photolabile linker-based surface activation

    International Nuclear Information System (INIS)

    Jang, K.; Mawatari, K.; Kitamori, T.; Xu, Y.; Sato, K.; Tanaka, Y.

    2012-01-01

    We report on a straightforward method for creating micropatterns of multiple biomolecules. The anti-fouling agent 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer and a photolabile linker (PL) were covalently linked to an amino-terminated silane surface. Patterns were generated by selective removal of the MPC polymer via UV irradiation. Multiple micropatterns of fluorescein isothiocyanate (FITC)-labeled bovine serum albumin (BSA) and rhodamine-labeled goat fragment antigen-binding fragments (FAB) were deposited on a same glass substrate. We also employed micropatterning of multiple biomolecules in that Texas red-labeled BSA and FITC-labeled rabbit anti-mouse IgG were placed inside a microchannel. (author)

  16. Impact of cathepsin B-sensitive triggers and hydrophilic linkers on in vitro efficacy of novel site-specific antibody-drug conjugates.

    Science.gov (United States)

    Bryden, Francesca; Martin, Camille; Letast, Stéphanie; Lles, Eva; Viéitez-Villemin, Inmaculada; Rousseau, Anaïs; Colas, Cyril; Brachet-Botineau, Marie; Allard-Vannier, Emilie; Larbouret, Christel; Viaud-Massuard, Marie-Claude; Joubert, Nicolas

    2018-03-14

    Herein we describe the synthesis and evaluation of four novel HER2-targeting, cathepsin B-sensitive antibody-drug conjugates bearing a monomethylauristatin E (MMAE) cytotoxic payload, constructed via the conjugation of cleavable linkers to trastuzumab using a site-specific bioconjugation methodology. These linkers vary by both cleavable trigger motif and hydrophilicity, containing one of two cathepsin B sensitive dipeptides (Val-Cit and Val-Ala), and engendered with either hydrophilic or hydrophobic character via application of a PEG 12 spacer. Through evaluation of physical properties, in vitro cytotoxicity, and receptor affinity of the resulting antibody-drug conjugates (ADCs), we have demonstrated that while both dipeptide triggers are effective, the increased hydrophobicity of the Val-Ala pair limits its utility within this type of linker. In addition, while PEGylation augments linker hydrophilicity, this change does not translate to more favourable ADC hydrophilicity or potency. While all described structures demonstrated excellent and similar in vitro cytotoxicity, the ADC with the ValCitPABMMAE linker shows the most promising combination of in vitro potency, structural homogeneity, and hydrophilicity, warranting further evaluation into its therapeutic potential.

  17. Preparation, structural analysis and bioactivity of ribonuclease A-albumin conjugate: tetra-conjugation or PEG as the linker.

    Science.gov (United States)

    Li, Chunju; Lin, Qixun; Wang, Jun; Shen, Lijuan; Ma, Guanghui; Su, Zhiguo; Hu, Tao

    2012-12-31

    Ribonuclease A (RNase A) is a therapeutic enzyme with cytotoxic action against tumor cells. Its clinical application is limited by the short half-life and insufficient stability. Conjugation of albumin can overcome the limitation, whereas dramatically decrease the enzymatic activity of RNase A. Here, three strategies were proposed to prepare the RNase A-bovine serum albumin (BSA) conjugates. R-SMCC-B (a conjugate of four RNase A attached with one BSA) and R-PEG-B (a mono-conjugate) were prepared using Sulfo-SMCC (a short bifunctional linker) and mal-PEG-NHS (a bifunctional PEG), respectively. Mal-PEG-NHS and hexadecylamine (HDA) were used to prepare the mono-conjugate, R-HDA-B, where HDA was adopted to bind BSA. The PEG linker can elongate the proximity between RNase A and BSA. In contrast, four RNase A were closely located on BSA in R-SMCC-B. R-SMCC-B showed the lowest K(m) and the highest relative enzymatic activity and k(cat)/K(m) in the three conjugates. Presumably, the tetravalent interaction of RNase A in R-SMCC-B can increase the binding affinity to its substrate. In addition, the slow release of BSA from R-HDA-B may increase the enzymatic activity of R-HDA-B. Our study is expected to provide strategies to develop protein-albumin conjugate with high therapeutic potential. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Wall to membrane linkers, stretch activated channels, and the detection of tension, voltage, temperature, auxin, and pH

    Science.gov (United States)

    Pickard, B. G.

    1992-01-01

    Introduction. The higher plant is a heterogeneous, mechanically prestressed structure continually subject to shifting forces. When a cell grows in a plant at gravitropic equilibrium, it must create localized maxima of shear in walls of neighboring cells. Such mechanical stress and strain are likely detected in a variety of ways. However, tension-sensitive ion channels are of particular interest because it appears that they are elaborately evolved for sensory function. We hypothesize that 1) the patchy patterns of high shear are focused via wall-to-membrane linkers onto the plasma membrane, where 2) they are translated by mechanosensory cation channels into corresponding patterns of high cytosolic Ca2+, which 3) initiate local enhancement of wall expansion. Further, we hypothesize that the local promotion of enhancement is achieved at least in part by local intensification of auxin transport across the plasma membrane. By implication, when an organ is asymmetrically pressed, rubbed, or bent or when it is displaced in the gravitational field, the net asymmetry of shear stress occurring across the organ would lead to asymmetric redistribution of auxin and corrective asymmetric growth. We shall describe a representative mechanosensitive Ca(2+) -selective cation channel (MCaC) with susceptibilities to xenobiotics implicating it as a force transducer in thigmo- and gravitropism. Then, we shall consider whether a putative wall-to-membrane linker (WML) could be a key feature of the molecular architecture permitting the stress distributed in the wall system to be focused on the channels.

  19. Probing the Influence of Linker Length and Flexibility in the Design and Synthesis of New Trehalase Inhibitors

    Directory of Open Access Journals (Sweden)

    Giampiero D’Adamio

    2018-02-01

    Full Text Available This work aims to synthesize new trehalase inhibitors selective towards the insect trehalase versus the porcine trehalase, in view of their application as potentially non-toxic insecticides and fungicides. The synthesis of a new pseudodisaccharide mimetic 8, by means of a stereoselective α-glucosylation of the key pyrrolizidine intermediate 13, was accomplished. The activity of compound 8 as trehalase inhibitor towards C. riparius trehalase was evaluated and the results showed that 8 was active in the μM range and showed a good selectivity towards the insect trehalase. To reduce the overall number of synthetic steps, simpler and more flexible disaccharide mimetics 9–11 bearing a pyrrolidine nucleus instead of the pyrrolizidine core were synthesized. The biological data showed the key role of the linker chain’s length in inducing inhibitory properties, since only compounds 9 (α,β-mixture, bearing a two-carbon atom linker chain, maintained activity as trehalase inhibitors. A proper change in the glucosyl donor-protecting groups allowed the stereoselective synthesis of the β-glucoside 9β, which was active in the low micromolar range (IC50 = 0.78 μM and 12-fold more potent (and more selective than 9α towards the insect trehalase.

  20. Parsing the roles of neck-linker docking and tethered head diffusion in the stepping dynamics of kinesin.

    Science.gov (United States)

    Zhang, Zhechun; Goldtzvik, Yonathan; Thirumalai, D

    2017-11-14

    Kinesin walks processively on microtubules (MTs) in an asymmetric hand-over-hand manner consuming one ATP molecule per 16-nm step. The individual contributions due to docking of the approximately 13-residue neck linker to the leading head (deemed to be the power stroke) and diffusion of the trailing head (TH) that contributes in propelling the motor by 16 nm have not been quantified. We use molecular simulations by creating a coarse-grained model of the MT-kinesin complex, which reproduces the measured stall force as well as the force required to dislodge the motor head from the MT, to show that nearly three-quarters of the step occurs by bidirectional stochastic motion of the TH. However, docking of the neck linker to the leading head constrains the extent of diffusion and minimizes the probability that kinesin takes side steps, implying that both the events are necessary in the motility of kinesin and for the maintenance of processivity. Surprisingly, we find that during a single step, the TH stochastically hops multiple times between the geometrically accessible neighboring sites on the MT before forming a stable interaction with the target binding site with correct orientation between the motor head and the [Formula: see text] tubulin dimer.

  1. Improving the performance of DomainDiscovery of protein domain boundary assignment using inter-domain linker index

    Directory of Open Access Journals (Sweden)

    Zomaya Albert Y

    2006-12-01

    Full Text Available Abstract Background Knowledge of protein domain boundaries is critical for the characterisation and understanding of protein function. The ability to identify domains without the knowledge of the structure – by using sequence information only – is an essential step in many types of protein analyses. In this present study, we demonstrate that the performance of DomainDiscovery is improved significantly by including the inter-domain linker index value for domain identification from sequence-based information. Improved DomainDiscovery uses a Support Vector Machine (SVM approach and a unique training dataset built on the principle of consensus among experts in defining domains in protein structure. The SVM was trained using a PSSM (Position Specific Scoring Matrix, secondary structure, solvent accessibility information and inter-domain linker index to detect possible domain boundaries for a target sequence. Results Improved DomainDiscovery is compared with other methods by benchmarking against a structurally non-redundant dataset and also CASP5 targets. Improved DomainDiscovery achieves 70% accuracy for domain boundary identification in multi-domains proteins. Conclusion Improved DomainDiscovery compares favourably to the performance of other methods and excels in the identification of domain boundaries for multi-domain proteins as a result of introducing support vector machine with benchmark_2 dataset.

  2. Determination of 2-alkylcyclobutanones by combining precolumn derivatization with 1-naphthalenyl hydrazine and ultra-performance liquid chromatography with fluorescence detection.

    Science.gov (United States)

    Meng, Xiangpeng; Tong, Tong; Wang, Lianrong; Liu, Hanxia; Chan, Wan

    2016-05-01

    2-Alkylcyclobutanones (2-ACBs) are uniquely formed when triglycerides-containing food products are exposed to ionizing radiation. Thus, 2-ACBs have been used as marker molecules to identify irradiated food. Most methods to determine 2-ACBs involve mass spectrometric detection after chromatographic separation. The spectrofluorometer is rarely used to determine 2-ACBs because these molecules do not fluoresce. In this study, we developed an ultra-performance liquid chromatography (UPLC) method to determine 2-ACBs. 2-ACBs were converted into fluorophores after reacting with 1-naphthalenyl hydrazine to facilitate their sensitive and selective detection using a fluorescence detector (FLD). Analysis of 2-ACBs using our developed UPLC-FLD method allows sensitive determination of 2-ACBs at a detection limit of 2 ng 2-ACBs per g of fat (30 pg/injection), which is significantly lower than that of existing analytical methods. After validation for trueness and precision, the method was applied to γ-irradiated chicken samples to determine their 2-ACB content. Comparative studies employing liquid chromatography-tandem mass spectrometric method revealed no systematic difference between the two methods, thereby demonstrating that the proposed UPLC-FLD method can be suitably used to determine 2-ACBs in irradiated foodstuffs. Graphical Abstract Determination of radiation-induced food-borne 2-dodecylcyclobutanone and 2-tetradecylcyclobutanone by combining 1-naphthalenyl hydrazine derivatization and ultra-performance liquid chromatography with fluorescence detection.

  3. Synthesis, Structure, and Cyclocondensation of the 4,4,4-Trifluoro-3,3-dihydroxy-2-methyl-1-(thien-2-yl-1-butanone with Hydroxylamine and Hydrazine

    Directory of Open Access Journals (Sweden)

    Alex F. C. Flores

    2018-01-01

    Full Text Available The synthesis of 4,4,4-trifluoro-3,3-dihydroxy-2-methyl-1-(thien-2-ylbutan-1-one (3 through acylation of 1,1-dimethoxy-1-(thien-2-ylpropane (1 with trifluoroacetic anhydride and its reactions with hydroxylamine and hydrazine was investigated. X-ray structural analysis of new trifluoromethyl-substituted dielectrophile 3 revealed that this hydrate exists as a racemate with inter- and intramolecular O-H·O bonds. The crystal structure shows alignment along axis b of pair molecules with the same configuration of the O2-H·O1 bond. For 5(3-trifluoromethyl-4-methyl-3(5-(thien-2-yl-1H-pyrazole (4, obtained via cyclocondensation of precursor 2 and hydrazine hydrochloride, X-ray structural analysis indicated that its rings are almost planar (torsion angle N2-C5-C6-C7–5.4° and that S1 at the thienyl moiety is anti-periplanar to N2 (torsion angle N2-C5-C6-S1 176.01; no disorder effect was observed for the thienyl ring.

  4. Hydrazine-hydrothermal syntheses, characterizations and photoelectrochemical properties of two quaternary chalcogenidoantimonates(III) BaCuSbQ{sub 3} (Q = S, Se)

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Chang; Hou, Peipei [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Chai, Wenxiang [College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Tian, Jiawei; Zheng, Xuerong; Shen, Yaying; Zhi, Mingjia; Zhou, Chunmei [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China); Liu, Yi, E-mail: liuyimse@zju.edu.cn [State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)

    2016-09-15

    Two isostructural quaternary chalcogenidoantimonates(III) BaCuSbQ{sub 3} (Q = S, Se): BaCuSbS{sub 3} (1) and BaCuSbSe{sub 3} (2) have been successfully synthesized through a facile hydrazine-hydrothermal method. Both two compounds crystallize in the orthorhombic space group and feature a three-dimensional (3D) channeled [Cu{sub 2}Sb{sub 2}Q{sub 6}]{sup 4-} framework, which is constructed by the distorted tetrahedral CuQ{sub 4} and pyramid SbQ{sub 3} units via vertex sharing. Both optical properties and theoretical studies show 1 and 2 are semiconductors with narrow band gaps. In addition, their photoelectrochemical properties have been investigated. - Highlights: • BaCuSbQ{sub 3} (Q = S, Se) were synthesized through a hydrazine-hydrothermal method. • BaCuSbQ{sub 3} (Q = S, Se) feature a 3D framework by single-crystal X-ray diffraction. • Experimental and theoretical studies confirm BaCuSbQ{sub 3} (Q = S, Se) are semiconductors. • Photoelectrochemical properties of BaCuSbQ{sub 3} (Q = S, Se) have been investigated.

  5. Preparation of FeO(OH Modified with Polyethylene Glycol and Its Catalytic Activity on the Reduction of Nitrobenzene with Hydrazine Hydrate

    Directory of Open Access Journals (Sweden)

    Ke Ying Cai

    2016-10-01

    Full Text Available Iron oxyhydroxide was prepared by dropping ammonia water to Fe(NO33.9H2O dispersed in polyethylene glycol (PEG 1000. The catalyst was characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and laser particle size analyzer. The results showed the catalyst modified with polyethylene glycol was amorphous. The addition of PEG during the preparation make the particle size of the catalyst was smaller and more uniform. The catalytic performance was tested in the reduction of nitroarenes to corresponding amines with hydrazine hydrate, and the catalyst showed excellent activity and stability. Copyright © 2016 BCREC GROUP. All rights reserved Received: 2nd February 2016; Revised: 26th April 2016; Accepted: 7th June 2016 How to Cite: Cai, K.Y., Liu, Y.S., Song, M., Zhou, Y.M., Liu, Q., Wang, X.H. (2016. Preparation of FeO(OH Modified with Polyethylene Glycol and Its Catalytic Activity on the Reduction of Nitrobenzene with Hydrazine Hydrate. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 363-368 (doi:10.9767/bcrec.11.3.576.363-368 Permalink/DOI: http://doi.org/10.9767/bcrec.11.3.576.363-368

  6. Crystallization and preliminary X-ray analysis of Acetivibrio cellulolyticus cellulosomal type II cohesin module: two versions having different linker lengths

    International Nuclear Information System (INIS)

    Noach, Ilit; Alber, Orly; Bayer, Edward A.; Lamed, Raphael; Levy-Assaraf, Maly; Shimon, Linda J. W.; Frolow, Felix

    2007-01-01

    The cloning, expression, purification, crystallization and preliminary X-ray characterization of two protein constructs of the second type II cohesin module from A. cellulolyticus ScaB are described. Both constructs contain the native N-terminal linker, but only one of them contains the full-length 45-residue C-terminal linker; the other contains a five-residue segment of this linker. The second type II cohesin module of the cellulosomal scaffoldin polypeptide ScaB from Acetivibrio cellulolyticus (CohB2) was cloned into two constructs: one containing a short (five-residue) C-terminal linker (CohB2-S) and the second incorporating the full native 45-residue linker (CohB2-L). Both constructs encode proteins that also include the full native six-residue N-terminal linker. The CohB2-S and CohB2-L proteins were expressed, purified and crystallized in the orthorhombic crystal system, but with different unit cells and symmetries: space group P2 1 2 1 2 1 with unit-cell parameters a = 90.36, b = 68.65, c = 111.29 Å for CohB2-S and space group P2 1 2 1 2 with unit-cell parameters a = 68.76, b = 159.22, c = 44.21 Å for CohB2-L. The crystals diffracted to 2.0 and 2.9 Å resolution, respectively. The asymmetric unit of CohB2-S contains three cohesin molecules, while that of CohB2-L contains two molecules

  7. The linker domain of poly(rC) binding protein 2 is a major determinant in poliovirus cap-independent translation.

    Science.gov (United States)

    Sean, Polen; Nguyen, Joseph H C; Semler, Bert L

    2008-09-01

    Poliovirus, a member of the enterovirus genus in the family Picornaviridae, is the causative agent of poliomyelitis. Translation of the viral genome is mediated through an internal ribosomal entry site (IRES) encoded within the 5' noncoding region (5' NCR). IRES elements are highly structured RNA sequences that facilitate the recruitment of ribosomes for translation. Previous studies have shown that binding of a cellular protein, poly(rC) binding protein 2 (PCBP2), to a major stem-loop structure in the genomic 5' NCR is necessary for the translation of picornaviruses containing type I IRES elements, including poliovirus, coxsackievirus, and human rhinovirus. PCBP1, an isoform that shares approximately 90% amino acid identity to PCBP2, cannot efficiently stimulate poliovirus IRES-mediated translation, most likely due to its reduced binding affinity to stem-loop IV within the poliovirus IRES. The primary differences between PCBP1 and PCBP2 are found in the so-called linker domain between the second and third K-homology (KH) domains of these proteins. We hypothesize that the linker region of PCBP2 augments binding to poliovirus stem-loop IV RNA. To test this hypothesis, we generated six PCBP1/PCBP2 chimeric proteins. The recombinant PCBP1/PCBP2 chimeric proteins were able to interact with poliovirus stem-loop I RNA and participate in protein-protein interactions. We demonstrated that the PCBP1/PCBP2 chimeric proteins with the PCBP2 linker, but not with the PCBP1 linker, were able to interact with poliovirus stem-loop IV RNA, and could subsequently stimulate poliovirus IRES-mediated translation. In addition, using a monoclonal anti-PCBP2 antibody (directed against the PCBP2 linker domain) in mobility shift assays, we showed that the PCBP2 linker domain modulates binding to poliovirus stem-loop IV RNA via a mechanism that is not inhibited by the antibody.

  8. Substitutions in conserved regions preceding and within the linker affect activity and flexibility of tRNase ZL, the long form of tRNase Z.

    Directory of Open Access Journals (Sweden)

    Makenzie Saoura

    Full Text Available The enzyme tRNase Z, a member of the metallo-β-lactamase family, endonucleolytically removes 3' trailers from precursor tRNAs, preparing them for CCA addition and aminoacylation. The short form of tRNase Z, tRNase ZS, functions as a homodimer and is found in all prokaryotes and some eukaryotes. The long form, tRNase ZL, related to tRNase ZS through tandem duplication and found only in eukaryotes, possesses ~2,000-fold greater catalytic efficiency than tRNase ZS. tRNase ZL consists of related but diverged amino and carboxy domains connected by a flexible linker (also referred to as a flexible tether and functions as a monomer. The amino domain retains the flexible arm responsible for substrate recognition and binding while the carboxy domain retains the active site. The linker region was explored by Ala-scanning through two conserved regions of D. melanogaster tRNase Z: NdomTprox, located at the carboxy end of the amino domain proximal to the linker, and Tflex, a flexible site in the linker. Periodic substitutions in a hydrophobic patch (F329 and L332 at the carboxy end of NdomTprox show 2,700 and 670-fold impairment relative to wild type, respectively, accompanied by reduced linker flexibility at N-T inside the Ndom- linker boundary. The Ala substitution for N378 in the Tflex region has 10-fold higher catalytic efficiency than wild type and locally decreased flexibility, while the Ala substitution at R382 reduces catalytic efficiency ~50-fold. These changes in pre-tRNA processing kinetics and protein flexibility are interpreted in light of a recent crystal structure for S. cerevisiae tRNase Z, suggesting transmission of local changes in hydrophobicity into the skeleton of the amino domain.

  9. Yeast linker histone Hho1p is required for efficient RNA polymerase I processivity and transcriptional silencing at the ribosomal DNA

    OpenAIRE

    Levy, Anat; Eyal, Miri; Hershkovits, Gitit; Salmon-Divon, Mali; Klutstein, Michael; Katcoff, Don Jay

    2008-01-01

    Nucleosome core particles in eukaryotes are linked by a stretch of DNA that is usually associated with a linker histone. Here, we show in yeast, that the presence of yeast linker histone Hho1p represses expression of a pol II transcribed gene (MET15) embedded in the rDNA. In vivo deletions of Hho1p sequences showed that the second globular domain is sufficient for that repression, whereas the presence of the N terminus is required for its derepression. In contrast, a run-on assay confirmed by...

  10. Effects of linker variation on the in vitro and in vivo characteristics of an 111In-labeled RGD peptide

    International Nuclear Information System (INIS)

    Dijkgraaf, Ingrid; Liu, Shuang; Kruijtzer, John A.W.; Soede, Annemieke C.; Oyen, Wim J.G.; Liskamp, Rob M.J.; Corstens, Frans H.M.; Boerman, Otto C.

    2007-01-01

    Introduction: Due to the selective expression of the α v β 3 integrin in tumors, radiolabeled arginine-glycine-aspartic acid (RGD) peptides are attractive candidates for tumor targeting. Minor modifications of these peptides could have a major impact on in vivo characteristics. In this study, we systematically investigated the effects of linker modification between two cyclic RGD sequences and DOTA (1,4,7,10-tetraazadodecane-N,N',N ' ,N'''-tetraacetic acid) on the in vitro and in vivo characteristics of the tracer. Methods: A dimeric RGD peptide was synthesized and conjugated either directly with DOTA or via different linkers: PEG 4 (polyethylene glycol), glutamic acid or lysine. The RGD peptides were radiolabeled with 111 In, and their in vitro and in vivo α v β 3 -binding characteristics were determined. Results: LogP values varied between -2.82±0.06 and -3.95±0.33. The IC 50 values for DOTA-E-[c(RGDfK)] 2 , DOTA-PEG 4 -E-[c(RGDfK)] 2 , DOTA-E-E-[c(RGDfK)] 2 and DOTA-K-E-[c(RGDfK)] 2 were comparable. Two hours after injection, the tumor uptakes of the 111 In-labeled compounds were not significantly different. The kidney accumulation of [ 111 In]-DOTA-K-E-[c(RGDfK)] 2 [4.05±0.20% of the injected dose per gram (ID/g)] was significantly higher as compared with that of [ 111 In]-DOTA-E-[c(RGDfK)] 2 (2.63±0.19% ID/g; P 111 In]-DOTA-E-E-[c(RGDfK)] 2 (2.16±0.21% ID/g; P 111 In]-DOTA-E-E-[c(RGDfK)] 2 (2.12±0.09% ID/g) was significantly higher as compared with that of [ 111 In]-DOTA-E-[c(RGDfK)] 2 (1.64±0.1% ID/g; P 111 In]-DOTA-K-E-[c(RGDfK)] 2 (1.52±0.04% ID/g; P v β 3 and tumor uptake. Insertion of lysine caused enhanced kidney retention; that of glutamic acid also resulted in enhanced retention in the kidneys. PEG 4 appeared to be the most suitable linker as compared with glutamic acid and lysine because it has the highest tumor-to-blood ratio and the lowest uptake in the kidney and liver

  11. Hydrazine APU Starter Development.

    Science.gov (United States)

    1983-06-01

    electrical solenoid valve is energized. Flywheel speed is monitored independently of the drive shaft speed (rotor speed) via a photo cell mounted in the...center of the top plate. The photocell detects the passage of a black stripe that is painted on the flywheel. Stall torque is monitored with a load cell ...zi Nt1 0m < -C3C C=, * r C ~ L 13 *36 *Si 0 IP *45 a T a *z a oz *it a *t a i a-a 1381 C,3( ( C ( C rcr ~ (C~rrC .C 6v 20 c, f4- 0 *0 0 04 *0 El 06 *0b

  12. Hydrazine Sulfate (PDQ)

    Science.gov (United States)

    ... NIH). NIH is the federal government’s center of biomedical research. The PDQ summaries are based on an independent ... NCCIH) are sponsoring a number of clinical trials (research studies) at medical centers to test CAM therapies for use in cancer. Conventional approaches to cancer ...

  13. 分子动力学模拟压水反应堆中联氨对水的影响%Molecular dynamics simulation for the impact of hydrazine on the water of pressurized water reactors

    Institute of Scientific and Technical Information of China (English)

    范永胜; 陈旭; 周维; 史顺平; 李勇

    2011-01-01

    本文采用分子动力学方法模拟在常温常压下(1 atm,298 K)和在压水堆环境下(155 atm,626 K),水分子数为256,联氨(N2H4)分子数为0,25,50,75等不同数目时,水和联氨粒子系统的动力性质和微观结构.同时探讨了联氨分子的引入对水中溶解氧的影响.从模拟结果可知,在常温常压下,当联氨的分子数为0,25,50,75时,粒子系统的均方位移会随联氨分子数的增加而增加;联氨分子数为0与为25,50,75比较时会少一个数量级;压水堆环境下,联氨分子数为50时的均方位移比常温常压下高出约4倍,但粒子系统的均方位移不随联氨的分子数增加而增加;联氨分子数为50时的均方位移高于分子数为25和75时的均方位移.此外,粒子系统的微观结构,从径向分布函数看,在常温常压下也会随着联氨分子浓度的增加而增加,这与联氨容易和水反应生成水合联氨的实际情况相符,而在压水堆环境下,联氨分子数为25,50与为0的水比较,径向分布均不会有大的变化,而分子数为75时会出现明显的增加.模拟数据表明,加入压水堆中的联氨对水中的溶解氧有明显的抑制作用,但并不是联氨的浓度越浓抑制作用就越强.对这种现象及其原因进行了较为全面的揭示.%In this paper, we used molecular dynamics to simulate dynamic properties and micro-structure of the water-hydrazine particle system under various conditions: chamber condition of 1 atm, 298 K; pressurized water reactor (PWR)environment of 155 atm, 626 K; with number of water molecules of 256, numbers of hydrazine ( N2H4) molecules of 0,25, 50 and 75. And we have also explored the impact on the dissolved oxygen in water when hydrazine molecule is added to the system. The simulation results show that in the chamber ambient, when the number of molecules of hydrazine varies from 0 to 25, 50 and 75, the mean square displacement (MSD) in the particle system will increase with the number of

  14. CD6 and Linker of Activated T Cells are Potential Interaction Partners for T Cell-Specific Adaptor Protein.

    Science.gov (United States)

    Hem, C D; Ekornhol, M; Granum, S; Sundvold-Gjerstad, V; Spurkland, A

    2017-02-01

    The T cell-specific adaptor protein (TSAd) contains several protein interaction domains, and is merging as a modulator of T cell activation. Several interaction partners for the TSAd proline-rich region and phosphotyrosines have been identified, including the Src and Tec family kinases lymphocyte-specific protein tyrosine kinase and interleukin 2-inducible T cell kinase. Via its Src homology 2 (SH2) domain, TSAd may thus function as a link between these enzymes and other signalling molecules. However, few binding partners to the TSAd SH2 domain in T cells are hitherto known. Through the use of in silico ligand prediction, peptide spot arrays, pull-down and immunoprecipitation experiments, we here report novel interactions between the TSAd SH2 domain and CD6 phosphotyrosine (pTyr) 629 and linker of activated T cells (LAT) pTyr 171 , pTyr 191 and pTyr 226 . © 2016 The Foundation for the Scandinavian Journal of Immunology.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-15

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

  16. Ag2S Quantum Dot-Sensitized Solar Cells by First Principles: The Effect of Capping Ligands and Linkers.

    Science.gov (United States)

    Amaya Suárez, Javier; Plata, Jose J; Márquez, Antonio M; Fernández Sanz, Javier

    2017-09-28

    Quantum dots solar cells, QDSCs, are one of the candidates for being a reliable alternative to fossil fuels. However, the well-studied CdSe and CdTe-based QDSCs present a variety of issues for their use in consumer-goods applications. Silver sulfide, Ag 2 S, is a promising material, but poor efficiency has been reported for QDSCs based on this compound. The potential influence of each component of QDSCs is critical and key for the development of more efficient devices based on Ag 2 S. In this work, density functional theory calculations were performed to study the nature of the optoelectronic properties for an anatase-TiO 2 (101) surface sensitized with different silver sulfide nanoclusters. We demonstrated how it is possible to deeply tune of its electronic properties by modifying the capping ligands and linkers to the surface. Finally, an analysis of the electron injection mechanism for this system is presented.

  17. Regulating repression: roles for the sir4 N-terminus in linker DNA protection and stabilization of epigenetic states.

    Directory of Open Access Journals (Sweden)

    Stephanie Kueng

    Full Text Available Silent information regulator proteins Sir2, Sir3, and Sir4 form a heterotrimeric complex that represses transcription at subtelomeric regions and homothallic mating type (HM loci in budding yeast. We have performed a detailed biochemical and genetic analysis of the largest Sir protein, Sir4. The N-terminal half of Sir4 is dispensable for SIR-mediated repression of HM loci in vivo, except in strains that lack Yku70 or have weak silencer elements. For HM silencing in these cells, the C-terminal domain (Sir4C, residues 747-1,358 must be complemented with an N-terminal domain (Sir4N; residues 1-270, expressed either independently or as a fusion with Sir4C. Nonetheless, recombinant Sir4C can form a complex with Sir2 and Sir3 in vitro, is catalytically active, and has sedimentation properties similar to a full-length Sir4-containing SIR complex. Sir4C-containing SIR complexes bind nucleosomal arrays and protect linker DNA from nucleolytic digestion, but less effectively than wild-type SIR complexes. Consistently, full-length Sir4 is required for the complete repression of subtelomeric genes. Supporting the notion that the Sir4 N-terminus is a regulatory domain, we find it extensively phosphorylated on cyclin-dependent kinase consensus sites, some being hyperphosphorylated during mitosis. Mutation of two major phosphoacceptor sites (S63 and S84 derepresses natural subtelomeric genes when combined with a serendipitous mutation (P2A, which alone can enhance the stability of either the repressed or active state. The triple mutation confers resistance to rapamycin-induced stress and a loss of subtelomeric repression. We conclude that the Sir4 N-terminus plays two roles in SIR-mediated silencing: it contributes to epigenetic repression by stabilizing the SIR-mediated protection of linker DNA; and, as a target of phosphorylation, it can destabilize silencing in a regulated manner.

  18. Gold-copper bimetallic nanoparticles supported on nano P zeolite modified carbon paste electrode as an efficient electrocatalyst and sensitive sensor for determination of hydrazine.

    Science.gov (United States)

    Amiripour, Fatemeh; Azizi, Seyed Naser; Ghasemi, Shahram

    2018-06-01

    In this report, a facile, efficient and low cost electrochemical sensor based on bimetallic Au-Cu nanoparticles supported on P nanozeolite modified carbon paste electrode (Au-Cu/NPZ/CPE) was constructed and its efficiency for determination of hydrazine in trace level was studied. For this purpose, agro waste material, stem sweep ash (SSA) was employed as the starting material (silica source) for the synthesis of nano P zeolite (NPZ). After characterization of the synthesized NPZ by analytical instruments (scanning electronic microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy), construction of Au-Cu/NPZ/CPE was performed by three steps procedure involving preparation of nano P zeolite modified carbon paste electrode (NPZ/CPE), introducing Cu +2 ions into nano zeolite structure by ion exchange and electrochemical reduction of Cu +2 ions upon applying constant potential. This procedure is followed by partial replacement of Cu by Au due to galvanic replacement reaction (GRR). The electrochemical properties of hydrazine at the surface of Au-Cu/NPZ/CPE was evaluated using cyclic voltammetry (CV), amperometry, and chronoamperometry methods in 0.1 M phosphate buffer solution (PBS). It was found that the prepared sensor has higher electrocatalytic activity at a relatively lower potential compared to other modified electrodes including Au/NPZ/CPE, Cu/NPZ/CPE, Au-Cu/CPE and etc. Moreover, the proposed electrochemical sensor presented the favorable analytical properties for determination of hydrazine such as low detection limit (0.04 µM), rapid response time (3 s), wide linear range (0.01-150 mM), and high sensitivity (99.53 µA mM -1 ) that are related to the synergic effect of bimetallic of Au-Cu, porous structure and enough surface area of NPZ. In addition, capability of Au-Cu/NPZ/CPE sensor was successfully tested in real samples with good accuracy and precision. Copyright

  19. Microencapsulation of Epoxidized Linseed Oil Liquid Cross-Linker in Poly(N-vinyl-pyrrolidone): Optimization by a Design-of-Experiments Approach

    NARCIS (Netherlands)

    Senatore, D.; Laven, J.; Benthem, van R.A.T.M.; La Camera, D.; With, de G.

    2010-01-01

    A liquid cross-linker, epoxidized linseed oil (ELO), was encapsulated in a plastic with a high glass transition temperature (poly(N-vinyl-2-pyrrolidone); PVP). The process parameters of the spray-drying employed were optimized by a Design-of-Experiments (DoE) approach. Three factors concerning both

  20. Modulation of procaspase-7 self-activation by PEST amino acid residues of the N-terminal prodomain and intersubunit linker.

    Science.gov (United States)

    Alves, Juliano; Garay-Malpartida, Miguel; Occhiucci, João M; Belizário, José E

    2017-12-01

    Procaspase-7 zymogen polypeptide is composed of a short prodomain, a large subunit (p20), and a small subunit (p10) connected to an intersubunit linker. Caspase-7 is activated by an initiator caspase-8 and -9, or by autocatalysis after specific cleavage at IQAD 198 ↓S located at the intersubunit linker. Previously, we identified that PEST regions made of amino acid residues Pro (P), Glu (E), Asp (D), Ser (S), Thr (T), Asn (N), and Gln (Q) are conserved flanking amino acid residues in the cleavage sites within a prodomain and intersubunit linker of all caspase family members. Here we tested the impact of alanine substitution of PEST amino acid residues on procaspase-7 proteolytic self-activation directly in Escherichia coli. The p20 and p10 subunit cleavage were significantly delayed in double caspase-7 mutants in the prodomain (N18A/P26A) and intersubunit linker (S199A/P201A), compared with the wild-type caspase-7. The S199A/P201A mutants effectively inhibited the p10 small subunit cleavage. However, the mutations did not change the kinetic parameters (k cat /K M ) and optimal tetrapeptide specificity (DEVD) of the purified mutant enzymes. The results suggest a role of PEST-amino acid residues in the molecular mechanism for prodomain and intersubunit cleavage and caspase-7 self-activation.

  1. Micromachined silicon acoustic delay line with 3D-printed micro linkers and tapered input for improved structural stability and acoustic directivity

    International Nuclear Information System (INIS)

    Cho, Y; Kumar, A; Xu, S; Zou, J

    2016-01-01

    Recent studies have shown that micromachined silicon acoustic delay lines can provide a promising solution to achieve real-time photoacoustic tomography without the need for complex transducer arrays and data acquisition electronics. To achieve deeper imaging depth and wider field of view, a longer delay time and therefore delay length are required. However, as the length of the delay line increases, it becomes more vulnerable to structural instability due to reduced mechanical stiffness. In this paper, we report the design, fabrication, and testing of a new silicon acoustic delay line enhanced with 3D printed polymer micro linker structures. First, mechanical deformation of the silicon acoustic delay line (with and without linker structures) under gravity was simulated by using finite element method. Second, the acoustic crosstalk and acoustic attenuation caused by the polymer micro linker structures were evaluated with both numerical simulation and ultrasound transmission testing. The result shows that the use of the polymer micro linker structures significantly improves the structural stability of the silicon acoustic delay lines without creating additional acoustic attenuation and crosstalk. In addition, the improvement of the acoustic acceptance angle of the silicon acoustic delay lines was also investigated to better suppress the reception of unwanted ultrasound signals outside of the imaging plane. These two improvements are expected to provide an effective solution to eliminate current limitations on the achievable acoustic delay time and out-of-plane imaging resolution of micromachined silicon acoustic delay line arrays. (paper)

  2. Synthetic incorporation of Nile Blue into DNA using 2′-deoxyriboside substitutes: Representative comparison of (R- and (S-aminopropanediol as an acyclic linker

    Directory of Open Access Journals (Sweden)

    Daniel Lachmann

    2010-02-01

    Full Text Available The Nile Blue chromophore was incorporated into oligonucleotides using “click” chemistry for the postsynthetic modification of oligonucleotides. These were synthesized using DNA building block 3 bearing an alkyne group and reacted with the azide 4. (R-3-amino-1,2-propanediol was applied as the linker between the phosphodiester bridges. Two sets of DNA duplexes were prepared. One set carried the chromophore in an A-T environment, the second set in a G-C environment. Both were characterized by optical spectroscopy. Sequence-dependent fluorescence quenching was applied as a sensitive tool to compare the stacking interactions with respect to the chirality of the acyclic linker attachment. The results were compared to recent results from duplexes that carried the Nile Blue label in a sequentially and structurally identical context, except for the opposite chirality of the linker ((S-3-amino-1,2-propandiol. Only minor, negligible differences were observed. Melting temperatures, UV–vis absorption spectra together with fluorescence quenching data indicate that Nile Blue stacks perfectly between the adjacent base pairs regardless of whether it has been attached via an S- or R-configured linker. This result was supported by geometrically optimized DNA models.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  4. Traceless Azido Linker for the Solid-Phase Synthesis of NH-1,2,3-Triazoles via Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2010-01-01

    A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibility...

  5. The ortho backbone amide linker (o-BAL) is an easily prepared and highly acid-labile handle for solid-phase synthesis

    DEFF Research Database (Denmark)

    Boas, Ulrik; Brask, Jesper; Christensen, J.B.

    2002-01-01

    The tris(alkoxy)benzyl backbone amide linker (BAL) has found widespread application in solid-phase synthesis. The key intermediate for preparation of para BAL (p-BAL) is 2,6-dimethoxy-4-hydroxybenzaldehyde; several reports on its synthesis have appeared. However, the ortho analogue of the handle (o...

  6. Diols and anions can control the formation of an exciplex between a pyridinium boronic acid with an aryl group connected via a propylene linker.

    Science.gov (United States)

    Huang, Yan-Jun; Jiang, Yun-Bao; Bull, Steven D; Fossey, John S; James, Tony D

    2010-11-21

    The exciplex formation between a pyridinium boronic acid and phenyl group connected via a propylene linker can be monitored using fluorescence. Addition of pinacol affords a cyclic boronate ester with enhanced Lewis acidity that increases the strength of its cation-π stacking interaction causing a four-fold fluorescence enhancement.

  7. Doxorubicin conjugation and drug linker chemistry alter the intravenous and pulmonary pharmacokinetics of a PEGylated Generation 4 polylysine dendrimer in rats.

    Science.gov (United States)

    Leong, Nathania J; Mehta, Dharmini; McLeod, Victoria M; Kelly, Brian D; Pathak, Rashmi; Owen, David J; Porter, Christopher Jh; Kaminskas, Lisa M

    2018-05-28

    PEGylated polylysine dendrimers have demonstrated potential as inhalable drug delivery systems that can improve the treatment of lung cancers. Their treatment potential may be enhanced by developing constructs that display prolonged lung retention, together with good systemic absorption, the capacity to passively target lung tumours from the blood and highly selective, yet rapid liberation in the tumour microenvironment. This study sought to characterise how the nature of cathepsin B cleavable peptide linkers, used to conjugate doxorubicin to a PEGylated (PEG570) G4 polylysine dendrimer, affect drug liberation kinetics and intravenous and pulmonary pharmacokinetics in rats. The construct bearing a self-emolative diglycolic acid-V-Citrulline linker exhibited faster doxorubicin release kinetics compared to constructs bearing self emolative diglycolic acid-GLFG, or non-self emolative glutaric acid-GLFG linkers. The V-Citrulline construct exhibited slower plasma clearance, but faster absorption from the lungs than a GLFG construct, although mucociliary clearance and urinary elimination were unchanged. Doxorubicin-conjugation enhanced localisation in the bronchoalveolar lavage fluid compared to lung tissue, suggesting that projection of doxorubicin from the dendrimer surface reduced tissue uptake. These data show that the linker chemistry employed to conjugate drugs to PEGylated carriers can affect drug release profiles and systemic and lung disposition. Copyright © 2018. Published by Elsevier Inc.

  8. Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling

    Energy Technology Data Exchange (ETDEWEB)

    Rastogi, Shiva K., E-mail: srastogi@uidaho.edu [University of Idaho, Department of Chemistry (United States); Denn, Benjamin D.; Branen, A. Larry [University of Idaho, Coeur D' Alene, Biosensors and Nanotechnology Application Laboratory (BNAL) (United States)

    2012-01-15

    This study demonstrates a one versus two-step synthesis of fluorescent gold quantum dots (F-AuQDs) and nano clusters (F-AuNCs) functionalized with thiolated organic linkers using reduction of gold precursor in N,N Prime -dimethylformamide in 1 h of reaction. The F-AuQDs and F-AuNCs show fluorescence emission at 425 {+-} 5 nm upon excitation at 345 {+-} 5 nm of wavelength, with good water solubility and stability. Five different thiolated organic binary linkers consisting of various functional groups including: carboxylic acid, hydroxyl, and aromatic amine, were conjugated with the F-AuQDs and F-AuNCs. The formation mechanism and functionalization of the F-AuQDs and F-AuNCs was characterized using UV-vis absorption spectra, UV-vis light, fluorescent emission spectra, pH, TEM, and FTIR. The fluorescence emission of the F-AuQDs and F-AuNCs is greatly dependent on the thio-linker. This novel one-step approach provides facile and fast synthesis of F-AuQDs and F-AuNCs over the two-step method, with less than 5 h of reaction and workup compared to more than 28 h of reaction for the two-step approach. These thio-linker functionalized F-AuQDs and F-AuNCs have a wide application in fluorescent labeling of biomolecules, optical devices, imaging, energy transfer, and biosensing.

  9. Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota, E-mail: dorota.maciejewska@wum.edu.pl

    2015-11-01

    Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, {sup 13}C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate

  10. The Effects of Anchor Groups on (1) TiO2-Catalyzed Photooxidation and (2) Linker-Assisted Assembly on TiO2

    Science.gov (United States)

    Anderson, Ian Mark

    Quantum dot-sensitized solar cells (QDSSCs) are a popular target for research due to their potential for highly efficient, easily tuned absorption. Typically, light is absorbed by quantum dots attached to a semiconductor substrate, such as TiO2, via bifunctional linker molecules. This research aims to create a patterned monolayer of linker molecules on a TiO2 film, which would in turn allow the attachment of a patterned layer of quantum dots. One method for the creation of a patterned monolayer is the functionalization of a TiO2 film with a linker molecule, followed by illumination with a laser at 355 nm. This initiates a TiO 2-catalyzed oxidation reaction, causing loss of surface coverage. A second linker molecule can then be adsorbed onto the TiO2 surface in the illuminated area. Towards that end, the behaviors of carboxylic and phosphonic acids adsorbed on TiO2 have been studied. TiO2 films were functionalized by immersion in solutions a single adsorbate and surface coverage was determined by IR spectroscopy. It is shown that phosphonic acids attain higher surface coverage than carboxylic acids, and will displace them from TiO2 when in a polar solvent. Alkyl chain lengths, which can influence stabilities of monolayers, are shown not to have an effect on this relationship. Equilibrium binding data for the adsorption of n-hexadecanoic acid to TiO2 from a THF solution are presented. It is shown that solvent polarity can affect monolayer stability; carboxylates and phosphonates undergo more desorption into polar solvents than nonpolar. Through illumination, it was possible to remove nearly all adsorbed linkers from TiO2. However, the illuminated areas were found not to be receptive to attachment by a second adsorbate. A possible reason for this behavior is presented. I also report on the synthesis and characterization of a straight-chain, thiol-terminated phosphonic acid. Initial experiments involving monolayer formation and quantum dot attachment are presented

  11. Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

    International Nuclear Information System (INIS)

    Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota

    2015-01-01

    Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, 13 C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate). - Highlights:

  12. Structural and Functional Analysis of the Signal-Transducing Linker in the pH-Responsive One-Component System CadC of Escherichia coli.

    Science.gov (United States)

    Buchner, Sophie; Schlundt, Andreas; Lassak, Jürgen; Sattler, Michael; Jung, Kirsten

    2015-07-31

    The pH-responsive one-component signaling system CadC in Escherichia coli belongs to the family of ToxR-like proteins, whose members share a conserved modular structure, with an N-terminal cytoplasmic winged helix-turn-helix DNA-binding domain being followed by a single transmembrane helix and a C-terminal periplasmic pH-sensing domain. In E. coli CadC, a cytoplasmic linker comprising approximately 50 amino acids is essential for transmission of the signal from the sensor to the DNA-binding domain. However, the mechanism of transduction is poorly understood. Using NMR spectroscopy, we demonstrate here that the linker region is intrinsically disordered in solution. Furthermore, mutational analyses showed that it tolerates a range of amino acid substitutions (altering polarity, rigidity and α-helix-forming propensity), is robust to extension but is sensitive to truncation. Indeed, truncations either reversed the expression profile of the target operon cadBA or decoupled expression from external pH altogether. CadC dimerizes via its periplasmic domain, but light-scattering analysis provided no evidence for dimerization of the isolated DNA-binding domain, with or without the linker region. However, bacterial two-hybrid analysis revealed that CadC forms stable dimers in a stimulus- and linker-dependent manner, interacting only at pHpH. Thus, we propose that the disordered CadC linker is required for transducing the pH-dependent response of the periplasmic sensor into a structural rearrangement that facilitates dimerization of the cytoplasmic CadC DNA-binding domain. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption.

    Science.gov (United States)

    Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva; Tyagi, Madhusudan; Chen, Ping; Yildirim, Taner; Zhou, Wei

    2013-07-17

    UiO-66 is a highly important prototypical zirconium metal-organic framework (MOF) compound because of its excellent stabilities not typically found in common porous MOFs. In its perfect crystal structure, each Zr metal center is fully coordinated by 12 organic linkers to form a highly connected framework. Using high-resolution neutron power diffraction technique, we found the first direct structural evidence showing that real UiO-66 material contains significant amount of missing-linker defects, an unusual phenomenon for MOFs. The concentration of the missing-linker defects is surprisingly high, ∼10% in our sample, effectively reducing the framework connection from 12 to ∼11. We show that by varying the concentration of the acetic acid modulator and the synthesis time, the linker vacancies can be tuned systematically, leading to dramatically enhanced porosity. We obtained samples with pore volumes ranging from 0.44 to 1.0 cm(3)/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m(2)/g, the largest values of which are ∼150% and ∼60% higher than the theoretical values of defect-free UiO-66 crystal, respectively. The linker vacancies also have profound effects on the gas adsorption behaviors of UiO-66, in particular CO2. Finally, comparing the gas adsorption of hydroxylated and dehydroxylated UiO-66, we found that the former performs systematically better than the latter (particularly for CO2) suggesting the beneficial effect of the -OH groups. This finding is of great importance because hydroxylated UiO-66 is the practically more relevant, non-air-sensitive form of this MOF. The preferred gas adsorption on the metal center was confirmed by neutron diffraction measurements, and the gas binding strength enhancement by the -OH group was further supported by our first-principles calculations.

  14. Crystal structure of the Src family kinase Hck SH3-SH2 linker regulatory region supports an SH3-dominant activation mechanism.

    Science.gov (United States)

    Alvarado, John J; Betts, Laurie; Moroco, Jamie A; Smithgall, Thomas E; Yeh, Joanne I

    2010-11-12

    Most mammalian cell types depend on multiple Src family kinases (SFKs) to regulate diverse signaling pathways. Strict control of SFK activity is essential for normal cellular function, and loss of kinase regulation contributes to several forms of cancer and other diseases. Previous x-ray crystal structures of the SFKs c-Src and Hck revealed that intramolecular association of their Src homology (SH) 3 domains and SH2 kinase linker regions has a key role in down-regulation of kinase activity. However, the amino acid sequence of the Hck linker represents a suboptimal ligand for the isolated SH3 domain, suggesting that it may form the polyproline type II helical conformation required for SH3 docking only in the context of the intact structure. To test this hypothesis directly, we determined the crystal structure of a truncated Hck protein consisting of the SH2 and SH3 domains plus the linker. Despite the absence of the kinase domain, the structures and relative orientations of the SH2 and SH3 domains in this shorter protein were very similar to those observed in near full-length, down-regulated Hck. However, the SH2 kinase linker adopted a modified topology and failed to engage the SH3 domain. This new structure supports the idea that these noncatalytic regions work together as a "conformational switch" that modulates kinase activity in a manner unique to the SH3 domain and linker topologies present in the intact Hck protein. Our results also provide fresh structural insight into the facile induction of Hck activity by HIV-1 Nef and other Hck SH3 domain binding proteins and implicate the existence of innate conformational states unique to individual Src family members that "fine-tune" their sensitivities to activation by SH3-based ligands.

  15. Employing a hydrazine linked asymmetric double naphthalene hybrid for efficient naked eye detection of F-: Crystal structure with real application for F-

    Science.gov (United States)

    Bhattacharyya, Arghyadeep; Makhal, Subhash Chandra; Ghosh, Soumen; Guchhait, Nikhil

    2018-06-01

    An asymmetric hydrazide, (12E, 13E)-2-((naphthalen-1-yl) methylene)-1-(1-(2-hydroxynaphthalen-6-yl) ethylidene) hydrazine (abbreviated as AH) is synthesized and characterized by standard techniques and crystal structure of AH has been obtained. The naked eye detection of F- in aqueous acetonitrile (acetonitrile: water = 7:3/v:v) by AH has been investigated by UV-Visible titration and in presence of other anions, the limit of detection being 1.31 × 10-6(M). The mechanism of F- sensing has been explored by 1H NMR titration. AH undergoes hydrogen bonding with F- followed by deprotonation. The practical utility of AH has been explored by successful test kit response and color change in toothpaste solution.

  16. Evaluation of Electrochemical Characteristics on Graphene Coated Austenitic and Martensitic Stainless Steels for Metallic Bipolar Plates in PEMFC Fabricated with Hydrazine Reduction Methods

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Seong-Yun; Lee, Jae-Bong [School of Advanced Materials Engineering, Kookmin University, Seoul (Korea, Republic of)

    2016-04-15

    Graphene was coated on austenitic and martensitic stainless steels to simulate the metallic bipolar plate of proton exchange membrane fuel cell (PEMFC). Graphene oxide (GO) was synthesized and was reduced to reduced graphene oxide (rGO) via a hydrazine process. rGO was confirmed by FE-SEM, Raman spectroscopy and XPS. Interfacial contact resistance (ICR) between the bipolar plate and the gas diffusion layer (GDL) was measured to confirm the electrical conductivity. Both ICR and corrosion current density decreased on graphene coated stainless steels. Corrosion resistance was also improved with immersion time in cathodic environments and satisfied the criteria of the Department of Energy (DOE), USA. The total concentrations of metal ions dissolved from graphene coated stainless steels were reduced. Furthermore hydrophobicity was improved by increasing the contact angle.

  17. Prolinimines: N-Amino-l-Pro-methyl Ester (Hydrazine) Schiff Bases from a Fish Gastrointestinal Tract-Derived Fungus, Trichoderma sp. CMB-F563.

    Science.gov (United States)

    Mohamed, Osama G; Khalil, Zeinab G; Capon, Robert J

    2018-01-19

    A rice cultivation of a fish gastrointestinal tract-derived fungus, Trichoderma sp. CMB-F563, yielded natural products incorporating a rare hydrazine moiety, embedded within a Schiff base. Structures inclusive of absolute configurations were assigned to prolinimines A-D (1-4) on the basis of detailed spectroscopic and C 3 Marfey's analysis, as well as biosynthetic considerations, biomimetic total synthesis, and chemical transformations. Of note, monomeric 1 proved to be acid labile and, during isolation, underwent quantitative transformation to dimeric 3 and trimeric 4. Prolinimines are only the second reported natural products incorporating an N-amino-Pro residue, the first to include l-Pro, the first to occur as Schiff bases, and the first to be isolated from a microorganism.

  18. Determination of 17-oxosteroid glucuronides and sulfates in urine and serum by fluorescence high-performance liquid chromatography using dansyl hydrazine as a prelabeling reagent.

    Science.gov (United States)

    Kawasaki, T; Maeda, M; Tsuji, A

    1982-12-10

    A fluorescence high-performance liquid chromatographic method is described for the direct determination of conjugated 17-oxosteroids in biological fluids without hydrolysis. Conjugated 17-oxosteroids are extracted with Sep-Pak C18 cartridge, labeled with dansyl hydrazine in trichloroacetic acid--benzene solution and then separated by high-performance liquid chromatography on reversed-phase muBondapak C18 column using 0.01 M sodium acetate in methanol-water-acetic acid (65:35:1, v/v) as the mobile phase. The eluate is monitored by a fluorophotometer at 365 nm (excitation) and 520 nm (emission). Linearities of fluorescence intensities (peak heights) with the amounts of various conjugated 17-oxosteroids were obtained between 10 pmol and 100 pmol. This method is sensitive, reliable and useful for the simultaneous determination of conjugated 17-oxosteroids in urine and serum.

  19. Simple determination of hydrazine in waste water by headspace solid-phase micro extraction and gas chromatography-tandem mass spectrometry after derivatization with trifluoro pentanedione.

    Science.gov (United States)

    Oh, Jin-Aa; Shin, Ho-Sang

    2017-01-15

    A headspace solid-phase micro extraction (HS-SPME) and gas chromatography-tandem mass spectrometric (GC-MS/MS) method is described to detect hydrazine after derivatization with 1,1,1-trifluoro-2,4-pentanedione (1,1,1-TFPD) to 3-methyl-5-(trifluoromethyl) pyrazole in industrial waste water. The following optimal HS-SPME conditions were used: 85 μm-carboxen-polydimethylsiloxane fibre, 100 mg L -1 TFPD, saturated NaCl, an extraction/derivatization temperature of 80 °C, a heating time of 40 min, and a pH of 9.5. Under the established conditions, the detection and quantification limits were 0.002 μg L -1 and 0.007 μg L -1  by using 5 mL of waste water and the intra- and inter-day relative standard deviations were less than 10.2% at concentrations of 0.02 and 0.1 μg L -1 . The calibration curve showed good linearity, with r 2  = 0.998; the accuracy was in the range of 98.0-103%; and the precision of the assay was less than 10.2% in industrial waste water. Hydrazine was detected over a concentration range of 0.011-0.074 μg L -1 in 5 of 20 waste water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Study of Supported Nickel Catalysts Prepared by Aqueous Hydrazine Method. Hydrogenating Properties and Hydrogen Storage: Support Effect. Silver Additive Effect; Catalyseurs de nickel supportes prepares par la methode de l'hydrazine aqueuse. Proprietes hydrogenantes et stockage d'hydrogene. Effet du support. Effet de l'ajout d'argent

    Energy Technology Data Exchange (ETDEWEB)

    Wojcieszak, R

    2006-06-15

    We have studied Ni or NiAg nano-particles obtained by the reduction of nickel salts (acetate or nitrate) by hydrazine and deposited by simple or EDTA-double impregnation on various supports ({gamma}-Al{sub 2}O{sub 3}, amorphous or crystallized SiO{sub 2}, Nb{sub 2}O{sub 5}, CeO{sub 2} and carbon). Prepared catalysts were characterized by different methods (XRD, XPS, low temperature adsorption and desorption of N{sub 2}, FTIR and FTIR-Pyridine, TEM, STEM, EDS, H{sub 2}-TPR, H{sub 2}-adsorption, H{sub 2}-TPD, isopropanol decomposition) and tested in the gas phase hydrogenation of benzene or as carbon materials in the hydrogen storage at room temperature and high pressure. The catalysts prepared exhibited better dispersion and activity than classical catalysts. TOF's of NiAg/SiO{sub 2} or Ni/carbon catalysts were similar to Pt catalysts in benzene hydrogenation. Differences in support acidity or preparation method and presence of Ag as metal additive play a crucial role in the chemical reduction of Ni by hydrazine and in the final properties of the materials. Ni/carbon catalysts could store significant amounts of hydrogen at room temperature and high pressure (0.53%/30 bars), probably through the hydrogen spillover effect. (author)

  1. Directing the breathing behavior of pillared-layered metal-organic frameworks via a systematic library of functionalized linkers bearing flexible substituents.

    Science.gov (United States)

    Henke, Sebastian; Schneemann, Andreas; Wütscher, Annika; Fischer, Roland A

    2012-06-06

    Flexible metal-organic frameworks (MOFs), also referred to as soft porous crystals (SPCs), show reversible structural transitions dependent on the nature and quantity of adsorbed guest molecules. In recent studies it has been reported that covalent functionalization of the organic linker can influence or even integrate framework flexibility ("breathing") in MOFs. However, rational fine-tuning of such responsive properties is very desirable but challenging as well. Here we present a powerful approach for the targeted manipulation of responsiveness and framework flexibility of an important family of pillared-layered MOFs based on the parent structure [Zn(2)(bdc)(2)(dabco)](n) (bdc = 1,4-benzenedicarboxylate; dabco = 1,4-diazabicyclo[2.2.2]octane). A library of functionalized bdc-type linkers (fu-bdc), which bear additional dangling side groups at different positions of the benzene core (alkoxy groups of varying chain length with diverse functionalities and polarity), was generated. Synthesis of the materials [Zn(2)(fu-bdc)(2)(dabco)](n) yields the respective collection of highly responsive MOFs. The parent MOF is only weakly flexible; however, the substituted frameworks of [Zn(2)(fu-bdc)(2)(dabco)](n) contract drastically upon guest removal and expand again upon adsorption of DMF (N,N-dimethylformamide), EtOH, or CO(2), etc., while N(2) is hardly adsorbed and does not open the narrow-pored form. These "breathing" dynamics are attributed to the dangling side chains that act as immobilized "guests", which interact with mobile guest molecules as well as with themselves and with the framework backbone. The structural details of the guest-free, contracted form and the gas sorption behavior (phase transition pressure, hysteresis loop) are highly dependent on the nature of the substituent at the linker and can therefore be adjusted using our approach. Combining our library of functionalized linkers with the concept of mixed-component MOFs (solid solutions) offers very rich

  2. Linker-free 3D assembly of nanocrystals with tunable unit size for reversible lithium ion storage

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Da; Lee, Jim Yang, E-mail: cheleejy@nus.edu.sg [Department of Chemical and Biomolecular Engineering, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, 119260 (Singapore)

    2011-09-02

    A simple and scalable procedure combining hydrothermal synthesis with post-synthesis calcination was developed to produce a linker-free, thermally stable, mesoscale 3D ordered assembly of spinel-type ZnCo{sub 2}O{sub 4} nanocrystals. The mesoscale assembly with distinctively sharp edges was formed by close-packing the ZnCo{sub 2}O{sub 4} nanocrystal building blocks with a unit size changeable by the synthesis temperature. A self-templating mechanism based on the topotactic transformation of an oxalato-bridged precursor coordination compound was proposed for the assembly. The packaging of crystalline ZnCo{sub 2}O{sub 4} nanoparticles, an active lithium ion storage compound, into a dense organized structure is an effective way to increase the volumetric capacity of ZnCo{sub 2}O{sub 4} nanoparticles for reversible lithium ion storage. The highly ordered 3D assembly of ZnCo{sub 2}O{sub 4} demonstrated excellent reversible lithium ion storage properties and a specific capacity ({approx}800 mAh g{sup -1}) much higher than that of carbon (typically {approx} 350 mAh g{sup -1}).

  3. Multivalent peptidic linker enables identification of preferred sites of conjugation for a potent thialanstatin antibody drug conjugate.

    Directory of Open Access Journals (Sweden)

    Sujiet Puthenveetil

    Full Text Available Antibody drug conjugates (ADCs are no longer an unknown entity in the field of cancer therapy with the success of marketed ADCs like ADCETRIS and KADCYLA and numerous others advancing through clinical trials. The pursuit of novel cytotoxic payloads beyond the mictotubule inhibitors and DNA damaging agents has led us to the recent discovery of an mRNA splicing inhibitor, thailanstatin, as a potent ADC payload. In our previous work, we observed that the potency of this payload was uniquely tied to the method of conjugation, with lysine conjugates showing much superior potency as compared to cysteine conjugates. However, the ADC field is rapidly shifting towards site-specific ADCs due to their advantages in manufacturability, characterization and safety. In this work we report the identification of a highly efficacious site-specific thailanstatin ADC. The site of conjugation played a critical role on both the in vitro and in vivo potency of these ADCs. During the course of this study, we developed a novel methodology of loading a single site with multiple payloads using an in situ generated multi-drug carrying peptidic linker that allowed us to rapidly screen for optimal conjugation sites. Using this methodology, we were able to identify a double-cysteine mutant ADC delivering four-loaded thailanstatin that was very efficacious in a gastric cancer xenograft model at 3mg/kg and was also shown to be efficacious against T-DM1 resistant and MDR1 overexpressing tumor cell lines.

  4. Multivalent peptidic linker enables identification of preferred sites of conjugation for a potent thialanstatin antibody drug conjugate.

    Science.gov (United States)

    Puthenveetil, Sujiet; He, Haiyin; Loganzo, Frank; Musto, Sylvia; Teske, Jesse; Green, Michael; Tan, Xingzhi; Hosselet, Christine; Lucas, Judy; Tumey, L Nathan; Sapra, Puja; Subramanyam, Chakrapani; O'Donnell, Christopher J; Graziani, Edmund I

    2017-01-01

    Antibody drug conjugates (ADCs) are no longer an unknown entity in the field of cancer therapy with the success of marketed ADCs like ADCETRIS and KADCYLA and numerous others advancing through clinical trials. The pursuit of novel cytotoxic payloads beyond the mictotubule inhibitors and DNA damaging agents has led us to the recent discovery of an mRNA splicing inhibitor, thailanstatin, as a potent ADC payload. In our previous work, we observed that the potency of this payload was uniquely tied to the method of conjugation, with lysine conjugates showing much superior potency as compared to cysteine conjugates. However, the ADC field is rapidly shifting towards site-specific ADCs due to their advantages in manufacturability, characterization and safety. In this work we report the identification of a highly efficacious site-specific thailanstatin ADC. The site of conjugation played a critical role on both the in vitro and in vivo potency of these ADCs. During the course of this study, we developed a novel methodology of loading a single site with multiple payloads using an in situ generated multi-drug carrying peptidic linker that allowed us to rapidly screen for optimal conjugation sites. Using this methodology, we were able to identify a double-cysteine mutant ADC delivering four-loaded thailanstatin that was very efficacious in a gastric cancer xenograft model at 3mg/kg and was also shown to be efficacious against T-DM1 resistant and MDR1 overexpressing tumor cell lines.

  5. Biocompatible Porous Polyester-Ether Hydrogel Scaffolds with Cross-Linker Mediated Biodegradation and Mechanical Properties for Tissue Augmentation

    Directory of Open Access Journals (Sweden)

    Berkay Ozcelik

    2018-02-01

    Full Text Available Porous polyester-ether hydrogel scaffolds (PEHs were fabricated using acid chloride/alcohol chemistry and a salt templating approach. The PEHs were produced from readily available and cheap commercial reagents via the reaction of hydroxyl terminated poly(ethylene glycol (PEG derivatives with sebacoyl, succinyl, or trimesoyl chloride to afford ester cross-links between the PEG chains. Through variation of the acid chloride cross-linkers used in the synthesis and the incorporation of a hydrophobic modifier (poly(caprolactone (PCL, it was possible to tune the degradation rates and mechanical properties of the resulting hydrogels. Several of the hydrogel formulations displayed exceptional mechanical properties, remaining elastic without fracture at compressive strains of up to 80%, whilst still displaying degradation over a period of weeks to months. A subcutaneous rat model was used to study the scaffolds in vivo and revealed that the PEHs were infiltrated with well vascularised tissue within two weeks and had undergone significant degradation in 16 weeks without any signs of toxicity. Histological evaluation for immune responses revealed that the PEHs incite only a minor inflammatory response that is reduced over 16 weeks with no evidence of adverse effects.

  6. Optimization and characterization of biomolecule immobilization on silicon substrates using (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde linker

    International Nuclear Information System (INIS)

    Gunda, Naga Siva Kumar; Singh, Minashree; Norman, Lana; Kaur, Kamaljit; Mitra, Sushanta K.

    2014-01-01

    In the present work, we developed and optimized a technique to produce a thin, stable silane layer on silicon substrate in a controlled environment using (3-aminopropyl)triethoxysilane (APTES). The effect of APTES concentration and silanization time on the formation of silane layer is studied using spectroscopic ellipsometry and Fourier transform infrared spectroscopy (FTIR). Biomolecules of interest are immobilized on optimized silane layer formed silicon substrates using glutaraldehyde linker. Surface analytical techniques such as ellipsometry, FTIR, contact angle measurement system, and atomic force microscopy are employed to characterize the bio-chemically modified silicon surfaces at each step of the biomolecule immobilization process. It is observed that a uniform, homogenous and highly dense layer of biomolecules are immobilized with optimized silane layer on the silicon substrate. The developed immobilization method is successfully implemented on different silicon substrates (flat and pillar). Also, different types of biomolecules such as anti-human IgG (rabbit monoclonal to human IgG), Listeria monocytogenes, myoglobin and dengue capture antibodies were successfully immobilized. Further, standard sandwich immunoassay (antibody–antigen–antibody) is employed on respective capture antibody coated silicon substrates. Fluorescence microscopy is used to detect the respective FITC tagged detection antibodies bound to the surface after immunoassay.

  7. Silica-bound copper(II)triazacyclononane as a phosphate esterase: effect of linker length and surface hydrophobicity.

    Science.gov (United States)

    Bodsgard, Brett R; Clark, Robert W; Ehrbar, Anthony W; Burstyn, Judith N

    2009-04-07

    A series of silica-bound Cu(ii) triazacyclononane materials was prepared to study the effect of linker length and surface hydrophobicity on the hydrolysis of phosphate esters. The general synthetic approach for these heterogeneous reagents was rhodium-catalyzed hydrosilation between an alkenyl-modified triazacyclononane and hydride-modified silica followed by metallation with a Cu(ii) salt. Elemental analysis confirmed that organic functionalization of the silica gel was successful and provided an estimate of the surface concentration of triazacyclononane. EPR spectra were consistent with square pyramidal Cu(ii), indicating that Cu(ii) ions were bound to the immobilized macrocycles. The hydrolytic efficacies of these heterogeneous reagents were tested with bis(p-nitrophenyl)phosphate (BNPP) and diethyl 4-nitrophenyl phosphate (paraoxon). The agent that performed best was an octyl-linked, propanol-blocked material. This material had the most hydrophilic surface and the most accessible active site, achieving a rate maximum on par with the other materials, but in fewer cycles and without an induction period.

  8. Solid phase synthesis of mitochondrial triphenylphosphonium-vitamin E metabolite using a lysine linker for reversal of oxidative stress.

    Directory of Open Access Journals (Sweden)

    Mohanad Mossalam

    Full Text Available Mitochondrial targeting of antioxidants has been an area of interest due to the mitochondria's role in producing and metabolizing reactive oxygen species. Antioxidants, especially vitamin E (α-tocopherol, have been conjugated to lipophilic cations to increase their mitochondrial targeting. Synthetic vitamin E analogues have also been produced as an alternative to α-tocopherol. In this paper, we investigated the mitochondrial targeting of a vitamin E metabolite, 2,5,7,8-tetramethyl-2-(2'-carboxyethyl-6-hydroxychroman (α-CEHC, which is similar in structure to vitamin E analogues. We report a fast and efficient method to conjugate the water-soluble metabolite, α-CEHC, to triphenylphosphonium cation via a lysine linker using solid phase synthesis. The efficacy of the final product (MitoCEHC to lower oxidative stress was tested in bovine aortic endothelial cells. In addition the ability of MitoCEHC to target the mitochondria was examined in type 2 diabetes db/db mice. The results showed mitochondrial accumulation in vivo and oxidative stress decrease in vitro.

  9. The bacterial tubulin FtsZ requires its intrinsically disordered linker to direct robust cell wall construction.

    Science.gov (United States)

    Sundararajan, Kousik; Miguel, Amanda; Desmarais, Samantha M; Meier, Elizabeth L; Casey Huang, Kerwyn; Goley, Erin D

    2015-06-23

    The bacterial GTPase FtsZ forms a cytokinetic ring at midcell, recruits the division machinery and orchestrates membrane and peptidoglycan cell wall invagination. However, the mechanism for FtsZ regulation of peptidoglycan metabolism is unknown. The FtsZ GTPase domain is separated from its membrane-anchoring C-terminal conserved (CTC) peptide by a disordered C-terminal linker (CTL). Here we investigate CTL function in Caulobacter crescentus. Strikingly, production of FtsZ lacking the CTL (ΔCTL) is lethal: cells become filamentous, form envelope bulges and lyse, resembling treatment with β-lactam antibiotics. This phenotype is produced by FtsZ polymers bearing the CTC and a CTL shorter than 14 residues. Peptidoglycan synthesis still occurs downstream of ΔCTL; however, cells expressing ΔCTL exhibit reduced peptidoglycan crosslinking and longer glycan strands than wild type. Importantly, midcell proteins are still recruited to sites of ΔCTL assembly. We propose that FtsZ regulates peptidoglycan metabolism through a CTL-dependent mechanism that extends beyond simple protein recruitment.

  10. Synthesis of Cassava Waste Pulp-Acrylamide Super Absorbent: Effect of Initiator and Cross-Linker Concentration

    Directory of Open Access Journals (Sweden)

    Zainal Alim Mas’ud

    2013-05-01

    Full Text Available Cassava waste pulp (CWP contains high carbohydrates that can be modified into super absorbent polymer (SAP through grafting and cross-linking copolymerization. Acrylamide (AM was grafted onto CWP with ammonium persulfate (APS as the initiator and N,N'-methylene-bis-acrylamide (MBA as the cross-linker under atmospheric nitrogen. The effect of APS and MBA concentrations on water absorption capacity of saponified SAP was studied, while the evaluation of grafting ratio (GR and grafting efficiency (GRE was conducted on unsaponified SAP. The grafting success was indicated by the occurrence of IR peaks at wave numbers of 573, 765, 858, and 1667 cm-1. In the saponified SAP, the very intense characteristic band at 1562 cm-1 is due to C=O asymmetric stretching in the carboxylate anion. Saponification increases significantly water absorption capacity compared to that of unsaponified SAP (from 39.79 g/g to 578.23 g/g. The highest water absorption capacity is reached at 0.74% APS and 0.09% MBA. The percentage of GRE and GR tends to increase with increasing APS concentration until reaching the highest value and then decreases. Effect of MBA concentration on water absorption capacity, GR, and on GRE is similar to the effect of initiator concentration on GR and GRE.

  11. NIR-Cyanine Dye Linker: a Promising Candidate for Isochronic Fluorescence Imaging in Molecular Cancer Diagnostics and Therapy Monitoring.

    Science.gov (United States)

    Komljenovic, Dorde; Wiessler, Manfred; Waldeck, Waldemar; Ehemann, Volker; Pipkorn, Ruediger; Schrenk, Hans-Hermann; Debus, Jürgen; Braun, Klaus

    2016-01-01

    Personalized anti-cancer medicine is boosted by the recent development of molecular diagnostics and molecularly targeted drugs requiring rapid and efficient ligation routes. Here, we present a novel approach to synthetize a conjugate able to act simultaneously as an imaging and as a chemotherapeutic agent by coupling functional peptides employing solid phase peptide synthesis technologies. Development and the first synthesis of a fluorescent dye with similarity in the polymethine part of the Cy7 molecule whose indolenine-N residues were substituted with a propylene linker are described. Methylating agent temozolomide is functionalized with a tetrazine as a diene component whereas Cy7-cell penetrating peptide conjugate acts as a dienophilic reaction partner for the inverse Diels-Alder click chemistry-mediated ligation route yielding a theranostic conjugate, 3-mercapto-propionic-cyclohexenyl-Cy7-bis-temozolomide-bromide-cell penetrating peptide. Synthesis route described here may facilitate targeted delivery of the therapeutic compound to achieve sufficient local concentrations at the target site or tissue. Its versatility allows a choice of adequate imaging tags applicable in e.g. PET, SPECT, CT, near-infrared imaging, and therapeutic substances including cytotoxic agents. Imaging tags and therapeutics may be simultaneously bound to the conjugate applying click chemistry. Theranostic compound presented here offers a solid basis for a further improvement of cancer management in a precise, patient-specific manner.

  12. Linker-free 3D assembly of nanocrystals with tunable unit size for reversible lithium ion storage

    International Nuclear Information System (INIS)

    Deng, Da; Lee, Jim Yang

    2011-01-01

    A simple and scalable procedure combining hydrothermal synthesis with post-synthesis calcination was developed to produce a linker-free, thermally stable, mesoscale 3D ordered assembly of spinel-type ZnCo 2 O 4 nanocrystals. The mesoscale assembly with distinctively sharp edges was formed by close-packing the ZnCo 2 O 4 nanocrystal building blocks with a unit size changeable by the synthesis temperature. A self-templating mechanism based on the topotactic transformation of an oxalato-bridged precursor coordination compound was proposed for the assembly. The packaging of crystalline ZnCo 2 O 4 nanoparticles, an active lithium ion storage compound, into a dense organized structure is an effective way to increase the volumetric capacity of ZnCo 2 O 4 nanoparticles for reversible lithium ion storage. The highly ordered 3D assembly of ZnCo 2 O 4 demonstrated excellent reversible lithium ion storage properties and a specific capacity (∼800 mAh g -1 ) much higher than that of carbon (typically ∼ 350 mAh g -1 ).

  13. Construction, Structural Diversity and Properties of Five Coordination Polymers Based on 5-Nitroisophthalate and Bis(imidazole) Linkers

    Science.gov (United States)

    Arıcı, Mürsel

    2018-06-01

    Five coordination polymers, namely, [Cd(μ3-5-nip)(μ-obix)]n (1), [Co(μ3-5-nip)(μ-obix)]n (2), [Zn(μ-5-nip)(μ-obix)]n (3 and 4) and [Cd(μ-5-nip)(μ-bisobix)]n (5) (5-nip: 5-nitroisophthalate, obix: 1,2-bis(imidazol-1ylmethyl)benzene, bisobix: 1,2-bis(2-isopropylimidazol-1ylmethyl)benzene) were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). X-ray results showed that the complexes displayed structural diversity depending on metal ions and conformations of bis(imidazole) linkers. Complexes 1 and 2 were 1D structures and obix ligand displayed cis-conformation. Complexes 3 and 4 exhibited 2D and 3D structures with same components depending on obix conformation. In complex 5, 3D+3D→3D interpenetrated structure was obtained with dia topology when bisobix having sterically hindered groups on imidazole rings was used. Moreover, thermal, photoluminescence and optical properties of the complexes were also investigated.

  14. Demonstration of Improved Charge Transfer in Graphene/Au Nanorods Plasmonic Hybrids Stabilized by Benzyl Thiol Linkers

    Directory of Open Access Journals (Sweden)

    Giuseppe Valerio Bianco

    2016-01-01

    Full Text Available Hybrids based on graphene decorated with plasmonic gold (Au nanostructures are being investigated as possible materials combination to add to graphene functionalities of tunable plasmon resonance and enhanced absorption at selected wavelength in the visible-near-infrared region of the spectrum. Here, we report a solution drop-casting approach for fabricating stable hybrids based on chemical vapor deposition (CVD graphene and Au nanorods, which are able to activate effective charge transfer from graphene. We demonstrate that CVD graphene functionalization by benzyl thiol (BZT provides the linker to strong anchoring, via S-Au bonds, Au nanorods to graphene. Optical measurements by spectroscopic ellipsometry give evidence of the introduction of plasmon resonances at 1.85 and 2.25 eV in the Au nanorods/BZT/graphene hybrids, which enable surface enhanced Raman scattering (SERS detection. Furthermore, an effective electron transfer from graphene to Au nanorods, resulting in an enhancement of p-type doping of graphene with a consequent decrease of its sheet resistance, is probed by Raman spectroscopy and corroborated by electrical measurements.

  15. Phosphonate self-assembled monolayers as organic linkers in solid-state quantum dot sensetized solar cells

    KAUST Repository

    Ardalan, Pendar

    2010-06-01

    We have employed X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-vis) spectroscopy, infrared (IR) spectroscopy, water contact angle (WCA) measurements, ellipsometry, and electrical measurements to study the effects of self-assembled monolayers (SAMs) with phosphonic acid headgroups on the bonding and performance of cadmium sulfide (CdS) solid-state quantum dot sensitized solar cells (QDSSCs). ∼2 to ∼6 nm size CdS quantum dots (QDs) were grown on the SAM-passivated TiO2 surfaces by successive ionic layer adsorption and reaction (SILAR). Our results show differences in the bonding of the CdS QDs at the TiO2 surfaces with a SAM linker. Moreover, our data indicate that presence of a SAM increases the CdS uptake on TiO2 as well as the performance of the resulting devices. Importantly, we observe ∼2 times higher power conversion efficiencies in the devices with a SAM compared to those that lack a SAM. © 2010 IEEE.

  16. Optimization and characterization of biomolecule immobilization on silicon substrates using (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde linker

    Energy Technology Data Exchange (ETDEWEB)

    Gunda, Naga Siva Kumar [Department of Mechanical Engineering, University of Alberta, Edmonton, Canada T6G 2G8 (Canada); Singh, Minashree [Department of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Canada T6G 1C9 (Canada); Norman, Lana [Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada T6G 2V4 (Canada); Kaur, Kamaljit [Department of Pharmacy and Pharmaceutical Sciences, University of Alberta, Edmonton, Canada T6G 1C9 (Canada); Mitra, Sushanta K., E-mail: sushanta.mitra@ualberta.ca [Department of Mechanical Engineering, University of Alberta, Edmonton, Canada T6G 2G8 (Canada)

    2014-06-01

    In the present work, we developed and optimized a technique to produce a thin, stable silane layer on silicon substrate in a controlled environment using (3-aminopropyl)triethoxysilane (APTES). The effect of APTES concentration and silanization time on the formation of silane layer is studied using spectroscopic ellipsometry and Fourier transform infrared spectroscopy (FTIR). Biomolecules of interest are immobilized on optimized silane layer formed silicon substrates using glutaraldehyde linker. Surface analytical techniques such as ellipsometry, FTIR, contact angle measurement system, and atomic force microscopy are employed to characterize the bio-chemically modified silicon surfaces at each step of the biomolecule immobilization process. It is observed that a uniform, homogenous and highly dense layer of biomolecules are immobilized with optimized silane layer on the silicon substrate. The developed immobilization method is successfully implemented on different silicon substrates (flat and pillar). Also, different types of biomolecules such as anti-human IgG (rabbit monoclonal to human IgG), Listeria monocytogenes, myoglobin and dengue capture antibodies were successfully immobilized. Further, standard sandwich immunoassay (antibody–antigen–antibody) is employed on respective capture antibody coated silicon substrates. Fluorescence microscopy is used to detect the respective FITC tagged detection antibodies bound to the surface after immunoassay.

  17. Influence of vibronic contribution on light harvesting efficiency of NKX-2587 derivatives with oligothiophene as π-conjugated linker

    Science.gov (United States)

    Yang, Pan; Zhang, Yang; Li, Ming; Shen, Wei; He, Rongxing

    2018-01-01

    Based on the NKX-2587 molecule we designed ten sensitizers with 1-10 thiophene moieties to investigate how the number of thiophene unit in the spacer influences the absorption spectra of sensitizer in dye sensitized solar cells (DSSCs). The parameters of short-circuit current density (Jsc), open circuit voltage (Voc), the light harvesting efficiency (LHE), injection driving force (Δ Ginject), and transferred electron number (nc), were calculated and discussed in detail. Results indicated that the increasing of thiophene units makes for the enhancement of oscillator strengths (f), although the red shift of vertical electronic absorption spectra is small. For the designed sensitizers with 1-5 thiophene units, their ΔGinject and nc raise gradually with the increasing of thiophene number. However, for those sensitizers with 6-10 thiophene units, the ΔGinject and nc decrease continuously with the increasing of thiophene units. In order to study how the oligothiophene as π-conjugated linker affects light harvesting efficiency of DSSCs, the vibrationally resolved electronic spectra of five metal-free NKX-2587 derivatives with 1-5 thiophene units were simulated within the Franck-Condon approximation including the Herzberg-Teller and Duschinsky effects. The present theoretical results provided helpful guidance for understanding the sources of spectral intensities of dye molecules, and a valuable method for rational design of new molecules to improve the energy conversion efficiency (η) of DSSCs.

  18. Structure and properties of Al-MIL-53-ADP, a breathing MOF based on the aliphatic linker molecule adipic acid.

    Science.gov (United States)

    Reinsch, Helge; Pillai, Renjith S; Siegel, Renée; Senker, Jürgen; Lieb, Alexandra; Maurin, Guillaume; Stock, Norbert

    2016-03-14

    The new aluminium based metal-organic framework [Al(OH)(O2C-C4H8-CO2)]·H2O denoted as Al-MIL-53-ADP-lp (lp stands for large pore) was synthesised under solvothermal conditions. This solid is an analogue of the archetypical aluminium terephthalate Al-MIL-53 based on the aliphatic single-chain linker molecule adipic acid (H2ADP, hexanedioic acid). In contrast to its aromatic counterparts, Al-MIL-53-ADP exhibits a structural breathing behaviour solely upon dehydration/rehydration. The crystal structure of the anhydrous compound denoted as Al-MIL-53-ADP-np (np stands for narrow pore) was determined by a combination of forcefield-based computations and Rietveld refinement of the powder X-ray diffraction data while the structure of the hydrated form Al-MIL-53-ADP-lp was derived computationally by a combination of force field based methods and Density Functional Theory calculations. Both structures were further supported by (1)H, (13)C and (27)Al high-resolution NMR MAS 1D data coupled again with simulations. Al-MIL-53-ADP was further characterised by means of vibrational spectroscopy, elemental analysis, thermogravimetry and water vapour sorption.

  19. A Dual-Purpose Linker for Alpha Helix Stabilization and Imaging Agent Conjugation to Glucagon-Like Peptide-1 Receptor Ligands

    Science.gov (United States)

    Zhang, Liang; Navaratna, Tejas; Liao, Jianshan; Thurber, Greg M.

    2016-01-01

    Peptides display many characteristics of efficient imaging agents such as rapid targeting, fast background clearance, and low non-specific cellular uptake. However, poor stability, low affinity, and loss of binding after labeling often preclude their use in vivo. Using the glucagon-like peptide-1 receptor (GLP-1R) ligands exendin and GLP-1 as a model system, we designed a novel alpha helix stabilizing linker to simultaneously address these limitations. The stabilized and labeled peptides showed an increase in helicity, improved protease resistance, negligible loss or an improvement in binding affinity, and excellent in vivo targeting. The ease of incorporating azidohomoalanine in peptides and efficient reaction with the dialkyne linker enables this technique to potentially be used as a general method for labeling alpha helices. This strategy should be useful for imaging beta cells in diabetes research and in developing and testing other peptide targeting agents. PMID:25594741

  20. Mutation of Gly717Phe in human topoisomerase 1B has an effect on enzymatic function, reactivity to the camptothecin anticancer drug and on the linker domain orientation

    DEFF Research Database (Denmark)

    Wang, Zhenxing; D'Annessa, Ilda; Tesauro, Cinzia

    2015-01-01

    –DNA covalent adduct. In this work the role of the Gly717 residue, located in a α-helix structure bridging the active site and the linker domain, has been investigated mutating it in Phe. The mutation gives rise to drug resistance in vivo as observed through a viability assay of yeast cells. In vitro activity...... assays show that the mutant is characterized by a fast religation rate, only partially reduced by the presence of the drug. Comparative molecular dynamics simulations of the native and mutant proteins indicate that the mutation of Gly717 affects the motion orientation of the linker domain, changing its...... interaction with the DNA substrate, likely affecting the strand rotation and religation rate. The mutation also causes a slight rearrangement of the active site and of the drug binding site, providing an additional explanation for the lowered effect of camptothecin toward the mutant....

  1. A two-dimensional ZnII coordination polymer constructed from benzene-1,2,3-tricarboxylic acid and N,N'-bis[(pyridin-4-yl)methylidene]hydrazine.

    Science.gov (United States)

    Wang, Xiangfei; Yang, Fang; Tang, Meng; Yuan, Limin; Liu, Wenlong

    2015-07-01

    The hydrothermal synthesis of the novel complex poly[aqua(μ4-benzene-1,2,3-tricarboxylato)[μ2-4,4'-(hydrazine-1,2-diylidenedimethanylylidene)dipyridine](μ3-hydroxido)dizinc(II)], [Zn(C9H3O6)(OH)(C12H10N4)(H2O)]n, is described. The benzene-1,2,3-tricarboxylate ligand connects neighbouring Zn4(OH)2 secondary building units (SBUs) producing an infinite one-dimensional chain. Adjacent one-dimensional chains are connected by the N,N'-bis[(pyridin-4-yl)methylidene]hydrazine ligand, forming a two-dimensional layered structure. Adjacent layers are stacked to generate a three-dimensional supramolecular architecture via O-H...O hydrogen-bond interactions. The thermal stability of this complex is described and the complex also appears to have potential for application as a luminescent material.

  2. Synthesis, Characterization, and Biological Evaluation of certain 6-methyl-2(3H)-benzo-1, 3-thiazolyl-1’-ethylidene-2-(o, p- Substituted Acetophenones) Hydrazine Analogs

    Science.gov (United States)

    Alang, G; Kaur, G; Kaur, R; Singh, A; Tiwari, R

    2010-01-01

    In the present study, five new derivatives (GG4 to GG8) of benzothiazoles were synthesized and evaluated against Staphylococcus aureus (MTCC 737), Pseudomonas aeruginosa (MTCC 424), Escherichia coli (MTCC 1687), and yeast-like fungi Candida tropicalis. p-Toluidine on treatment with ammonium thiocynate formed 2-benzothiazolamines (II), which on reaction with hydrazine hydrate formed a hydrazino derivative (III). Compounds GG4 to GG8 were synthesized by reacting the hydrazine derivative with different acetophenones. All the synthesized compounds were identified by IR and 1H-NMR, and antimicrobial activity was performed on the synthesized compounds. Presence of NO2, Br, OCH3, and Cl groups to the substituted benzothiazole enhanced the antibacterial and antifungal activities. PMID:21264101

  3. Learning a weighted sequence model of the nucleosome core and linker yields more accurate predictions in Saccharomyces cerevisiae and Homo sapiens.

    Directory of Open Access Journals (Sweden)

    Sheila M Reynolds

    2010-07-01

    Full Text Available DNA in eukaryotes is packaged into a chromatin complex, the most basic element of which is the nucleosome. The precise positioning of the nucleosome cores allows for selective access to the DNA, and the mechanisms that control this positioning are important pieces of the gene expression puzzle. We describe a large-scale nucleosome pattern that jointly characterizes the nucleosome core and the adjacent linkers and is predominantly characterized by long-range oscillations in the mono, di- and tri-nucleotide content of the DNA sequence, and we show that this pattern can be used to predict nucleosome positions in both Homo sapiens and Saccharomyces cerevisiae more accurately than previously published methods. Surprisingly, in both H. sapiens and S. cerevisiae, the most informative individual features are the mono-nucleotide patterns, although the inclusion of di- and tri-nucleotide features results in improved performance. Our approach combines a much longer pattern than has been previously used to predict nucleosome positioning from sequence-301 base pairs, centered at the position to be scored-with a novel discriminative classification approach that selectively weights the contributions from each of the input features. The resulting scores are relatively insensitive to local AT-content and can be used to accurately discriminate putative dyad positions from adjacent linker regions without requiring an additional dynamic programming step and without the attendant edge effects and assumptions about linker length modeling and overall nucleosome density. Our approach produces the best dyad-linker classification results published to date in H. sapiens, and outperforms two recently published models on a large set of S. cerevisiae nucleosome positions. Our results suggest that in both genomes, a comparable and relatively small fraction of nucleosomes are well-positioned and that these positions are predictable based on sequence alone. We believe that the

  4. Learning a weighted sequence model of the nucleosome core and linker yields more accurate predictions in Saccharomyces cerevisiae and Homo sapiens.

    Science.gov (United States)

    Reynolds, Sheila M; Bilmes, Jeff A; Noble, William Stafford

    2010-07-08

    DNA in eukaryotes is packaged into a chromatin complex, the most basic element of which is the nucleosome. The precise positioning of the nucleosome cores allows for selective access to the DNA, and the mechanisms that control this positioning are important pieces of the gene expression puzzle. We describe a large-scale nucleosome pattern that jointly characterizes the nucleosome core and the adjacent linkers and is predominantly characterized by long-range oscillations in the mono, di- and tri-nucleotide content of the DNA sequence, and we show that this pattern can be used to predict nucleosome positions in both Homo sapiens and Saccharomyces cerevisiae more accurately than previously published methods. Surprisingly, in both H. sapiens and S. cerevisiae, the most informative individual features are the mono-nucleotide patterns, although the inclusion of di- and tri-nucleotide features results in improved performance. Our approach combines a much longer pattern than has been previously used to predict nucleosome positioning from sequence-301 base pairs, centered at the position to be scored-with a novel discriminative classification approach that selectively weights the contributions from each of the input features. The resulting scores are relatively insensitive to local AT-content and can be used to accurately discriminate putative dyad positions from adjacent linker regions without requiring an additional dynamic programming step and without the attendant edge effects and assumptions about linker length modeling and overall nucleosome density. Our approach produces the best dyad-linker classification results published to date in H. sapiens, and outperforms two recently published models on a large set of S. cerevisiae nucleosome positions. Our results suggest that in both genomes, a comparable and relatively small fraction of nucleosomes are well-positioned and that these positions are predictable based on sequence alone. We believe that the bulk of the

  5. Epigenetics and autism spectrum disorder: A report of an autism case with mutation in H1 linker histone HIST1H1e and literature review.

    Science.gov (United States)

    Duffney, Lara J; Valdez, Purnima; Tremblay, Martine W; Cao, Xinyu; Montgomery, Sarah; McConkie-Rosell, Allyn; Jiang, Yong-Hui

    2018-04-27

    Genetic mutations in genes encoding proteins involved in epigenetic machinery have been reported in individuals with autism spectrum disorder (ASD), intellectual disability, congenital heart disease, and other disorders. H1 histone linker protein, the basic component in nucleosome packaging and chromatin organization, has not been implicated in human disease until recently. We report a de novo deleterious mutation of histone cluster 1 H1 family member e (HIST1H1E; c.435dupC; p.Thr146Hisfs*50), encoding H1 histone linker protein H1.4, in a 10-year-old boy with autism and intellectual disability diagnosed through clinical whole exome sequencing. The c.435dupC at the 3' end of the mRNA leads to a frameshift and truncation of the positive charge in the carboxy-terminus of the protein. An expression study demonstrates the mutation leads to reduced protein expression, supporting haploinsufficiency of HIST1H1E protein and loss of function as an underlying mechanism of dysfunction in the brain. Taken together with other recent cases with mutations of HIST1H1E in intellectual disability, the evidence supporting the link to causality in disease is strong. Our finding implicates the deficiency of H1 linker histone protein in autism. The systematic review of candidate genes implicated in ASD revealed that 42 of 215 (19.5%) genes are directly involved in epigenetic regulations and the majority of these genes belong to histone writers, readers, and erasers. While the mechanism of how haploinsufficiency of HIST1H1E causes autism is entirely unknown, our report underscores the importance of further study of the function of this protein and other histone linker proteins in brain development. © 2018 Wiley Periodicals, Inc.

  6. Funktionalisierte Linker für Metallorganische Gerüstverbindungen, deren postsynthetische Modifikation und polar markierte Schutzgruppen für terminale Alkine

    OpenAIRE

    Roy, Pascal

    2011-01-01

    Metal-organic frameworks (MOFs) form the class of porous materials with the highest surface areas. This characteristic property combined with the variability of both building blocks, the inorganic node and the organic linker, makes many scientists dream of materials with very special chemical, electronic, optic and/or magnetic properties. For individual applications both building blocks, but also possibly in the framework embedded guests, play a crucial role. This work describes the synthe...

  7. Assessing the adsorption selectivity of linker functionalized, moisture-stable metal-organic framework thin films by means of an environment-controlled quartz crystal microbalance.

    Science.gov (United States)

    Bétard, Angélique; Wannapaiboon, Suttipong; Fischer, Roland A

    2012-11-04

    The stepwise thin film deposition of the robust, hydrophobic [Zn(4)O(dmcapz)(3)](n) (dmcapz = 3,5-dimethyl-4-carboxy-pyrazolato) is reported. The adsorption of small organic probe molecules, including alkanols, toluene, aniline and xylenes, was monitored by an environment-controlled quartz crystal microbalance setup. The adsorption selectivity was tuned by introducing alkyl side chains in the dmcapz linker.

  8. Learning a Weighted Sequence Model of the Nucleosome Core and Linker Yields More Accurate Predictions in Saccharomyces cerevisiae and Homo sapiens

    Science.gov (United States)

    Reynolds, Sheila M.; Bilmes, Jeff A.; Noble, William Stafford

    2010-01-01

    DNA in eukaryotes is packaged into a chromatin complex, the most basic element of which is the nucleosome. The precise positioning of the nucleosome cores allows for selective access to the DNA, and the mechanisms that control this positioning are important pieces of the gene expression puzzle. We describe a large-scale nucleosome pattern that jointly characterizes the nucleosome core and the adjacent linkers and is predominantly characterized by long-range oscillations in the mono, di- and tri-nucleotide content of the DNA sequence, and we show that this pattern can be used to predict nucleosome positions in both Homo sapiens and Saccharomyces cerevisiae more accurately than previously published methods. Surprisingly, in both H. sapiens and S. cerevisiae, the most informative individual features are the mono-nucleotide patterns, although the inclusion of di- and tri-nucleotide features results in improved performance. Our approach combines a much longer pattern than has been previously used to predict nucleosome positioning from sequence—301 base pairs, centered at the position to be scored—with a novel discriminative classification approach that selectively weights the contributions from each of the input features. The resulting scores are relatively insensitive to local AT-content and can be used to accurately discriminate putative dyad positions from adjacent linker regions without requiring an additional dynamic programming step and without the attendant edge effects and assumptions about linker length modeling and overall nucleosome density. Our approach produces the best dyad-linker classification results published to date in H. sapiens, and outperforms two recently published models on a large set of S. cerevisiae nucleosome positions. Our results suggest that in both genomes, a comparable and relatively small fraction of nucleosomes are well-positioned and that these positions are predictable based on sequence alone. We believe that the bulk of the

  9. Identification of unique interactions between the flexible linker and the RecA-like domains of DEAD-box helicase Mss116

    International Nuclear Information System (INIS)

    Zhang, Yuan; Palla, Mirkó; Liao, Jung-Chi; Sun, Andrew

    2013-01-01

    DEAD-box RNA helicases are ATP-dependent proteins implicated in nearly all aspects of RNA metabolism. The yeast DEAD-box helicase Mss116 is unique in its functions of splicing group I and group II introns and activating mRNA translation, but the structural understanding of why it performs these unique functions remains unclear. Here we used sequence analysis and molecular dynamics simulation to identify residues in the flexible linker specific for yeast Mss116, potentially associated with its unique functions. We first identified residues that are 100% conserved in Mss116 of different species of the Saccharomycetaceae family. The amino acids of these conserved residues were then compared with the amino acids of the corresponding residue positions of other RNA helicases to identify residues that have distinct amino acids from other DEAD-box proteins. Four residues in the flexible linker, i.e. N334, E335, P336 and H339, are conserved and Mss116-specific. Molecular dynamics simulation was conducted for the wild-type Mss116 structure and mutant models to examine mutational effects of the linker on the conformational equilibrium. Relatively short MD simulation runs (within 20 ns) were enough for us to observe mutational effects, suggesting serious structural perturbations by these mutations. The mutation of E335 depletes the interactions between E335 and K95 in domain 1. The interactions between N334/P336 and N496/I497 of domain 2 are also abolished by mutation. Our results suggest that tight interactions between the Mss116-specific flexible linker and the two RecA-like domains may be mechanically required to crimp RNA for the unique RNA processes of yeast Mss116. (paper)

  10. Identification of unique interactions between the flexible linker and the RecA-like domains of DEAD-box helicase Mss116

    Science.gov (United States)

    Zhang, Yuan; Palla, Mirkó; Sun, Andrew; Liao, Jung-Chi

    2013-09-01

    DEAD-box RNA helicases are ATP-dependent proteins implicated in nearly all aspects of RNA metabolism. The yeast DEAD-box helicase Mss116 is unique in its functions of splicing group I and group II introns and activating mRNA translation, but the structural understanding of why it performs these unique functions remains unclear. Here we used sequence analysis and molecular dynamics simulation to identify residues in the flexible linker specific for yeast Mss116, potentially associated with its unique functions. We first identified residues that are 100% conserved in Mss116 of different species of the Saccharomycetaceae family. The amino acids of these conserved residues were then compared with the amino acids of the corresponding residue positions of other RNA helicases to identify residues that have distinct amino acids from other DEAD-box proteins. Four residues in the flexible linker, i.e. N334, E335, P336 and H339, are conserved and Mss116-specific. Molecular dynamics simulation was conducted for the wild-type Mss116 structure and mutant models to examine mutational effects of the linker on the conformational equilibrium. Relatively short MD simulation runs (within 20 ns) were enough for us to observe mutational effects, suggesting serious structural perturbations by these mutations. The mutation of E335 depletes the interactions between E335 and K95 in domain 1. The interactions between N334/P336 and N496/I497 of domain 2 are also abolished by mutation. Our results suggest that tight interactions between the Mss116-specific flexible linker and the two RecA-like domains may be mechanically required to crimp RNA for the unique RNA processes of yeast Mss116.

  11. Optimization of the Alkyl Linker of TO Base Surrogate in Triplex-Forming PNA for Enhanced Binding to Double-Stranded RNA.

    Science.gov (United States)

    Sato, Takaya; Sato, Yusuke; Nishizawa, Seiichi

    2017-03-23

    A series of triplex-forming peptide nucleic acid (TFP) probes carrying a thiazole orange (TO) base surrogate through an alkyl linker was synthesized, and the interactions between these so-called tFIT probes and purine-rich sequences within double-stranded RNA (dsRNA) were examined. We found that the TO base surrogate linker significantly affected both the binding affinity and the fluorescence response upon triplex formation with the target dsRNA. Among the probes examined, the TO base surrogate connected through the propyl linker in the tFIT probes increased the binding affinity by a factor of ten while maintaining its function as the fluorescent universal base. Isothermal titration calorimetry experiments revealed that the increased binding affinity resulted from the gain in the binding enthalpy, which could be explained by the enhanced π-stacking interaction between the TO base surrogate and the dsRNA part of the triplex. We expect that these results will provide a molecular basis for designing strong binding tFIT probes for fluorescence sensing of various kinds of purine-rich dsRNAs sequences including those carrying a pyrimidine-purine inversion. The obtained data also offers a new insight into further development of the universal bases incorporated in TFP. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. The role of H1 linker histone subtypes in preserving the fidelity of elaboration of mesendodermal and neuroectodermal lineages during embryonic development.

    Directory of Open Access Journals (Sweden)

    Giang D Nguyen

    Full Text Available H1 linker histone proteins are essential for the structural and functional integrity of chromatin and for the fidelity of additional epigenetic modifications. Deletion of H1c, H1d and H1e in mice leads to embryonic lethality by mid-gestation with a broad spectrum of developmental alterations. To elucidate the cellular and molecular mechanisms underlying H1 linker histone developmental functions, we analyzed embryonic stem cells (ESCs depleted of H1c, H1d and H1e subtypes (H1-KO ESCs by utilizing established ESC differentiation paradigms. Our study revealed that although H1-KO ESCs continued to express core pluripotency genes and the embryonic stem cell markers, alkaline phosphatase and SSEA1, they exhibited enhanced cell death during embryoid body formation and during specification of mesendoderm and neuroectoderm. In addition, we demonstrated deregulation in the developmental programs of cardiomyocyte, hepatic and pancreatic lineage elaboration. Moreover, ectopic neurogenesis and cardiomyogenesis occurred during endoderm-derived pancreatic but not hepatic differentiation. Furthermore, neural differentiation paradigms revealed selective impairments in the specification and maturation of glutamatergic and dopaminergic neurons with accelerated maturation of glial lineages. These impairments were associated with deregulation in the expression profiles of pro-neural genes in dorsal and ventral forebrain-derived neural stem cell species. Taken together, these experimental observations suggest that H1 linker histone proteins are critical for the specification, maturation and fidelity of organ-specific cellular lineages derived from the three cardinal germ layers.

  13. Surface expression and subunit specific control of steady protein levels by the Kv7.2 helix A-B linker.

    Directory of Open Access Journals (Sweden)

    Paloma Aivar

    Full Text Available Kv7.2 and Kv7.3 are the main components of the neuronal voltage-dependent M-current, which is a subthreshold potassium conductance that exerts an important control on neuronal excitability. Despite their predominantly intracellular distribution, these channels must reach the plasma membrane in order to control neuronal activity. Thus, we analyzed the amino acid sequence of Kv7.2 to identify intrinsic signals that may control its surface expression. Removal of the interlinker connecting helix A and helix B of the intracellular C-terminus produces a large increase in the number of functional channels at the plasma membrane. Moreover, elimination of this linker increased the steady-state amount of protein, which was not associated with a decrease of protein degradation. The magnitude of this increase was inversely correlated with the number of helix A - helix B linkers present in the tetrameric channel assemblies. In contrast to the remarkable effect on the amount of Kv7.2 protein, removal of the Kv7.2 linker had no detectable impact on the steady-state levels of Kv7.3 protein.

  14. Development and characterization of polyclonal antibodies against the linker region of the telomere-binding protein TRF2

    Directory of Open Access Journals (Sweden)

    Nadya V. Ilicheva

    2018-03-01

    Full Text Available Background: TRF2 (telomeric repeat binding factor 2 is an essential component of the telomere-binding protein complex shelterin. TRF2 induces the formation of a special structure of telomeric DNA and counteracts activation of DNA damage-response pathways telomeres. TRF2 has a poorly characterized linker region (udTRF2 between its homodimerization and DNA-binding domains. Some lines of evidence have shown that this region could be involved in TRF2 interaction with nuclear lamina. Results: In this study, the fragment of the TERF2 gene encoding udTRF2 domain of telomere-binding protein TRF2 was produced by PCR and cloned into the pET32a vector. The resulting plasmid pET32a-udTRF2 was used for the expression of the recombinant udTRF2 in E. coli RosettaBlue (DE3. The protein was isolated and purified using ammonium sulfate precipitation followed by ion-exchange chromatography. The purified recombinant protein udTRF2 was injected into guinea pigs to generate polyclonal antibodies. The ability of anti-udTRF2 antibodies to bind endogenous TRF2 in human skin fibroblasts was tested by western blotting and immunofluorescent staining. Conclusions: In this study, the recombinant protein udTRF2 and antibodies to it were generated. Both protein and antibodies will provide a useful tool for investigation of the functions of the udTRF2 domain and its role in the interaction between TRF2 and nuclear lamina. Keywords: Chromosomes, Molecular cloning, Nuclear lamina, Nucleoprotein complexes, Polyclonal antibodies, Recombinant polypeptide, Shelterin, Telomere-binding protein TRF2, Telomeres, Telomeric DNA, TTAGGG repeats

  15. Stomach Chitinase from Japanese Sardine Sardinops melanostictus: Purification, Characterization, and Molecular Cloning of Chitinase Isozymes with a Long Linker

    Directory of Open Access Journals (Sweden)

    Satoshi Kawashima

    2016-01-01

    Full Text Available Fish express two different chitinases, acidic fish chitinase-1 (AFCase-1 and acidic fish chitinase-2 (AFCase-2, in the stomach. AFCase-1 and AFCase-2 have different degradation patterns, as fish efficiently degrade chitin ingested as food. For a comparison with the enzymatic properties and the primary structures of chitinase isozymes obtained previously from the stomach of demersal fish, in this study, we purified chitinase isozymes from the stomach of Japanese sardine Sardinops melanostictus, a surface fish that feeds on plankton, characterized the properties of these isozymes, and cloned the cDNAs encoding chitinases. We also predicted 3D structure models using the primary structures of S. melanostictus stomach chitinases. Two chitinase isozymes, SmeChiA (45 kDa and SmeChiB (56 kDa, were purified from the stomach of S. melanostictus. Moreover, two cDNAs, SmeChi-1 encoding SmeChiA, and SmeChi-2 encoding SmeChiB were cloned. The linker regions of the deduced amino acid sequences of SmeChi-1 and SmeChi-2 (SmeChi-1 and SmeChi-2 are the longest among the fish stomach chitinases. In the cleavage pattern groups toward short substrates and the phylogenetic tree analysis, SmeChi-1 and SmeChi-2 were classified into AFCase-1 and AFCase-2, respectively. SmeChi-1 and SmeChi-2 had catalytic domains that consisted of a TIM-barrel (β/α8–fold structure and a deep substrate-binding cleft. This is the first study showing the 3D structure models of fish stomach chitinases.

  16. In-Doped ZnO Hexagonal Stepped Nanorods and Nanodisks as Potential Scaffold for Highly-Sensitive Phenyl Hydrazine Chemical Sensors.

    Science.gov (United States)

    Umar, Ahmad; Kim, Sang Hoon; Kumar, Rajesh; Al-Assiri, Mohammad S; Al-Salami, A E; Ibrahim, Ahmed A; Baskoutas, Sotirios

    2017-11-21

    Herein, we report the growth of In-doped ZnO (IZO) nanomaterials, i.e., stepped hexagonal nanorods and nanodisks by the thermal evaporation process using metallic zinc and indium powders in the presence of oxygen. The as-grown IZO nanomaterials were investigated by several techniques in order to examine their morphological, structural, compositional and optical properties. The detailed investigations confirmed that the grown nanomaterials, i.e., nanorods and nanodisks possess well-crystallinity with wurtzite hexagonal phase and grown in high density. The room-temperature PL spectra exhibited a suppressed UV emissions with strong green emissions for both In-doped ZnO nanomaterials, i.e., nanorods and nanodisks. From an application point of view, the grown IZO nanomaterials were used as a potential scaffold to fabricate sensitive phenyl hydrazine chemical sensors based on the I-V technique. The observed sensitivities of the fabricated sensors based on IZO nanorods and nanodisks were 70.43 μA·mM -1 cm -2 and 130.18 μA·mM -1 cm -2 , respectively. For both the fabricated sensors, the experimental detection limit was 0.5 μM, while the linear range was 0.5 μM-5.0 mM. The observed results revealed that the simply grown IZO nanomaterials could efficiently be used to fabricate highly sensitive chemical sensors.

  17. A combined experimental and DFT study of a novel unsymmetrical azine 2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl) ethylidene) hydrazine

    Science.gov (United States)

    Vijaya, P.; Sankaran, K. R.

    2015-03-01

    A novel unsymmetrical azine 2-(4-methoxybenzylidene)-1-(1-(4-isobutylphenyl) ethylidene) hydrazine (UA) was prepared and characterized by IR, 1H and 13C NMR spectral studies. A 2D - potential energy scan (PES) of p-isobutylacetophenone (IBAP) was the portal to the conformational analysis of UA by density functional theory (DFT) methods using 6-31G(d,p) basis set by Gaussian 03 program. The theoretical IR frequencies were found to be in good agreement with the experimental values. The IR frequencies of UA were analyzed by means of Potential energy Distribution (PED %) calculation using Vibrational Energy Distribution Analysis (VEDA 4) program. The experimental NMR chemical shift values of UA were compared with the theoretical values obtained by DFT method. Nonlinear optical behavior of the unsymmetrical azine is also examined by the theoretically predicted values of dipole moment (μ), polarizability (α0) and first hyperpolarizability (βtot). Stability of the UA molecule has been analyzed using NBO analysis. The electrochemistry of UA studied experimentally by cyclic voltammetry is complemented by the computational analysis of the anionic form of the molecule UA. The determination of various global and local reactivity descriptors in the context of chemical reactivity is also performed and the electrophilicity at the vital atomic sites in UA is revealed. Bader's Atoms in molecules (AIM) theory of UA indicated the presence of intramolecular hydrogen bonding in the molecule. The molecular electrostatic potential (MEP) and HOMO-LUMO orbital analysis are also performed for the molecule UA.

  18. Hydrazine and hydrogen coinjection to mitigate stress corrosion cracking of structural materials in boiling water reactors (7). Effects of bulk water chemistry on ECP distribution inside a crack

    International Nuclear Information System (INIS)

    Wada, Yoichi; Ishida, Kazushige; Tachibana, Masahiko; Aizawa, Motohiro; Fuse, Motomasa

    2007-01-01

    Water chemistry in a simulated crack (crack) has been studied to understand the mechanisms of stress corrosion cracking in a boiling water reactor environment. Electrochemical corrosion potential (ECP) in a crack made in an austenite type 304 stainless steel specimen was measured. The ECP distribution along the simulated crack was strongly affected by bulk water chemistry and bulk flow. When oxygen concentration was high in the bulk water, the potential difference between the crack tip and the outside of the crack (ΔE), which must be one motive force for crack growth, was about 0.3V under a stagnant condition. When oxygen was removed from the bulk water, ECP inside and outside the crack became low and uniform and ΔE became small. The outside ECP was also lowered by depositing platinum on the steel specimen surface and adding stoichiometrically excess hydrogen to oxygen to lower ΔE. This was effective only when bulk water did not flow. Under the bulk water flow condition, water-borne oxygen caused an increase in ECP on the untreated surface inside the crack. This also caused a large ΔE. The ΔE effect was confirmed by crack growth rate measurements with a catalyst-treated specimen. Therefore, lowering the bulk oxidant concentration by such measures as hydrazine hydrogen coinjection, which is currently under development, is important for suppressing the crack growth. (author)

  19. SYNTHESIS AND CRYSTAL STRUCTURE OF A NA(I COMPLEX WITH 4,4’-BIPYRIDINE AND 2-FORMYL- BENZENESULFONATE-HYDRAZINE

    Directory of Open Access Journals (Sweden)

    TAI XI-SHI

    2015-07-01

    Full Text Available A Na(I complex, [Na(4,4’-bipyridine2·(H2O4]·L·OH·2H2O (L = 2-formyl-benzenesulfonate-hydrazine, has been synthesized. And its structure was determined by X-ray single crystal diffraction analysis. The Na(I complex belongs to orthorhombic, space group C2221 with a = 7.9162(16 Å, b = 18.451(4 Å, c = 26.397(5 Å, V= 3855.7(13 Å3, Z = 4, Dc = 1.394 mg·m-3, μ = 0.218 mm-1, F(000 =1689, and final R1 = 0.0683, ωR2 = 0.2017. The result shows that the Na(I center is six-coordination with a N2O4 distorted octahedral coordination environment. The Na(I complex forms 1D chain structure by the π-π stacking interaction.

  20. ZnO nanorods/ZnS·(1,6-hexanediamine)(0.5) hybrid nanoplates hierarchical heteroarchitecture with improved electrochemical catalytic properties for hydrazine.

    Science.gov (United States)

    Wu, Zhengcui; Wu, Yaqin; Pei, Tonghui; Wang, Huan; Geng, Baoyou

    2014-03-07

    Novel hierarchical heteronanostructures of ZnO nanorods/ZnS·(HDA)0.5 (HDA = 1,6-hexanediamine) hybrid nanoplates on a zinc substrate are successfully synthesized on a large scale by combining hydrothermal growth (for ZnO nanorods) and liquid chemical conversion (for ZnS·(HDA)0.5 nanoplates) techniques. The formation of ZnS·(HDA)0.5 hybrid nanoplates branches takes advantage of the preferential binding of 1,6-hexanediamine on specific facets of ZnS, which makes the thickening rate much lower than the lateral growth rate. The ZnS·(HDA)0.5 hybrid nanoplates have a layered structure with 1,6-hexanediamine inserted into interlayers of wurtzite ZnS through the bonding of nitrogen. The number density and thickness of the secondary ZnS·(HDA)0.5 nanoplates can be conveniently engineered by variation of the sulfur source and straightforward adjustment of reactant concentrations such as 1,6-hexanediamine and the sulfur source. The fabricated ZnO/ZnS·(HDA)0.5 heteronanostructures show improved electrochemical catalytic properties for hydrazine compared with the primary ZnO nanorods. Due to its simplicity and efficiency, this approach could be similarly used to fabricate varieties of hybrid heterostructures made of materials with an intrinsic large lattice mismatch.

  1. Determination of hydrazine in drinking water: Development and multivariate optimization of a rapid and simple solid phase microextraction-gas chromatography-triple quadrupole mass spectrometry protocol.

    Science.gov (United States)

    Gionfriddo, Emanuela; Naccarato, Attilio; Sindona, Giovanni; Tagarelli, Antonio

    2014-07-04

    In this work, the capabilities of solid phase microextraction were exploited in a fully optimized SPME-GC-QqQ-MS analytical approach for hydrazine assay. A rapid and easy method was obtained by a simple derivatization reaction with propyl chloroformate and pyridine carried out directly in water samples, followed by automated SPME analysis in the same vial without further sample handling. The affinity of the different derivatized compounds obtained towards five commercially available SPME coatings was evaluated, in order to achieve the best extraction efficiency. GC analyses were carried out using a GC-QqQ-MS instrument in selected reaction monitoring (SRM) acquisition mode which has allowed the achievement of high specificity by selecting appropriate precursor-product ion couples improving the capability in analyte identification. The multivariate approach of experimental design was crucial in order to optimize derivatization reaction, SPME process and tandem mass spectrometry parameters. Accuracy of the proposed protocol, tested at 60, 200 and 800 ng L(-1), provided satisfactory values (114.2%, 83.6% and 98.6%, respectively), whereas precision (RSD%) at the same concentration levels were of 10.9%, 7.9% and 7.7% respectively. Limit of detection and quantification of 4.4 and 8.3 ng L(-1) were obtained. The reliable application of the proposed protocol to real drinking water samples confirmed its capability to be used as analytical tool for routine analyses. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Ni-Pt nanoparticles growing on metal organic frameworks (MIL-96) with enhanced catalytic activity for hydrogen generation from hydrazine at room temperature.

    Science.gov (United States)

    Wen, Lan; Du, Xiaoqiong; Su, Jun; Luo, Wei; Cai, Ping; Cheng, Gongzhen

    2015-04-07

    Well-dispersed bimetallic Ni-Pt nanoparticles (NPs) with different compositions have been successfully grown on the MIL-96 by a simple liquid impregnation method using NaBH4 as the reducing agent. Powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray spectroscopy, N2 adsorption-desorption, and inductively coupled plasma-atomic emission spectroscopy measurements were employed to characterize the NiPt/MIL-96. Catalytic activity of NiPt/MIL-96 catalysts was tested in the hydrogen generation from the aqueous alkaline solution of hydrazine at room temperature. These catalysts are composition dependent on their catalytic activity, while Ni64Pt36/MIL-96 exhibits the highest catalytic activity among all the catalysts tested, with a turnover frequency value of 114.3 h(-1) and 100% hydrogen selectivity. This excellent catalytic performance might be due to the synergistic effect of the MIL-96 support and NiPt NPs, while NiPt NPs supported on other conventional supports, such as SiO2, carbon black, γ-Al2O3, poly(N-vinyl-2-pyrrolidone) (PVP), and the physical mixture of NiPt and MIL-96, all of them exhibit inferior catalytic activity compared to that of NiPt/MIL-96.

  3. Noninvasive imaging of tumor integrin expression using 18F-labeled RGD dimer peptide with PEG4 linkers

    International Nuclear Information System (INIS)

    Liu, Zhaofei; Liu, Shuanglong; Wang, Fan; Liu, Shuang; Chen, Xiaoyuan

    2009-01-01

    Various radiolabeled Arg-Gly-Asp (RGD) peptides have been previously investigated for tumor integrin α v β 3 imaging. To further develop RGD radiotracers with enhanced tumor-targeting efficacy and improved in vivo pharmacokinetics, we designed a new RGD homodimeric peptide with two PEG 4 spacers (PEG 4 = 15-amino-4,7,10,13-tetraoxapentadecanoic acid) between the two monomeric RGD motifs and one PEG 4 linker on the glutamate α-amino group ( 18 F-labeled PEG 4 -E[PEG 4 -c(RGDfK)] 2 , P-PRGD2), as a promising agent for noninvasive imaging of integrin expression in mouse models. P-PRGD2 was labeled with 18 F via 4-nitrophenyl 2- 18 F-fluoropropionate ( 18 F-FP) prosthetic group. In vitro and in vivo characteristics of the new dimeric RGD peptide tracer 18 F-FP-P-PRGD2 were investigated and compared with those of 18 F-FP-P-RGD2 ( 18 F-labeled RGD dimer without two PEG 4 spacers between the two RGD motifs). The ability of 18 F-FP-P-PRGD2 to image tumor vascular integrin expression was evaluated in a 4T1 murine breast tumor model. With the insertion of two PEG 4 spacers between the two RGD motifs, 18 F-FP-P-PRGD2 showed enhanced integrin α v β 3 -binding affinity, increased tumor uptake and tumor-to-nontumor background ratios compared with 18 F-FP-P-RGD2 in U87MG tumors. MicroPET imaging with 18 F-FP-P-PRGD2 revealed high tumor contrast and low background in tumor-bearing nude mice. Biodistribution studies confirmed the in vivo integrin α v β 3 -binding specificity of 18 F-FP-P-RGD2. 18 F-FP-P-PRGD2 can specifically image integrin α v β 3 on the activated endothelial cells of tumor neovasculature. 18 F-FP-P-PRGD2 can provide important information on integrin expression on the tumor vasculature. The high integrin binding affinity and specificity, excellent pharmacokinetic properties and metabolic stability make the new RGD dimeric tracer 18 F-FP-P-PRGD2 a promising agent for PET imaging of tumor angiogenesis and for monitoring the efficacy of antiangiogenic

  4. Dissociation Behavior of a TEMPO-Active Ester Cross-Linker for Peptide Structure Analysis by Free Radical Initiated Peptide Sequencing (FRIPS) in Negative ESI-MS.

    Science.gov (United States)

    Hage, Christoph; Ihling, Christian H; Götze, Michael; Schäfer, Mathias; Sinz, Andrea

    2017-01-01

    We have synthesized a homobifunctional amine-reactive cross-linking reagent, containing a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy) and a benzyl group (Bz), termed TEMPO-Bz-linker, to derive three-dimensional structural information of proteins. The aim for designing this novel cross-linker was to facilitate the mass spectrometric analysis of cross-linked products by free radical initiated peptide sequencing (FRIPS). In an initial study, we had investigated the fragmentation behavior of TEMPO-Bz-derivatized peptides upon collision activation in (+)-electrospray ionization collision-induced dissociation tandem mass spectrometry (ESI-CID-MS/MS) experiments. In addition to the homolytic NO-C bond cleavage FRIPS pathway delivering the desired odd-electron product ions, an alternative heterolytic NO-C bond cleavage, resulting in even-electron product ions mechanism was found to be relevant. The latter fragmentation route clearly depends on the protonation of the TEMPO-Bz-moiety itself, which motivated us to conduct (-)-ESI-MS, CID-MS/MS, and MS 3 experiments of TEMPO-Bz-cross-linked peptides to further clarify the fragmentation behavior of TEMPO-Bz-peptide molecular ions. We show that the TEMPO-Bz-linker is highly beneficial for conducting FRIPS in negative ionization mode as the desired homolytic cleavage of the NO-C bond is the major fragmentation pathway. Based on characteristic fragments, the isomeric amino acids leucine and isoleucine could be discriminated. Interestingly, we observed pronounced amino acid side chain losses in cross-linked peptides if the cross-linked peptides contain a high number of acidic amino acids. Graphical Abstract ᅟ.

  5. Effects of the Amino Acid Linkers on the Melanoma-Targeting and Pharmacokinetic Properties of Indium-111-labeled Lactam Bridge-Cyclized α-MSH Peptides

    Science.gov (United States)

    Guo, Haixun; Yang, Jianquan; Gallazzi, Fabio; Miao, Yubin

    2011-01-01

    The purpose of this study was to examine the profound effects of the amino acid linkers on the melanoma targeting and pharmacokinetic properties of novel 111In-labeled lactam bridge-cyclized DOTA-[X]-CycMSHhex {1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic acid-[X]-c[Asp-His-dPhe-Arg-Trp-Lys]-CONH2, X=GlyGlyNle, GlyGluNle or NleGlyGlu} peptides. Methods Three novel DOTA-GGNle-CycMSHhex, DOTA-GENle-CycMSHhex and DOTA-NleGE-CycMSHhex peptides were designed and synthesized. The melanocortin-1 (MC1) receptor binding affinities of the peptides were determined in B16/F1 melanoma cells. The melanoma targeting and pharmacokinetic properties of 111In-DOTA-GGNle-CycMSHhex and 111In-DOTA-GENle-CycMSHhex were determined in B16/F1 melanoma-bearing C57 mice. Results DOTA-GGNle-CycMSHhex and DOTA-GENle-CycMSHhex displayed 2.1 and 11.5 nM MC1 receptor binding affinities, whereas DOTA-NleGE-CycMSHhex showed 873.4 nM MC1 receptor binding affinity. The introduction of the -GlyGly- linker maintained high melanoma uptake while decreased the renal and liver uptakes of 111In-DOTA-GlyGlyNle-CycMSHhex. The tumor uptake values of 111In-DOTA-GGNle-CycMSHhex were 19.05 ± 5.04 and 18.6 ± 3.56 % injected dose/gram (%ID/g) at 2 and 4 h post-injection. 111In-DOTA-GGNle-CycMSHhex exhibited 28, 32 and 42% less renal uptake values than 111In-DOTA-Nle-CycMSHhex we reported previously, and 61, 65 and 68% less liver uptake values than 111In-DOTA-Nle-CycMSHhex at 2, 4 and 24 h post-injection, respectively. Conclusion The amino acid linkers exhibited the profound effects on the melanoma targeting and pharmacokinetic properties of the 111In-labeled lactam bridge-cyclized α-MSH peptides. Introduction of the -GlyGly- linker maintained high melanoma uptake while reducing the renal and liver uptakes of 111In-DOTA-GlyGlyNle-CycMSHhex, highlighting its potential as an effective imaging probe for melanoma detection, as well as a therapeutic peptide for melanoma treatment when labeled with a therapeutic

  6. Effects of the amino acid linkers on the melanoma-targeting and pharmacokinetic properties of 111In-labeled lactam bridge-cyclized alpha-MSH peptides.

    Science.gov (United States)

    Guo, Haixun; Yang, Jianquan; Gallazzi, Fabio; Miao, Yubin

    2011-04-01

    The purpose of this study was to examine the profound effects of the amino acid linkers on the melanoma-targeting and pharmacokinetic properties of (111)In-labeled lactam bridge-cyclized DOTA-[X]-CycMSH(hex) {1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid-[X]-c[Asp-His-dPhe-Arg-Trp-Lys]-CONH(2); X = GGNle, GENle, or NleGE; GG = -Gly-Gly- and GE = -Gly-Glu-} peptides. Three novel peptides (DOTA-GGNle-CycMSH(hex), DOTA-GENle-CycMSH(hex), and DOTA-NleGE-CycMSH(hex)) were designed and synthesized. The melanocortin-1 (MC1) receptor-binding affinities of the peptides were determined in B16/F1 melanoma cells. The melanoma-targeting and pharmacokinetic properties of (111)In-DOTA-GGNle-CycMSH(hex) and (111)In-DOTA-GENle-CycMSH(hex) were determined in B16/F1 melanoma-bearing C57 mice. DOTA-GGNle-CycMSH(hex) and DOTA-GENle-CycMSH(hex) displayed 2.1 and 11.5 nM MC1 receptor-binding affinities, whereas DOTA-NleGE-CycMSH(hex) showed 873.4 nM MC1 receptor-binding affinity. The introduction of the -GG- linker maintained high melanoma uptake while decreasing kidney and liver uptake of (111)In-DOTA-GGNle-CycMSH(hex). The tumor uptake of (111)In-DOTA-GGNle-CycMSH(hex) was 19.05 ± 5.04 and 18.6 ± 3.56 percentage injected dose per gram at 2 and 4 h after injection, respectively. (111)In-DOTA-GGNle-CycMSH(hex) exhibited 28%, 32%, and 42% less kidney uptake than (111)In-DOTA-Nle-CycMSH(hex) we reported previously, and 61%, 65%, and 68% less liver uptake than (111)In-DOTA-Nle-CycMSH(hex) at 2, 4, and 24 h after injection, respectively. The amino acid linkers exhibited profound effects on the melanoma-targeting and pharmacokinetic properties of the (111)In-labeled lactam bridge-cyclized α-melanocyte-stimulating hormone peptides. Introduction of the -GG- linker maintained high melanoma uptake while reducing kidney and liver uptake of (111)In-DOTA-GGNle-CycMSH(hex), highlighting its potential as an effective imaging probe for melanoma detection, as well as a therapeutic peptide

  7. Saccharomyces cerevisiae Linker Histone Hho1p Functionally Interacts with Core Histone H4 and Negatively Regulates the Establishment of Transcriptionally Silent Chromatin*

    OpenAIRE

    Yu, Qun; Kuzmiak, Holly; Zou, Yanfei; Olsen, Lars; Defossez, Pierre-Antoine; Bi, Xin

    2009-01-01

    Saccharomyces cerevisiae linker histone Hho1p is not essential for cell viability, and very little is known about its function in vivo. We show that deletion of HHO1 (hho1Δ) suppresses the defect in transcriptional silencing caused by a mutation in the globular domain of histone H4. hho1Δ also suppresses the reduction in HML silencing by the deletion of SIR1 that is involved in the establishment of silent chromatin at HML. We further show that hho1Δ suppresses chan...

  8. ZnO nanorods/ZnS.(1,6-hexanediamine)0.5 hybrid nanoplates hierarchical heteroarchitecture with improved electrochemical catalytic properties for hydrazine

    Science.gov (United States)

    Wu, Zhengcui; Wu, Yaqin; Pei, Tonghui; Wang, Huan; Geng, Baoyou

    2014-02-01

    Novel hierarchical heteronanostructures of ZnO nanorods/ZnS.(HDA)0.5 (HDA = 1,6-hexanediamine) hybrid nanoplates on a zinc substrate are successfully synthesized on a large scale by combining hydrothermal growth (for ZnO nanorods) and liquid chemical conversion (for ZnS.(HDA)0.5 nanoplates) techniques. The formation of ZnS.(HDA)0.5 hybrid nanoplates branches takes advantage of the preferential binding of 1,6-hexanediamine on specific facets of ZnS, which makes the thickening rate much lower than the lateral growth rate. The ZnS.(HDA)0.5 hybrid nanoplates have a layered structure with 1,6-hexanediamine inserted into interlayers of wurtzite ZnS through the bonding of nitrogen. The number density and thickness of the secondary ZnS.(HDA)0.5 nanoplates can be conveniently engineered by variation of the sulfur source and straightforward adjustment of reactant concentrations such as 1,6-hexanediamine and the sulfur source. The fabricated ZnO/ZnS.(HDA)0.5 heteronanostructures show improved electrochemical catalytic properties for hydrazine compared with the primary ZnO nanorods. Due to its simplicity and efficiency, this approach could be similarly used to fabricate varieties of hybrid heterostructures made of materials with an intrinsic large lattice mismatch.Novel hierarchical heteronanostructures of ZnO nanorods/ZnS.(HDA)0.5 (HDA = 1,6-hexanediamine) hybrid nanoplates on a zinc substrate are successfully synthesized on a large scale by combining hydrothermal growth (for ZnO nanorods) and liquid chemical conversion (for ZnS.(HDA)0.5 nanoplates) techniques. The formation of ZnS.(HDA)0.5 hybrid nanoplates branches takes advantage of the preferential binding of 1,6-hexanediamine on specific facets of ZnS, which makes the thickening rate much lower than the lateral growth rate. The ZnS.(HDA)0.5 hybrid nanoplates have a layered structure with 1,6-hexanediamine inserted into interlayers of wurtzite ZnS through the bonding of nitrogen. The number density and thickness of the

  9. Tuning the field distribution and fabrication of an Al@ZnO core-shell nanostructure for a SPR-based fiber optic phenyl hydrazine sensor.

    Science.gov (United States)

    Tabassum, Rana; Kaur, Parvinder; Gupta, Banshi D

    2016-05-27

    We report the fabrication and characterization of a surface plasmon resonance (SPR)-based fiber optic sensor that uses coatings of silver and aluminum (Al)-zinc oxide (ZnO) core-shell nanostructure (Al@ZnO) for the detection of phenyl hydrazine (Ph-Hyd). To optimize the volume fraction (f) of Al in ZnO and the thickness of the core-shell nanostructure layer (d), the electric field intensity along the normal to the multilayer system is simulated using the two-dimensional multilayer matrix method. The Al@ZnO core-shell nanostructure is prepared using the laser ablation technique. Various probes are fabricated with different values of f and an optimized thickness of core-shell nanostructure for the characterization of the Ph-Hyd sensor. The performance of the Ph-Hyd sensor is evaluated in terms of sensitivity. It is found that the Ag/Al@ZnO nanostructure core-shell-coated SPR probe with f = 0.25 and d = 0.040 μm possesses the maximum sensitivity towards Ph-Hyd. These results are in agreement with the simulated ones obtained using electric field intensity. In addition, the performance of the proposed probe is compared with that of probes coated with (i) Al@ZnO nanocomposite, (ii) Al nanoparticles and (iii) ZnO nanoparticles. It is found that the probe coated with an Al@ZnO core-shell nanostructure shows the largest resonance wavelength shift. The detailed mechanism of the sensing (involving chemical reactions) is presented. The sensor also manifests optimum performance at pH 7.

  10. Design and construction of new potentiometric sensors for determination of Al3+ ion based on (Z)-2-(2-methyl benzylidene)-1-(2,4-dinitrophenyl) hydrazine.

    Science.gov (United States)

    Mizani, F; Salmanzadeh Ardabili, S; Ganjaliab, M R; Faridbod, F; Payehghadr, M; Azmoodeh, M

    2015-04-01

    (Z)-2-(2-methyl benzylidene)-1-(2,4-dinitrophenyl) hydrazine (L) was used as an active component of PVC membrane electrode (PME), coated graphite electrode (CGE) and coated silver wire electrode (CWE) for sensing Al(3+) ion. The electrodes exhibited linear Nernstian responses to Al(3+) ion in the concentration range of 1.0×10(-6) to 1.0×10(-1)M (for PME, LOD=8.8×10(-7)M), 5.5×10(-7) to 2.0×10(-1)M (for CWE, LOD=3.3×10(-7)M) and 1.5×10(-7) to 1.0×10(-1)M (for CGE, LOD=9.2×10(-8)M). The best performances were observed with the membranes having the composition of L:PVC:NPOE:NaTPB in the ratio of 5:35:57:3 (w/w; mg). The electrodes have a response time of 6s and an applicable pH range of 3.5-9.1. The sensors have a lifetime of about 15weeks and exhibited excellent selectivity over a number of mono-, bi-, and tri-valent cations including alkali, alkaline earth metal, heavy and transition metal ions. Analytical utility of the proposed sensor has been further tested by using it as an indicator electrode in the potentiometric titration of Al(3+) with EDTA. The electrode was also successfully applied for the determination of Al(3+) ion in real and pharmaceutical samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Synthetic surfactant- and cross-linker-free preparation of highly stable lipid-polymer hybrid nanoparticles as potential oral delivery vehicles.

    Science.gov (United States)

    Wang, Taoran; Xue, Jingyi; Hu, Qiaobin; Zhou, Mingyong; Chang, Chao; Luo, Yangchao

    2017-06-05

    The toxicity associated with concentrated synthetic surfactants and the poor stability at gastrointestinal condition are two major constraints for practical applications of solid lipid nanoparticles (SLN) as oral delivery vehicles. In this study, a synthetic surfactant-free and cross-linker-free method was developed to fabricate effective, safe, and ultra-stable lipid-polymer hybrid nanoparticles (LPN). Bovine serum albumin (BSA) and dextran varying in molecular weights were first conjugated through Maillard reaction and the conjugates were exploited to emulsify solid lipid by a solvent diffusion and sonication method. The multilayer structure was formed by self-assembly of BSA-dextran micelles to envelope solid lipid via a pH- and heating-induced facile process with simultaneous surface deposition of pectin. The efficiency of different BSA-dextran conjugates was systematically studied to prepare LPN with the smallest size, the most homogeneous distribution and the greatest stability. The molecular interactions were characterized by Fourier transform infrared and fluorescence spectroscopies. Both nano spray drying and freeze-drying methods were tested to produce spherical and uniform pectin-coated LPN powders that were able to re-assemble nanoscale structure when redispersed in water. The results demonstrated the promise of a synthetic surfactant- and cross-linker-free technique to prepare highly stable pectin-coated LPN from all natural biomaterials as potential oral delivery vehicles.

  12. Site specific replacements of a single loop nucleoside with a dibenzyl linker may switch the activity of TBA from anticoagulant to antiproliferative.

    Science.gov (United States)

    Scuotto, Maria; Rivieccio, Elisa; Varone, Alessia; Corda, Daniela; Bucci, Mariarosaria; Vellecco, Valentina; Cirino, Giuseppe; Virgilio, Antonella; Esposito, Veronica; Galeone, Aldo; Borbone, Nicola; Varra, Michela; Mayol, Luciano

    2015-09-18

    Many antiproliferative G-quadruplexes (G4s) arise from the folding of GT-rich strands. Among these, the Thrombin Binding Aptamer (TBA), as a rare example, adopts a monomolecular well-defined G4 structure. Nevertheless, the potential anticancer properties of TBA are severely hampered by its anticoagulant action and, consequently, no related studies have appeared so far in the literature. We wish to report here that suitable chemical modifications in the TBA sequence can preserve its antiproliferative over anticoagulant activity. Particularly, we replaced one residue of the TT or TGT loops with a dibenzyl linker to develop seven new quadruplex-forming TBA based sequences (TBA-bs), which were studied for their structural (CD, CD melting, 1D NMR) and biological (fibrinogen, PT and MTT assays) properties. The three-dimensional structures of the TBA-bs modified at T13 (TBA-bs13) or T12 (TBA-bs12), the former endowed with selective antiproliferative activity, and the latter acting as potently as TBA in both coagulation and MTT assays, were further studied by 2D NMR restrained molecular mechanics. The comparative structural analyses indicated that neither the stability, nor the topology of the G4s, but the different localization of the two benzene rings of the linker was responsible for the loss of the antithrombin activity for TBA-bs13. © Crown copyright 2015.

  13. Quercetin-glutamic acid conjugate with a non-hydrolysable linker; a novel scaffold for multidrug resistance reversal agents through inhibition of P-glycoprotein.

    Science.gov (United States)

    Kim, Mi Kyoung; Kim, Yunyoung; Choo, Hyunah; Chong, Youhoon

    2017-02-01

    Previously, we have reported remarkable effect of a quercetin-glutamic acid conjugate to reverse multidrug resistance (MDR) of cancer cells to a broad spectrum of anticancer agents through inhibition of P-glycoprotein (Pgp)-mediated drug efflux. Due to the hydrolysable nature, MDR-reversal activity of the quercetin conjugate was attributed to its hydrolysis product, quercetin. However, several lines of evidence demonstrated that the intact quercetin-glutamic acid conjugate has stronger MDR-reversal activity than quercetin. In order to evaluate this hypothesis and to identify a novel scaffold for MDR-reversal agents, we prepared quercetin conjugates with a glutamic acid attached at the 7-O position via a non-hydrolysable linker. Pgp inhibition assay, Pgp ATPase assay, and MDR-reversal activity assay were performed, and the non-hydrolysable quercetin conjugates showed significantly higher activities compared with those of quercetin. Unfortunately, the quercetin conjugates were not as effective as verapamil in Pgp-inhibition and thereby reversing MDR, but it is worth to note that the structurally modified quercetin conjugates with a non-cleavable linker showed significantly improved MDR-reversal activity compared with quercetin. Taken together, the quercetin conjugates with appropriate structural modifications were shown to have a potential to serve as a scaffold for the design of novel MDR-reversal agents. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Two-dimensional layer architecture assembled by Keggin polyoxotungstate, Cu(II)-EDTA complex and sodium linker: Synthesis, crystal structures, and magnetic properties

    International Nuclear Information System (INIS)

    Liu Hong; Xu Lin; Gao Guanggang; Li Fengyan; Yang Yanyan; Li Zhikui; Sun Yu

    2007-01-01

    Reaction of Keggin polyoxotungstate with copper(II)-EDTA (EDTA=ethylenediamine tetraacetate) complex under mild conditions led to the formation of hybrid inorganic-organic compounds Na 4 (OH)[(Cu 2 EDTA)PW 12 O 40 ].17H 2 O (1) and Na 4 [(Cu 2 EDTA)SiW 12 O 40 ].19H 2 O (2). The single-crystal X-ray diffraction analyses reveal their two structural features: (1) one-dimensional chain structure consisting of Keggin polyoxotungstate and copper(II)-EDTA complex; (2) Two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker. The results of magnetic measurements in the temperature range 300-2 K indicated the existence of ferromagnetic exchange interactions between the Cu II ions for both compounds. In addition, TGA analysis, IR spectra, and electrochemical properties were also investigated to well characterize these two compounds. - Graphical abstract: Two new polyoxometalate-based hybrids, Na 4 (OH)[Cu 2 (EDTA)PW 12 O 40 ].17H 2 O (1) and Na 4 [Cu 2 (EDTA)SiW 12 O 40 ].19H 2 O (2), have been synthesized and structurally characterized, which consist of one-dimensional chain structure assembled by Keggin polyoxotungstate and copper(II)-EDTA complex. The chains are further connected to form two-dimensional layer architecture assembled by the one-dimensional chain structure and sodium linker

  15. Structure of calmodulin complexed with an olfactory CNG channel fragment and role of the central linker: Residual dipolar couplings to evaluate calmodulin binding modes outside the kinase family

    International Nuclear Information System (INIS)

    Contessa, Gian Marco; Orsale, Maria; Melino, Sonia; Torre, Vincent; Paci, Maurizio; Desideri, Alessandro; Cicero, Daniel O.

    2005-01-01

    The NMR high-resolution structure of calmodulin complexed with a fragment of the olfactory cyclic-nucleotide gated channel is described. This structure shows features that are unique for this complex, including an active role of the linker connecting the N- and C-lobes of calmodulin upon binding of the peptide. Such linker is not only involved in the formation of an hydrophobic pocket to accommodate a bulky peptide residue, but it also provides a positively charged region complementary to a negative charge of the target. This complex of calmodulin with a target not belonging to the kinase family was used to test the residual dipolar coupling (RDC) approach for the determination of calmodulin binding modes to peptides. Although the complex here characterized belongs to the (1--14) family, high Q values were obtained with all the 1:1 complexes for which crystalline structures are available. Reduction of the RDC data set used for the correlation analysis to structured regions of the complex allowed a clear identification of the binding mode. Excluded regions comprise calcium binding loops and loops connecting the EF-hand motifs

  16. Crucial role of dynamic linker histone binding and divalent ions for DNA accessibility and gene regulation revealed by mesoscale modeling of oligonucleosomes

    Science.gov (United States)

    Collepardo-Guevara, Rosana; Schlick, Tamar

    2012-01-01

    Monte Carlo simulations of a mesoscale model of oligonucleosomes are analyzed to examine the role of dynamic-linker histone (LH) binding/unbinding in high monovalent salt with divalent ions, and to further interpret noted chromatin fiber softening by dynamic LH in monovalent salt conditions. We find that divalent ions produce a fiber stiffening effect that competes with, but does not overshadow, the dramatic softening triggered by dynamic-LH behavior. Indeed, we find that in typical in vivo conditions, dynamic-LH binding/unbinding reduces fiber stiffening dramatically (by a factor of almost 5, as measured by the elasticity modulus) compared with rigidly fixed LH, and also the force needed to initiate chromatin unfolding, making it consistent with those of molecular motors. Our data also show that, during unfolding, divalent ions together with LHs induce linker-DNA bending and DNA–DNA repulsion screening, which guarantee formation of heteromorphic superbeads-on-a-string structures that combine regions of loose and compact fiber independently of the characteristics of the LH–core bond. These structures might be important for gene regulation as they expose regions of the DNA selectively. Dynamic control of LH binding/unbinding, either globally or locally, in the presence of divalent ions, might constitute a mechanism for regulation of gene expression. PMID:22790986

  17. Mutations in B3GALT6, which encodes a glycosaminoglycan linker region enzyme, cause a spectrum of skeletal and connective tissue disorders.

    Science.gov (United States)

    Nakajima, Masahiro; Mizumoto, Shuji; Miyake, Noriko; Kogawa, Ryo; Iida, Aritoshi; Ito, Hironori; Kitoh, Hiroshi; Hirayama, Aya; Mitsubuchi, Hiroshi; Miyazaki, Osamu; Kosaki, Rika; Horikawa, Reiko; Lai, Angeline; Mendoza-Londono, Roberto; Dupuis, Lucie; Chitayat, David; Howard, Andrew; Leal, Gabriela F; Cavalcanti, Denise; Tsurusaki, Yoshinori; Saitsu, Hirotomo; Watanabe, Shigehiko; Lausch, Ekkehart; Unger, Sheila; Bonafé, Luisa; Ohashi, Hirofumi; Superti-Furga, Andrea; Matsumoto, Naomichi; Sugahara, Kazuyuki; Nishimura, Gen; Ikegawa, Shiro

    2013-06-06

    Proteoglycans (PGs) are a major component of the extracellular matrix in many tissues and function as structural and regulatory molecules. PGs are composed of core proteins and glycosaminoglycan (GAG) side chains. The biosynthesis of GAGs starts with the linker region that consists of four sugar residues and is followed by repeating disaccharide units. By exome sequencing, we found that B3GALT6 encoding an enzyme involved in the biosynthesis of the GAG linker region is responsible for a severe skeletal dysplasia, spondyloepimetaphyseal dysplasia with joint laxity type 1 (SEMD-JL1). B3GALT6 loss-of-function mutations were found in individuals with SEMD-JL1 from seven families. In a subsequent candidate gene study based on the phenotypic similarity, we found that B3GALT6 is also responsible for a connective tissue disease, Ehlers-Danlos syndrome (progeroid form). Recessive loss-of-function mutations in B3GALT6 result in a spectrum of disorders affecting a broad range of skeletal and connective tissues characterized by lax skin, muscle hypotonia, joint dislocation, and spinal deformity. The pleiotropic phenotypes of the disorders indicate that B3GALT6 plays a critical role in a wide range of biological processes in various tissues, including skin, bone, cartilage, tendon, and ligament. Copyright © 2013 The American Society of Human Genetics. Published by Elsevier Inc. All rights reserved.

  18. The effect of linker of electrodes prepared from sol–gel ionic liquid precursor and carbon nanoparticles on dioxygen electroreduction bioelectrocatalysis

    International Nuclear Information System (INIS)

    Szot, Katarzyna; Lynch, Robert P.; Lesniewski, Adam; Majewska, Ewa; Sirieix-Plenet, Juliette; Gaillon, Laurent; Opallo, Marcin

    2011-01-01

    The effect of linker of three-dimensional, hydrophilic-carbon-nanoparticle film-electrodes prepared by layer-by-layer method on redox probe accumulation and bioelectrocatalytic dioxygen reduction was studied and compared for two different electrode scaffolds. The linker in both of these scaffolds was based on the same ionic liquid sol–gel precursor, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium bis(trifluoromethyl-sulfonyl)imide. The first electrode type was prepared by alternative immersion of tin doped indium oxide substrate in an aqueous suspension of carbon nanoparticles modified with phenyl sulphonic groups and a sol composed of ionic liquid sol–gel precursor and tetramethoxysilane. For the second electrode type sol was replaced by a methanolic suspension of silicate submicroparticles with appended imidazolium functional groups. In both films 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) anions accumulate irreversibly. In the case of the first electrode electrostatic attraction plays the more important role in comparison to the case of the second where stable adsorption of the redox probe takes place. After adsorption of bilirubin oxidase, electrodes obtained from sol and carbon nanoparticles exhibit modest bioelectrocatalytic activity towards dioxygen reduction at pH 4.8, however those obtained from oppositely charged particles are much more efficient. The magnitude of the associated catalytic current in both cases depends on the number of immersion and withdrawal steps. Interestingly, mediatorless catalysis at electrodes obtained from oppositely charged particles is more efficient than mediated catalysis.

  19. Reaction of 1-bromo-3-chloropropane with tellurium and dimethyl telluride in the system of hydrazine hydrate-alkali; Reaktsiya 1-brom-3-khlorpropana s tellurom i dimetilditelluridom v sisteme gidrazin-gidrat-shcheloch'

    Energy Technology Data Exchange (ETDEWEB)

    Russavskaya, N V; Levanova, E P; Sukhomazova, Eh N; Grabel' nykh, V A; Elaev, A V; Klyba, L V; Zhanchipova, E R; Albanov, A I; Korotaeva, I M; Toryashinova, D S.D.; Korchevin, N A [SO RAN, Irkutskij Inst. Khimii imeni A.E. Favorskogo, Irkutsk (Russian Federation)

    2006-05-15

    A synthesis of oligomeric substance of thiocol type, the poly(trimethyleneditelluride), from 1-bromo-3-chloropropane and elemental tellurium is performed using a hydrazine hydrate-alkali system. Reductive splitting of the tellurocol followed by alkylation with methyl iodide give rise to preparation of bis(methyltelluro)propane, which was synthesized also from dimethyl telluride and 1,3-dihalopropanes using the N{sub 2}H{sub 4}{center_dot}H{sub 2}O/KOH system. The reaction products were characterized by elementary analysis, NMR, and IR spectra. Mass spectra of the synthesized low molecular weight organotellurium compounds are considered.

  20. Lymphatic transport and lymph node targeting of methotrexate-conjugated PEGylated dendrimers are enhanced by reducing the length of the drug linker or masking interactions with the injection site.

    Science.gov (United States)

    Ryan, Gemma M; McLeod, Victoria M; Mehta, Dharmini; Kelly, Brian D; Stanislawski, Pauline C; Owen, David J; Kaminskas, Lisa M; Porter, Christopher J H

    2017-11-01

    Drug conjugation to dendrimer-based delivery systems has been shown to enhance delivery to the lymphatic system after subcutaneous administration. Dendrimer interaction with components of the interstitium at the injection site, however, may prevent drainage from the injection site. The current study sought to vary the length of a linker employed to conjugate methotrexate (MTX) to a PEGylated dendrimer, in an attempt to reduce MTX interaction with interstitial binding sites and enhance lymphatic drainage. Dendrimers with shorter linkers resulted in higher lymphatic drainage, presumably via shielding of interaction sites by the PEG mantle, but were not retained in lymph nodes. Improved drainage of dendrimers with longer linkers was achieved through coadministration with dextran to mask interactions at the injection site while maintaining retention within the node. Enhanced drug exposure to the lymph node has the potential to enhance the treatment of lymph-node resident cancer metastases. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. In-vitro DNA binding and cleavage studies with pBR322 of N,N-Bis(3{beta}-acetoxy-5{alpha}-cholest-6-yl-idene)hydrazine

    Energy Technology Data Exchange (ETDEWEB)

    Tabassum, Zishan [School of Industrial Technology, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Muddassir, Mohd [Department of Chemistry, Aligarh Muslim University, Aligarh 202002, U.P. (India); Sulaiman, Othman [School of Industrial Technology, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Arjmand, Farukh [Department of Chemistry, Aligarh Muslim University, Aligarh 202002, U.P. (India)

    2012-08-15

    The DNA binding studies of the triterpenoid derivative, cholesterol, N,N-Bis(3{beta}-acetoxy-5{alpha}-cholest-6-yl-idene)hydrazine (L) with CT DNA were carried out by employing different optical methods viz, UV-vis and fluorescence spectroscopy. The ligand binds to DNA through hydrophobic interaction with K{sub b} value found to be 4.7 Multiplication-Sign 10{sup 3} M{sup -1}. These observations have been validated also by fluorescence spectroscopy. (L) exhibits a remarkable DNA cleavage activity with pBR322 DNA in the presence of different activators and the DNA is probably cleaved by an other than oxidative mechanism, possibly by a discernable hydrolytic pathway. In the presence of major and minor groove binding agents, (L) prefers major groove binding of the DNA. - Highlights: Black-Right-Pointing-Pointer DNA binding studies of the triterpenoid derivative, cholesterol, N,N-Bis(3{beta}-acetoxy-5{alpha}-cholest-6-yl-idene)hydrazine. Black-Right-Pointing-Pointer The ligand binds to DNA through hydrophobic interaction with K{sub b} value found to be 4.7 Multiplication-Sign 10{sup 3} M{sup -1}. Black-Right-Pointing-Pointer DNA is probably cleaved by an other than oxidative mechanism, possibly by a discernable hydrolytic pathway. Black-Right-Pointing-Pointer In the presence of major and minor groove binding agents, the (L) prefers major groove binding of the DNA.

  2. In-vitro DNA binding and cleavage studies with pBR322 of N,N-Bis(3β-acetoxy-5α-cholest-6-yl-idene)hydrazine

    International Nuclear Information System (INIS)

    Tabassum, Zishan; Muddassir, Mohd; Sulaiman, Othman; Arjmand, Farukh

    2012-01-01

    The DNA binding studies of the triterpenoid derivative, cholesterol, N,N-Bis(3β-acetoxy-5α-cholest-6-yl-idene)hydrazine (L) with CT DNA were carried out by employing different optical methods viz, UV–vis and fluorescence spectroscopy. The ligand binds to DNA through hydrophobic interaction with K b value found to be 4.7×10 3 M −1 . These observations have been validated also by fluorescence spectroscopy. (L) exhibits a remarkable DNA cleavage activity with pBR322 DNA in the presence of different activators and the DNA is probably cleaved by an other than oxidative mechanism, possibly by a discernable hydrolytic pathway. In the presence of major and minor groove binding agents, (L) prefers major groove binding of the DNA. - Highlights: ► DNA binding studies of the triterpenoid derivative, cholesterol, N,N-Bis(3β-acetoxy-5α-cholest-6-yl-idene)hydrazine. ► The ligand binds to DNA through hydrophobic interaction with K b value found to be 4.7×10 3 M −1 . ► DNA is probably cleaved by an other than oxidative mechanism, possibly by a discernable hydrolytic pathway. ► In the presence of major and minor groove binding agents, the (L) prefers major groove binding of the DNA.

  3. A potential method using Ge{iPrNC[N(SiMe_3)_2]NiPr}{sub 2}, (Et{sub 3}Si){sub 2}Te and anhydrous hydrazine for germanium tellurides

    Energy Technology Data Exchange (ETDEWEB)

    Du, Liyong; Du, Shulei; Ding, Yuqiang [School of Chemical and Material Engineering, Jiangnan University, Wuxi (China)

    2017-12-29

    A germanium(II)-guanidine derivative of formula Ge{iPrNC[N(SiMe_3)_2]NiPr}{sub 2} (1) was synthesized and characterized by {sup 1}H NMR, {sup 13}C NMR, elemental analysis, and X-ray diffraction method. Thermal property was also studied to identify its thermal stability and volatility. More importantly, compound 1 was synthesized to develop a new method for germanium tellurides, where anhydrous hydrazine was introduced to prompt the activity of germanium(II) guanidines (or derivatives) towards (Et{sub 3}Si){sub 2}Te. Solution reaction of compound 1, (Et{sub 3}Si){sub 2}Te, and anhydrous hydrazine was investigated to pre-identify the feasibility of this combination for ALD process. The EDS data of the black precipitate from this reaction verified the potential of this method to manufacture germanium tellurides. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. Introduction of an 8-aminooctanoic acid linker enhances uptake of 99mTc-labeled lactam bridge-cyclized α-MSH peptide in melanoma.

    Science.gov (United States)

    Guo, Haixun; Miao, Yubin

    2014-12-01

    The purpose of this study was to examine the effects of amino acid, hydrocarbon, and polyethylene glycol (PEG) linkers on the melanoma targeting and imaging properties of (99m)Tc-labeled lactam bridge-cyclized HYNIC-linker-Nle-CycMSHhex (hydrazinonicotinamide-linker-Nle-c[Asp-His-DPhe-Arg-Trp-Lys]-CONH2) peptides. Four novel peptides (HYNIC-GGGNle-CycMSHhex, HYNIC-GSGNle-CycMSHhex, HYNIC-PEG2Nle-CycMSHhex, and HYNIC-AocNle-CycMSHhex) were designed and synthesized. The melanocortin-1 receptor binding affinities of the peptides were determined in B16/F1 melanoma cells. The biodistribution of (99m)Tc(ethylenediaminediacetic acid [EDDA])-HYNIC-GGGNle-CycMSHhex, (99m)Tc(EDDA)-HYNIC-GSGNle-CycMSHhex, (99m)Tc(EDDA)-HYNIC-PEG2Nle-CycMSHhex, and (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex were determined in B16/F1 melanoma-bearing C57 mice at 2 h after injection to select a lead peptide for further evaluation. The melanoma targeting and imaging properties of (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex were further examined because of its high melanoma uptake. The inhibitory concentrations of 50% (IC50) for HYNIC-GGGNle-CycMSHhex, HYNIC-GSGNle-CycMSHhex, HYNIC-PEG2Nle-CycMSHhex, and HYNIC-AocNle-CycMSHhex were 0.7 ± 0.1, 0.8 ± 0.09, 0.4 ± 0.08, and 0.3 ± 0.06 nM, respectively, in B16/F1 melanoma cells. Among these four (99m)Tc-labeled peptides, (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex displayed the highest melanoma uptake (22.3 ± 1.72 percentage injected dose/g) at 2 h after injection. (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex exhibited high tumor-to-normal-organ uptake ratios except for the kidneys. The tumor-to-kidney uptake ratios of (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex were 3.29, 3.63, and 6.78 at 2, 4, and 24 h, respectively, after injection. The melanoma lesions were clearly visualized by SPECT/CT using (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex as an imaging probe at 2 h after injection. High melanoma uptake and fast urinary clearance of (99m)Tc(EDDA)-HYNIC-AocNle-CycMSHhex highlighted its

  5. Introduction of an 8-Aminooctanoic Acid Linker Enhances the melanoma uptake of Tc-99m-labeled Lactam Bridge-Cyclized Alpha-MSH Peptide

    Science.gov (United States)

    Guo, Haixun; Miao, Yubin

    2015-01-01

    The purpose of this study was to examine the effects of amino acid, hydrocarbon and polyethylene glycol (PEG) linkers on melanoma targeting and imaging properties of 99mTc-labeled lactam bridge-cyclized HYNIC-linker-Nle-CycMSHhex {hydrazinonicotinamide-linker-Nle-c[Asp-His-DPhe-Arg-Trp-Lys]-CONH2} peptides. Methods four novel peptides {HYNIC-GGGNle-CycMSHhex, HYNIC-GSGNle-CycMSHhex, HYNIC-PEG2Nle-CycMSHhex and HYNIC-AocNle-CycMSHhex} were designed and synthesized. The melanocortin-1 (MC1) receptor binding affinities of the peptides were determined in B16/F1 melanoma cells. The biodistribution of 99mTc(EDDA)-HYNIC-GGGNle-CycMSHhex, 99mTc(EDDA)-HYNIC-GSGNle-CycMSHhex, 99mTc(EDDA)-HYNIC-PEG2Nle-CycMSHhex and 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex were determined in B16/F1 melanoma-bearing C57 mice at 2 h post-injection to select a lead peptide for further evaluation. The melanoma targeting and imaging properties of 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex were further examined because of its high melanoma uptake. Results The IC50 values of HYNIC-GGGNle-CycMSHhex, HYNIC-GSGNle-CycMSHhex, HYNIC-PEG2Nle-CycMSHhex, and HYNIC-AocNle-CycMSHhex were 0.7 ± 0.1, 0.8 ± 0.09, 0.4 ± 0.08, and 0.3 ± 0.06 nM in B16/F1 melanoma cells, respectively. Among these four 99mTc-labeled peptides, 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex displayed the highest melanoma uptake (22.3 ± 1.72% ID/g) at 2 h post-injection. 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex exhibited high tumor to normal organ uptake ratios except for the kidneys. The tumor/kidney uptake ratios of 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex were 3.29, 3.63 and 6.78 at 2, 4 and 24 h post-injection. The melanoma lesions were clearly visualized by single photon emission computed tomography (SPECT)/CT using 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex as an imaging probe at 2 h post-injection. Conclusion High melanoma uptake and fast urinary clearance of 99mTc(EDDA)-HYNIC-AocNle-CycMSHhex highlighted its potential for metastatic melanoma detection in the future

  6. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies.

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH 2 -CH=CH-CH 2 -) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than ~1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  7. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH2-CH=CH-CH2-) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than 1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  8. Adenoviral vectors expressing fusogenic membrane glycoproteins activated via matrix metalloproteinase cleavable linkers have significant antitumor potential in the gene therapy of gliomas.

    Science.gov (United States)

    Allen, Cory; McDonald, Cari; Giannini, Caterina; Peng, Kah Whye; Rosales, Gabriela; Russell, Stephen J; Galanis, Evanthia

    2004-11-01

    Fusogenic membrane glycoproteins (FMG) such as the gibbon ape leukemia virus envelope (GALV) glycoprotein are potent therapeutic transgenes with potential utility in the gene therapy of gliomas. Transfection of glioma cell lines with FMG expression constructs results in fusion with massive syncytia formation followed by cytotoxic cell death. Nevertheless, ubiquitous expression of the GALV receptor, Pit-1, makes targeting desirable in order to increase the specificity of the observed cytopathic effect. Here we report on use of matrix metalloproteinase (MMP)-cleavable linkers to target the cytotoxicity of FMG-expressing adenoviral vectors against gliomas. Replication-defective adenoviruses (Ad) were constructed expressing the hyperfusogenic version of the GALV glycoprotein linked to a blocking ligand (C-terminal extracellular domain of CD40 ligand) through either an MMP-cleavable linker (AdM40) or a non-cleavable linker (AdN40). Both viruses also co-expressed the green fluorescent protein (GFP) via an internal ribosomal entry site. The glioma cell lines U87, U118, and U251 characterized by zymography and MMP-2 activity assay as high, medium and low MMP expressors, respectively, the MMP-poor cell lines TE671 and normal human astrocytes were infected with AdM40 and AdN40 at different multiplicities of infection (MOIs) from 1-30. Fusion was quantitated by counting both number and size of syncytia. Infection of these cell lines with AdN40 did not result in fusion or cytotoxic cell death, despite the presence of infection, as demonstrated by GFP positivity, therefore indicating that the displayed CD40 ligand blocked GALV-induced fusion. Fusion was restored after infection of glioma cells with AdM40 at an MOI as low as 1 to an extent dependent on MMP expression and coxsackie adenovirus receptor (CAR) expression in the specific cell line. Western immunoblotting demonstrated the presence of the cleaved CD40 ligand in the supernatant of fused glioma cells. Use of the MMP

  9. Rapid, sensitive, and selective fluorescent DNA detection using iron-based metal-organic framework nanorods: Synergies of the metal center and organic linker.

    Science.gov (United States)

    Tian, Jingqi; Liu, Qian; Shi, Jinle; Hu, Jianming; Asiri, Abdullah M; Sun, Xuping; He, Yuquan

    2015-09-15

    Considerable recent attention has been paid to homogeneous fluorescent DNA detection with the use of nanostructures as a universal "quencher", but it still remains a great challenge to develop such nanosensor with the benefits of low cost, high speed, sensitivity, and selectivity. In this work, we report the use of iron-based metal-organic framework nanorods as a high-efficient sensing platform for fluorescent DNA detection. It only takes about 4 min to complete the whole "mix-and-detect" process with a low detection limit of 10 pM and a strong discrimination of single point mutation. Control experiments reveal the remarkable sensing behavior is a consequence of the synergies of the metal center and organic linker. This work elucidates how composition control of nanostructures can significantly impact their sensing properties, enabling new opportunities for the rational design of functional materials for analytical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. The Au-S bond and SAM-protein contact in long-range electron transfer of pure and biomimetic metalloproteins via functionalized alkanethiol linkers

    DEFF Research Database (Denmark)

    Chi, Qijin; Ford, Michael J.; Halder, Arnab

    disentangled a wealth of data to identify the nature of the crucial Au-S contact, all suggesting prevalence of a Au(0)-thiyl radical unit. Molecular packing is further determined by the SAM molecular structure and involves binding either to Au-atoms mined out of the surface or directly to a flat surface. We...... functionalized alkanethiols have emerged as core linkers. We have studied molecular linking in the long-range ET (LRET) processes in detail using electrochemistry, in situ STM and AFM, and electronic structure computations. A focus is the electronic structure of the Au-S link and the SAM packing. We have...... is exceedingly sensitive to the structure of the thiol-based SAM molecules, testifying to the crucial importance of SAM packing and Au-S binding, and of the SAM link to the protein. Some of the subtleties are illustrated simpler by similar size (5-6 nm) nanoparticles (NPs). Biomimetic NPs must possess a certain...

  11. Synthesis of Biotin Linkers with the Activated Triple Bond Donor [p-(N-propynoylaminotoluic Acid] (PATA for Efficient Biotinylation of Peptides and Oligonucleotides

    Directory of Open Access Journals (Sweden)

    Martina Jezowska

    2012-11-01

    Full Text Available Biotin is an important molecule for modern biological studies including, e.g., cellular transport. Its exclusive affinity to fluorescent streptavidin/avidin proteins allows ready and specific detection. As a consequence methods for the attachment of biotin to various biological targets are of high importance, especially when they are very selective and can also proceed in water. One useful method is Hüisgen dipolar [3+2]-cycloaddition, commonly referred to as “click chemistry”. As we reported recently, the activated triple bond donor p-(N-propynoylaminotoluic acid (PATA gives excellent results when used for conjugations at submicromolar concentrations. Thus, we have designed and synthesized two biotin linkers, with different lengths equipped with this activated triple bond donor and we proceeded with biotinylation of oligonucleotides and C-myc peptide both in solution and on solid support with excellent yields of conversion.

  12. Effects of the capping ligands, linkers and oxide surface on the electron injection mechanism of copper sulfide quantum dot-sensitized solar cells.

    Science.gov (United States)

    Suárez, Javier Amaya; Plata, Jose J; Márquez, Antonio M; Sanz, Javier Fdez

    2017-06-07

    Quantum dot-sensitized solar cells, QDSCs, are a clean and effective alternative to fossil fuels to reduce CO 2 emissions. However, the different components that constitute the QDSCs and the difficulty of isolating experimentally their effects on the performance of the whole system slow down the development of more efficient devices. In this work, DFT calculations are combined with a bottom-up approach to differentiate the effect of each component on the electronic structure and absorption spectra. First, Cu 2 S QDs were built including a U parameter to effectively describe the localization of electrons. The effect of capping agents is addressed using ligands with different electron-donating/withdrawing groups. The role of linkers and their adsorption on the oxide surface are also examined. Finally, we propose a main indirect electron injection mechanism based on the position of the peaks of the spectra.

  13. Steric effects in release of amides from linkers in solid-phase synthesis. Molecular mechanics modeling of key step in peptide and combinatorial chemistry

    DEFF Research Database (Denmark)

    Norrby, Per-Ola; Jensen, Knud Jørgen

    2006-01-01

    Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid-lability of the ba......Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid......-lability of the backbone amide linkage (BAL), which releases sec. amides, compared to C-terminal amide anchoring, which releases primary amides, was rationalized by steric relief upon cleavage. Thus, the relative stability of the carbenium ion formed from the linker in the acidolytic release is an insufficient measure...

  14. The JH2 domain and SH2-JH2 linker regulate JAK2 activity: A detailed kinetic analysis of wild type and V617F mutant kinase domains.

    Science.gov (United States)

    Sanz Sanz, Arturo; Niranjan, Yashavanthi; Hammarén, Henrik; Ungureanu, Daniela; Ruijtenbeek, Rob; Touw, Ivo P; Silvennoinen, Olli; Hilhorst, Riet

    2014-10-01

    JAK2 tyrosine kinase regulates many cellular functions. Its activity is controlled by the pseudokinase (JH2) domain by still poorly understood mechanisms. The V617F mutation in the pseudokinase domain activates JAK2 and causes myeloproliferative neoplasms. We conducted a detailed kinetic analysis of recombinant JAK2 tyrosine kinase domain (JH1) and wild-type and V617F tandem kinase (JH1JH2) domains using peptide microarrays to define the functions of the kinase domains. The results show that i) JAK2 follows a random Bi-Bi reaction mechanism ii) JH2 domain restrains the activity of the JH1 domain by reducing the affinity for ATP and ATP competitive inhibitors iii) V617F decreases affinity for ATP but increases catalytic activity compared to wild-type and iv) the SH2-JH2 linker region participates in controlling activity by reducing the affinity for ATP. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. A histidine-rich linker region in peptidylglycine α-amidating monooxygenase has the properties of a pH sensor.

    Science.gov (United States)

    Vishwanatha, Kurutihalli; Bäck, Nils; Mains, Richard E; Eipper, Betty A

    2014-05-02

    Decreasing luminal pH is thought to play a role in the entry of newly synthesized and endocytosed membrane proteins into secretory granules. The two catalytic domains of peptidylglycine α-amidating monooxygenase (PAM), a type I integral membrane protein, catalyze the sequential reactions that convert peptidyl-Gly substrates into amidated products. We explored the hypothesis that a conserved His-rich cluster (His-Gly-His-His) in the linker region connecting its two catalytic domains senses pH and affects PAM trafficking by mutating these His residues to Ala (Ala-Gly-Ala-Ala; H3A). Purified recombinant wild-type and H3A linker peptides were examined using circular dichroism and tryptophan fluorescence; mutation of the His cluster largely eliminated its pH sensitivity. An enzymatically active PAM protein with the same mutations (PAM-1/H3A) was expressed in HEK293 cells and AtT-20 corticotrope tumor cells. Metabolic labeling followed by immunoprecipitation revealed more rapid loss of newly synthesized PAM-1/H3A than PAM-1; although release of newly synthesized monofunctional PHM/H3A was increased, release of soluble bifunctional PAM/H3A, a product of the endocytic pathway, was decreased. Surface biotinylation revealed rapid loss of PAM-1/H3A, with no detectable return of the mutant protein to secretory granules. Consistent with its altered endocytic trafficking, little PAM-1/H3A was subjected to regulated intramembrane proteolysis followed by release of a small nuclear-targeted cytosolic fragment. AtT-20 cells expressing PAM-1/H3A adopted the morphology of wild-type AtT-20 cells; secretory products no longer accumulated in the trans-Golgi network and secretory granule exocytosis was more responsive to secretagogue.

  16. COMPLEXES CONTAINING HYDRAZINE AND BENZYL ...

    African Journals Online (AJOL)

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    Treatment of 2 in refluxing acetone in the presence of the ... Microanalyses were carried out at the Center for Nanotechnology, Department of. Chemistry ... product as mixtures of colourless prisms and needles containing methanol and water of.

  17. Studies on coordination chemistry and bioactivity of metal complexes of a bidentate NN schiff base, (2-pyridyl-methylene)(phenyl) hydrazine, produced from the condensation of pyridine-2-carboxaldehyde with phenylhydrazine

    International Nuclear Information System (INIS)

    Tarafder, M.T.H.; Zakaria, C.M.; Idrus, Razmi Mohd; Crouse, Karen A.; Ali, A.M.; Yamin, B.M.; Fun, H.-K.

    2003-07-01

    A bidentate Schiff base, (2-pyridyl-methylene)(phenyl) hydrazine, with NN donor sequence, was isolated from the condensation of pyridine-2-carboxaldehyde with phenylhydrazine in ethanol. Metal complexes of this ligand with Ni(II), Zn(It), and Cu(n) ions were synthesized and characterized by a variety of physico-chemical techniques. The structure of the Schiff base was solved by X-ray diffraction studies, which indicated that it was monoclinic with a space group of C2/c. The complexes were all four coordinated. The compounds were tested against four pathogenic bacteria and fungi. The nickel complex, [Ni(NN) 2 Cl 2 ], in particular, was found to be active against all the fungi tested. The complexes were however inactive against leukemic cell lines (CEM-SS). (author)

  18. Synthesis, physical-chemical properties, antimicrobial and antifungal activity of some 2-(2-((5-(adamantane-1-yl-4-R-1,2,4-triazole-3-ylthioacetyl-N-R1–hydrazine-carbothioamides

    Directory of Open Access Journals (Sweden)

    V. M. Odyntsova

    2017-12-01

    Full Text Available Special attention of pharmaceutical scientists is attracted to the creation of new potential substances. They select natural heterocyclic molecules that exhibit various types of pharmacological activity as basic structures. Adamantane derivatives, as well as a number of other framework compounds, in the vast majority are biologically active substances. This fact causes interest to the given classes of organic compounds as potential sources for the development of new drugs. Due to the high pharmacological action of 1,2,4-triazole derivatives, the combination of adamantane and 1,2,4-triazole in one molecule can lead to the formation of high-level pharmacological substances. The aim of this work is the synthesis of some 2- (2 - ((5- (adamantane-1-yl -4-R-1,2,4-triasole-3-yl thio acetyl -N-R1-hydrazine-carbothioamides, study of their physical and chemical properties, antimicrobial and antifungal activity. Materials and methods. The chemical names of the compounds are given in accordance with the requirements of the IUPAC nomenclature (1979 and the recommendations of the IUPAC (1993. Study of the physical and chemical properties of 2-(2-((5-(adamantane-1-yl-4-R-1,2,4-triazole-3-ylthioacetyl-N-R1-hydrazine-carbothioamides have been carried out on the certified and licensed equipment in the ZSMU physical-chemical laboratories. The melting temperature was determined by an open capillary method on the Opti Melt MPA 100. The elemental composition of the synthesized compounds was determined on the universal analyzer Elementar Vario L cube (CHNS (standard – sulfanilamide. 1H NMR spectra were recorded on a spectrometer Varian Mercury VX-200 (1H, 200 MHz in dimethylsulfoxide-d6solvent (tetramethylsilane - internal standard and are decoded using ADVASP(tmAnalyzer program (Umatek International Inc.. Chromatographic mass spectral studies were performed on a gas-liquid chromatograph Agilent 1260 Infinity HPLC equipped with an Agilent 6120 mass spectrometer

  19. Determination of trace selenium by solid substrate-room temperature phosphorescence enhancing method based on potassium chlorate oxidizing phenyl hydrazine-1,2-dihydroxynaphthalene-3,6-disulfonic acid system

    Science.gov (United States)

    Liu, Jia-Ming; Cui, Xiao-Jie; Li, Lai-Ming; Fu, Geng-Min; Lin, Shao-Xian; Yang, Min-Lan; Xu, Mei-Ying; Wu, Zhi-Qun

    2007-04-01

    A new method for the determination of trace selenium based on solid substrate-room temperature phosphorimetry (SS-RTP) has been established. This method was based on the fact that in HCl-KCl buffer solution, potassium chlorate could oxidize phenyl hydrazine to form chloridize diazo-ion after being heated at 100 °C for 20 min, and then the diazo-ion reacted with 1,2-dihydroxynaphthalene-3,6-disulfonic acid to form red azo-compound which could emit strong room temperature phosphorescence (RTP) signal on filter paper. Selenium could catalyze potassium chlorate oxidizing the reaction between phenyl hydrazine and 1,2-dihydroxynaphthalene-3,6-disulfonic acid, which caused the sharp enhancement of SS-RTP. Under the optimum condition, the relationship between the phosphorescence emission intensity (Δ Ip) and the content of selenium obeyed Beer's law when the concentration of selenium is within the range of 1.60-320 fg spot -1 (or 0.0040-0.80 ng ml -1 with a sample volume of 0.4 μl). The regression equation of working curve can be expressed as Δ Ip = 13.12 + 0.4839 CSe(IV) (fg spot -1) ( n = 6), with correlation coefficient r = 0.9991 and a detection limit of 0.28 fg spot -1 (corresponding to a concentration range of 7.0 × 10 -13 g ml -1 Se(IV), n = 11). After 11-fold measurement, R.S.D. were 2.8 and 3.5% for the samples containing 0.0040 and 0.80 ng ml -1 of Se(IV), respectively. This accurate and sensitive method with good repeatability has been successfully applied to the determination of trace selenium in Chinese wolfberry and egg yolk with satisfactory results. The mechanism of the enhancement of phosphorescence was also discussed.

  20. Synthesis of TiO2-loaded Co0.85Se thin films with heterostructure and their enhanced catalytic activity for p-nitrophenol reduction and hydrazine hydrate decomposition

    International Nuclear Information System (INIS)

    Zuo, Yong; Song, Ji-Ming; Niu, He-Lin; Mao, Chang-Jie; Zhang, Sheng-Yi; Shen, Yu-Hua

    2016-01-01

    P-nitrophenol (4-NP) and hydrazine hydrate are considered to be highly toxic pollutants in wastewater, and it is of great importance to remove them. Herein, TiO 2 -loaded Co 0.85 Se thin films with heterostructure were successfully synthesized by a hydrothermal route. The as-synthesized samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy and selective-area electron diffraction. The results demonstrate that TiO 2 nanoparticles with a size of about 10 nm are easily loaded on the surface of graphene-like Co 0.85 Se nanofilms, and the NH 3  · H 2 O plays an important role in the generation and crystallization of TiO 2 nanoparticles. Brunauer–Emmett–Teller measurement shows that the obtained nanocomposites have a larger specific surface area (199.3 m 2 g −1 ) than that of Co 0.85 Se nanofilms (55.17 m 2 g −1 ) and TiO 2 nanoparticles (19.49 m 2 g −1 ). The catalytic tests indicate Co 0.85 Se–TiO 2 nanofilms have the highest activity for 4-NP reduction and hydrazine hydrate decomposition within 10 min and 8 min, respectively, compared with the corresponding precursor Co 0.85 Se nanofilms and TiO 2 nanoparticles. The enhanced catalytic performance can be attributed to the larger specific surface area and higher rate of interfacial charge transfer in the heterojunction than that of the single components. In addition, recycling tests show that the as-synthesized sample presents stable conversion efficiency for 4-NP reduction. (paper)

  1. 177Lu-labeled HPMA copolymers utilizing cathepsin B and S cleavable linkers: Synthesis, characterization and preliminary in vivo investigation in a pancreatic cancer model

    International Nuclear Information System (INIS)

    Ogbomo, Sunny M.; Shi, Wen; Wagh, Nilesh K.; Zhou, Zhengyuan; Brusnahan, Susan K.; Garrison, Jered C.

    2013-01-01

    Introduction: A major barrier to the advancement of therapeutic nanomedicines has been the non-target toxicity caused by the accumulation of the drug delivery systems in organs associated with the reticuloendothelial system, particularly the liver and spleen. Herein, we report the development of peptide based metabolically active linkers (MALs) that are enzymatically cleaved by cysteine cathepsin B and S, two proteases highly expressed in the liver and spleen. The overall goal of this approach is to utilize the MALs to lower the non-target retention and toxicity of radiolabeled drug delivery systems, thus resulting in higher diagnostic and radiotherapeutic efficacy. Methods: In this study three MALs (MAL0, MAL1 and MAL2) were investigated. MAL1 and MAL2 are composed of known substrates of cathepsin B and S, respectively, while MAL0 is a non-cleavable control. Both MAL1 and MAL2 were shown to undergo enzymatic cleavage with the appropriate cathepsin protease. Subsequent to conjugation to the HPMA copolymer and radiolabeling with 177 Lu, the peptide–polymer conjugates were renamed 177 Lu-metabolically active copolymers ( 177 Lu-MACs) with the corresponding designations: 177 Lu-MAC0, 177 Lu-MAC1 and 177 Lu-MAC2. Results: In vivo evaluation of the 177 Lu-MACs was performed in an HPAC human pancreatic cancer xenograft mouse model. 177 Lu-MAC1 and 177 Lu-MAC2 demonstrated 3.1 and 2.1 fold lower liver retention, respectively, compared to control ( 177 Lu-MAC0) at 72 h post-injection. With regard to spleen retention, 177 Lu-MAC1 and 177 Lu-MAC2 each exhibited a nearly fourfold lower retention, relative to control, at the 72 h time point. However, the tumor accumulation of the 177 Lu-MAC0 was two to three times greater than 177 Lu-MAC1 and 177 Lu-MAC2 at the same time point. The MAL approach demonstrated the capability of substantially reducing the non-target retention of the 177 Lu-labeled HPMA copolymers. Conclusions: While further studies are needed to optimize the

  2. Rootletin interacts with C-Nap1 and may function as a physical linker between the pair of centrioles/basal bodies in cells.

    Science.gov (United States)

    Yang, Jun; Adamian, Michael; Li, Tiansen

    2006-02-01

    Rootletin, a major structural component of the ciliary rootlet, is located at the basal bodies and centrosomes in ciliated and nonciliated cells, respectively. Here we investigated its potential role in the linkage of basal bodies/centrioles and the mechanism involved in such linkages. We show that rootletin interacts with C-Nap1, a protein restricted at the ends of centrioles and functioning in centrosome cohesion in interphase cells. Their interaction in vivo is supported by their colocalization at the basal bodies/centrioles and coordinated association with the centrioles during the cell cycle. Ultrastructural examinations demonstrate that rootletin fibers connect the basal bodies in ciliated cells and are present both at the ends of and in between the pair of centrioles in nonciliated cells. The latter finding stands in contrast with C-Nap1, which is present only at the ends of the centrioles. Transient expression of C-Nap1 fragments dissociated rootletin fibers from the centrioles, resulting in centrosome separation in interphase. Overexpression of rootletin in cells caused multinucleation, micronucleation, and irregularity of nuclear shape and size, indicative of defects in chromosome separation. These data suggest that rootletin may function as a physical linker between the pair of basal bodies/centrioles by binding to C-Nap1.

  3. Impact of functional monomers, cross-linkers and porogens on morphology and recognition properties of 2-(3,4-dimethoxyphenyl)ethylamine imprinted polymers

    International Nuclear Information System (INIS)

    Lulinski, Piotr; Maciejewska, Dorota

    2011-01-01

    The main objective of this paper was to examined the impact of synthetic reagents on morphology and recognition properties of 2-(3,4-dimethoxyphenyl)ethylamine imprinted polymers. The effect of nine different functional monomers, five porogens and four cross-linkers on the binding capacity of particles was analyzed. The results revealed that the highest imprinting factor (1.81) showed the polymer obtained from methacrylic acid and ethylene glycol dimethacrylate in toluene. The binding capacities of imprinted (MIP1) and non-imprinted (NIP1) materials were 135.3 ± 9.8 and 74.8 ± 7.8 μmol g -1 , respectively. The specific surface areas were 55.05 ± 3.89 for MIP1 and 38.72 ± 2.40 m 2 g -1 for NIP1. The SEM analysis confirmed that the surface of MIP1 is rougher and denser than NIP1. Structural analysis supported by 13 C CP/MAS NMR spectra was also performed. The binding abilities of homoveratrylamine and eight structurally related compounds to MIP1 showed that strong interactions between carboxylic group in the polymer and amine group in the analyte together with its molecular volume govern the recognition mechanism.

  4. Expression, purification and characterization of hepatitis B virus X protein BH3-like motif-linker-Bcl-xL fusion protein for structural studies

    Directory of Open Access Journals (Sweden)

    Hideki Kusunoki

    2017-03-01

    Full Text Available Hepatitis B virus X protein (HBx is a multifunctional protein that interacts directly with many host proteins. For example, HBx interacts with anti-apoptotic proteins, Bcl-2 and Bcl-xL, through its BH3-like motif, which leads to elevated cytosolic calcium levels, efficient viral DNA replication and the induction of apoptosis. To facilitate sample preparation and perform detailed structural characterization of the complex between HBx and Bcl-xL, we designed and purified a recombinant HBx BH3-like motif-linker-Bcl-xL fusion protein produced in E. coli. The fusion protein was characterized by size exclusion chromatography, circular dichroism and nuclear magnetic resonance experiments. Our results show that the fusion protein is a monomer in aqueous solution, forms a stable intramolecular complex, and likely retains the native conformation of the complex between Bcl-xL and the HBx BH3-like motif. Furthermore, the HBx BH3-like motif of the intramolecular complex forms an α-helix. These observations indicate that the fusion protein should facilitate structural studies aimed at understanding the interaction between HBx and Bcl-xL at the atomic level.

  5. A limited 4 Å radial displacement of the S4-S5 linker is sufficient for internal gate closing in Kv channels.

    Science.gov (United States)

    Faure, Élise; Starek, Greg; McGuire, Hugo; Bernèche, Simon; Blunck, Rikard

    2012-11-16

    Voltage-gated ion channels are responsible for the generation of action potentials in our nervous system. Conformational rearrangements in their voltage sensor domains in response to changes of the membrane potential control pore opening and thus ion conduction. Crystal structures of the open channel in combination with a wealth of biophysical data and molecular dynamics simulations led to a consensus on the voltage sensor movement. However, the coupling between voltage sensor movement and pore opening, the electromechanical coupling, occurs at the cytosolic face of the channel, from where no structural information is available yet. In particular, the question how far the cytosolic pore gate has to close to prevent ion conduction remains controversial. In cells, spectroscopic methods are hindered because labeling of internal sites remains difficult, whereas liposomes or detergent solutions containing purified ion channels lack voltage control. Here, to overcome these problems, we controlled the state of the channel by varying the lipid environment. This way, we directly measured the position of the S4-S5 linker in both the open and the closed state of a prokaryotic Kv channel (KvAP) in a lipid environment using Lanthanide-based resonance energy transfer. We were able to reconstruct the movement of the covalent link between the voltage sensor and the pore domain and used this information as restraints for molecular dynamics simulations of the closed state structure. We found that a small decrease of the pore radius of about 3-4 Å is sufficient to prevent ion permeation through the pore.

  6. The C. elegans tailless/Tlx homolog nhr-67 regulates a stage-specific program of linker cell migration in male gonadogenesis.

    Science.gov (United States)

    Kato, Mihoko; Sternberg, Paul W

    2009-12-01

    Cell migration is a common event during organogenesis, yet little is known about how migration is temporally coordinated with organ development. We are investigating stage-specific programs of cell migration using the linker cell (LC), a migratory cell crucial for male gonadogenesis of C. elegans. During the L3 and L4 larval stages of wild-type males, the LC undergoes changes in its position along the migratory route, in transcriptional regulation of the unc-5 netrin receptor and zmp-1 zinc matrix metalloprotease, and in cell morphology. We have identified the tailless homolog nhr-67 as a cell-autonomous, stage-specific regulator of timing in LC migration programs. In nhr-67-deficient animals, each of the L3 and L4 stage changes is either severely delayed or never occurs, yet LC development before the early L3 stage or after the mid-L4 stage occurs with normal timing. We propose that there is a basal migration program utilized throughout LC migration that is modified by stage-specific regulators such as nhr-67.

  7. Development of a polymeric ionic liquid coating for direct-immersion solid-phase microextraction using polyhedral oligomeric silsesquioxane as cross-linker.

    Science.gov (United States)

    Chen, Chunyan; Liang, Xiaotong; Wang, Jianping; Zou, Ying; Hu, Huiping; Cai, Qingyun; Yao, Shouzhuo

    2014-06-27

    A novel solid-phase microextraction (SPME) fiber was developed by chemical binding of a crosslinked polymeric ionic liquid (PIL) on the surface of an anodized Ti wire, and was applied in direct-immersion mode for the extraction of perfluorinated compounds (PFCs) from water samples coupled with high performance liquid chromatography-tandem mass spectrometry analysis. The PIL coatings were synthesized by using 1-vinyl-3-hexylimidazolium hexafluorophosphate as monomer and methylacryloyl-substituted polyhedral oligomeric silsesquioxane (POSS) as cross-linker via free radical reaction. The proposed fiber coating exhibited high mechanical stability due to the chemical bonding between the coating and the Ti wire surface. The integration of POSS reagent enhanced the organic solvent resistance of the coating. The parameters affecting the extraction performance of the fiber coating including extraction time, pH of solution, ionic strength and desorption conditions were optimized. The developed PIL-POSS fiber showed good linearity (R<0.998) between 0.1 and 50ngmL(-1) with method detection limits ranging from 0.005 to 0.08ngmL(-1) depending on the analyte, and with relative standard deviation for single-fiber repeatability and fiber-to-fiber reproducibility less than 8.6% and 9.5%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Alginate-okra gum blend beads of diclofenac sodium from aqueous template using ZnSO4 as a cross-linker.

    Science.gov (United States)

    Sinha, Priyanka; Ubaidulla, U; Hasnain, M Saquib; Nayak, Amit Kumar; Rama, Bobba

    2015-08-01

    Zinc (Zn(2+))-ion induced diclofenac sodium (DS)-loaded alginate-okra (Hibiscus esculentus) gum (OG) blend beads was successfully formulated through Zn(2+)-ion induced ionic-gelation cross-linking method in a complete aqueous environment. Effects of polymer-blend ratio and cross-linker concentration on drug encapsulation efficiency (DEE) and cumulative drug release at 8 h (R8h) were optimized by 3(2)-factorial design. The optimized formulation of Zn(2+)-ion induced DS-loaded alginate-OG beads demonstrated 89.27±3.58% of DEE and 43.73±2.83% of R8h. The bead sizes were within 1.10±0.07 to 1.38±0.14 mm. The bead surface morphology was analyzed by SEM. The drug-polymer interaction in the optimized bead matrix was analyzed by FTIR and P-XRD. These beads exhibited sustained in vitro drug release over a prolonged period of 8h and followed controlled-release (zero-order) pattern with super case-II transport mechanism. The swelling and degradation of the optimized beads was influenced by the pH of test mediums, which might be suitable for intestinal drug delivery. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Dehydration of an azeotrope of ethanol/water by sodium carboxymethylcellulose membranes cross-linked with organic or inorganic cross-linker

    Directory of Open Access Journals (Sweden)

    2010-11-01

    Full Text Available To control the swelling of sodium carboxymethylcellulose (CMCNa membranes, mixtures of CMCNa and glutaraldehyde (GA and mixtures of CMCNa as an organic component and tetraethoxysilane (TEOS as an inorganic component were prepared, and CMCNa/GA cross-linked membranes and CMCNa/TEOS hybrid membranes were formed. In the separation of an ethanol/water azeotrope by pervaporation (PV, the effects of the GA or TEOS content on the water/ethanol selectivity and permeability of these CMCNa/GA cross-linked and CMCNa/TEOS hybrid membranes were investigated. Cross-linked and hybrid membranes containing up to 10 wt% GA or 10 wt% TEOS exhibited higher water/ethanol selectivity than CMCNa membrane without any cross-linker. This resulted from both increased density and depressed swelling of the membranes by the formation of a cross-linked structure. The relationship between the structure of the CMCNa/GA cross-linked membranes and CMCNa/TEOS hybrid membranes and their permeation and separation characteristics for an ethanol/water azeotrope during PV is discussed in detail.

  10. Linker for activation of T cells is displaced from lipid rafts and decreases in lupus T cells after activation via the TCR/CD3 pathway.

    Science.gov (United States)

    Abdoel, Nursamaa; Brun, Susana; Bracho, Carmen; Rodríguez, Martín A; Blasini, Ana M

    2012-03-01

    Systemic lupus erythematosus (SLE) is characterized by abnormal signal transduction mechanisms in T lymphocytes. Linker for activation of T cells (LAT) couples TCR/CD3 activation with downstream signaling pathways. We reported diminished ERK 1/2 kinase activity in TCR/CD3 stimulated lupus T cells. In this study we evaluated the expression, phosphorylation, lipid raft and immunological synapse (IS) localization and colocalization of LAT with key signalosome molecules. We observed a diminished expression and an abnormal localization of LAT in lipid rafts and at the IS in activated lupus T cells. LAT phosphorylation, capture by GST-Grb2 fusion protein, and coupling to Grb2 and PLCγ1, was similar in healthy control and lupus T cells. Our results suggest that an abnormal localization of LAT within lipid rafts and its accelerated degradation after TCR/CD3 activation may compromise the assembly of the LAT signalosome and downstream signaling pathways required for full MAPK activation in lupus T cells. Copyright © 2011 Elsevier Inc. All rights reserved.

  11. Simple, Fast and Selective Detection of Adenosine Triphosphate at Physiological pH Using Unmodified Gold Nanoparticles as Colorimetric Probes and Metal Ions as Cross-Linkers

    Directory of Open Access Journals (Sweden)

    Huan Pang

    2012-11-01

    Full Text Available We report a simple, fast and selective colorimetric assay of adenosine triphosphate (ATP using unmodified gold nanoparticles (AuNPs as probes and metal ions as cross-linkers. ATP can be assembled onto the surface of AuNPs through interaction between the electron-rich nitrogen atoms and the electron-deficient surface of AuNPs. Accordingly, Cu2+ ions induce a change in the color and UV/Vis absorbance of AuNPs by coordinating to the triphosphate groups and a ring nitrogen of ATP. A detection limit of 50 nM was achieved, which is comparable to or lower than that achievable by the currently used electrochemical, spectroscopic or chromatographic methods. The theoretical simplicity and high selectivity reported herein demonstrated that AuNPs-based colorimetric assay could be applied in a wide variety of fields by rationally designing the surface chemistry of AuNPs. In addition, our results indicate that ATP-modified AuNPs are less stable in Cu2+, Cd2+ or Zn2+-containing solutions due to the formation of the corresponding dimeric metal-ATP complexes.

  12. Physicochemical Characteristics and Slow Release Performances of Chlorpyrifos Encapsulated by Poly(butyl acrylate-co-styrene) with the Cross-Linker Ethylene Glycol Dimethacrylate.

    Science.gov (United States)

    Wang, Yu; Gao, Zideng; Shen, Feng; Li, Yang; Zhang, Sainan; Ren, Xueqin; Hu, Shuwen

    2015-06-03

    Chlorpyrifos' application and delivery to the target substrate needs to be controlled to improve its use. Herein, poly(butyl acrylate-co-styrene) (poly(BA/St)) and poly(BA/St/ethylene glycol dimethacrylate (EGDMA)) microcapsules loaded with chlorpyrifos as a slow release formulation were prepared by emulsion polymerization. The effects of structural characteristics on the chlorpyrifos microcapsule particle size, entrapment rate (ER), pesticide loading (PL), and release behaviors in ethyl alcohol were investigated. Fourier transform infrared and thermogravimetric analysis confirmed the successful entrapment of chlorpyrifos. The ER and PL varied with the BA/St monomer ratio, chlorpyrifos/monomer core-to-shell ratio, and EGDMA cross-linker content with consequence that suitable PL was estimated to be smaller than 3.09% and the highest ER was observed as 96.74%. The microcapsule particle size (88.36-101.8 nm) remained mostly constant. The extent of sustainable release decreased with increasing content of BA, St, or chlorpyrifos in the oil phase. Specifically, an adequate degree of cross-linking with EGMDA (0.5-2.5%) increased the extent of sustainable release considerably. However, higher levels of cross-linking with EGDMA (5-10%) reduced the extent of sustainable release. Chlorpyrifos release from specific microcapsules (monomer ratio 1:2 with 0.5% EGDMA or 5 g chlopyrifos) tended to be a diffusion-controlled process, while for others, the kinetics probably indicated the initial rupture release.

  13. Vitamin C-linker-conjugated tripeptide AHK stimulates BMP-2-induced osteogenic differentiation of mouse myoblast C2C12 cells.

    Science.gov (United States)

    Jung, Jung-Il; Park, Kyeong-Yong; Lee, Yura; Park, Mira; Kim, Jiyeon

    2018-03-15

    Vitamin C-linker-conjugated Ala-His-Lys tripeptide (Vit C-AHK) is a derivative of Vitamin C-conjugated tripeptides, which were originally developed as a component of a product for collagen synthesis enhancement or human dermal fibroblast growth. Here, we investigated the effect of Vit C-AHK on bone morphogenetic protein (BMP)-2-induced osteoblast differentiation in a cell culture model. Vit C-AHK enhanced proliferation of C2C12 cells and induction of BMP-2-induced alkaline phosphatase, a typical marker of osteoblast differentiation. Vit C-AHK also stimulated the phosphorylation and translocation of Smad1/5/8 to the nucleus and phosphorylation of mitogen-activated protein kinases (MAPKs) including ERK1/2 and p38. In addition, Vit C-AHK enhanced the BMP-2-induced mRNA expression of osteoblast differentiation-related genes such as ALP, BMP-2, Osteocalcin, and Runx2. Our results suggest that Vit C-AHK exerts an enhancing effect on osteoblast proliferation and differentiation through activation of Smad1/5/8 and MAPK ERK1/2 and p38 signaling and without significant cytotoxicity. These results provide important data for the development of peptide-based bone-regenerative agents and treatment of bone-related disorders. Copyright © 2018 International Society of Differentiation. Published by Elsevier B.V. All rights reserved.

  14. Preparation of 16β-Estradiol Derivative Libraries as Bisubstrate Inhibitors of 17β-Hydroxysteroid Dehydrogenase Type 1 Using the Multidetachable Sulfamate Linker

    Directory of Open Access Journals (Sweden)

    Donald Poirier

    2010-03-01

    Full Text Available Combinatorial chemistry is a powerful tool used to rapidly generate a large number of potentially biologically active compounds. In our goal to develop bisubstrate inhibitors of 17β-hydroxysteroid dehydrogenase type 1 (17β-HSD1 that interact with both the substrate (estrone or estradiol and the cofactor (NAD(PH binding sites, we used parallel solid-phase synthesis to prepare three libraries of 16β-estradiol derivatives with two or three levels of molecular diversity. From estrone, we first synthesized a sulfamate precursor that we loaded on trityl chloride resin using the efficient multidetachable sulfamate linker strategy recently developed in our laboratory. We then introduced molecular diversity [one or two amino acid(s followed by a carboxylic acid] on steroid nucleus by Fmoc peptide chemistry. Finally, after a nucleophilic cleavage, libraries of 30, 63 and 25 estradiol derivatives were provided. A library of 30 sulfamoylated estradiol derivatives was also generated by acidic cleavage and its members were screened for inhibition of steroid sulfatase. Biological evaluation on homogenated HEK-293 cells overexpressing 17β-HSD1 of the estradiol derivatives carrying different oligoamide-type chains at C-16 first revealed that three levels of molecular diversity (a spacer of two amino acids were necessary to interact with the adenosine part of the cofactor binding site. Second, the best inhibition was obtained when hydrophobic residues (phenylalanine were used as building blocks.

  15. A highly conserved glycine within linker I and the extreme C terminus of G protein alpha subunits interact cooperatively in switching G protein-coupled receptor-to-effector specificity

    DEFF Research Database (Denmark)

    Kostenis, Evi; Martini, Lene; Ellis, James

    2004-01-01

    Numerous studies have attested to the importance of the extreme C terminus of G protein alpha subunits in determining their selectivity of receptor recognition. We have previously reported that a highly conserved glycine residue within linker I is important for constraining the fidelity of receptor...... recognition by Galpha(q) proteins. Herein, we explored whether both modules (linker I and extreme C terminus) interact cooperatively in switching G protein-coupled receptor (GPCR)-to-effector specificity and created as models mutant Galpha(q) proteins in which glycine was replaced with various amino acids...... and the C-terminal five Galpha(q) residues with the corresponding Galpha(i) or Galpha(s) sequence. Coupling properties of the mutated Galpha(q) proteins were determined after coexpression with a panel of 13 G(i)-and G(s) -selective receptors and compared with those of Galpha proteins modified in only one...

  16. C-Terminally modified peptides via cleavage of the HMBA linker by O-, N- or S-nucleophiles

    DEFF Research Database (Denmark)

    Hansen, Jonas; Diness, Frederik; Meldal, Morten Peter

    2016-01-01

    A large variety of C-terminally modified peptides was obtained by nucleophilic cleavage of the ester bond in solid phase linked peptide esters of 4-hydroxymethyl benzamide (HMBA). The developed methods provided peptides, C-terminally functionalized as esters, amides and thioesters, with high purity...... directly from the resin in a single reaction step. A comprehensive screening of the reaction conditions and scope for nucleophilic cleavage of peptides from the HMBA linker was performed....

  17. The specificity of Av3 sea anemone toxin for arthropods is determined at linker DI/SS2-S6 in the pore module of target sodium channels.

    Science.gov (United States)

    Gur Barzilai, Maya; Kahn, Roy; Regev, Noa; Gordon, Dalia; Moran, Yehu; Gurevitz, Michael

    2014-10-15

    Av3 is a peptide neurotoxin from the sea anemone Anemonia viridis that shows specificity for arthropod voltage-gated sodium channels (Navs). Interestingly, Av3 competes with a scorpion α-toxin on binding to insect Navs and similarly inhibits the inactivation process, and thus has been classified as 'receptor site-3 toxin', although the two peptides are structurally unrelated. This raises questions as to commonalities and differences in the way both toxins interact with Navs. Recently, site-3 was partly resolved for scorpion α-toxins highlighting S1-S2 and S3-S4 external linkers at the DIV voltage-sensor module and the juxtaposed external linkers at the DI pore module. To uncover channel determinants involved in Av3 specificity for arthropods, the toxin was examined on channel chimaeras constructed with the external linkers of the mammalian brain Nav1.2a, which is insensitive to Av3, in the background of the Drosophila DmNav1. This approach highlighted the role of linker DI/SS2-S6, adjacent to the channel pore, in determining Av3 specificity. Point mutagenesis at DI/SS2-S6 accompanied by functional assays highlighted Trp404 and His405 as a putative point of Av3 interaction with DmNav1. His405 conservation in arthropod Navs compared with tyrosine in vertebrate Navs may represent an ancient substitution that explains the contemporary selectivity of Av3. Trp404 and His405 localization near the membrane surface and the hydrophobic bioactive surface of Av3 suggest that the toxin possibly binds at a cleft by DI/S6. A partial overlap in receptor site-3 of both toxins nearby DI/S6 may explain their binding competition capabilities.

  18. Synthesis and reactions of diazocarbonyl compounds. I. Reaction of 1-diazo-3-, 1-diazo-4-, and 1-diazo-5-phthalimidoalkan-2-ones with hydrazine hydrate. Synthesis of 1-diazo-3-, 1-diazo-4, and 1-diazo-5-arenesulfamoyl-alkan-2-ones

    International Nuclear Information System (INIS)

    Sipyagin, A.M.; Kartsev, V.G.

    1986-01-01

    The reaction of hydrazine hydrate with 1-diazo-3-, 1-diazo-4-, and 1-diazo-5-phthalimidoalkan-2-ones containing a substituent at the α position to the phthalimide group in the hydrocarbon chain leads to the formation of 1-diazo-3- and 1-diazo-4-(2-hydrazidophenylcarbamoyl)alkan-2-ones. On heating in the presence of an excess of hydrazine hydrate the reaction products are 1-diazo-3-, 1-diazo-4-, and 1-diazo-5-aminoalkan-2-ones. Various 1-diazo-3-, 1-diazo-4-, and 1-diazo-5-arenesulfamoyl-alkan-2-ones were synthesized in the reaction of arenesulfonyl chlorides with 1-diazo-3-, 1-diazo-4-, and 1-diazo-5-aminoalkan-2-ones in the presence of triethylamine

  19. Opposite effects of the S4-S5 linker and PIP2 on voltage-gated channel function: KCNQ1/KCNE1 and other channels

    Directory of Open Access Journals (Sweden)

    Frank S Choveau

    2012-07-01

    Full Text Available Voltage-gated potassium (Kv channels are tetramers, each subunit presenting six transmembrane segments (S1-S6, with each S1-S4 segments forming a voltage-sensing domain (VSD and the four S5-S6 forming both the conduction pathway and its gate. S4 segments control the opening of the intracellular activation gate in response to changes in membrane potential. Crystal structures of several voltage-gated ion channels in combination with biophysical and mutagenesis studies highlighted the critical role of the S4-S5 linker (S4S5L and of the S6 C-terminal part (S6T in the coupling between the VSD and the activation gate. Several mechanisms have been proposed to describe the coupling at a molecular scale. This review summarizes the mechanisms suggested for various voltage-gated ion channels, including a mechanism that we described for KCNQ1, in which S4S5L is acting like a ligand binding to S6T to stabilize the channel in a closed state. As discussed in this review, this mechanism may explain the reverse response to depolarization in HCN-like channels. As opposed to S4S5L, the phosphoinositide, phosphatidylinositol 4,5-bisphosphate (PIP2, stabilizes KCNQ1 channel in an open state. Many other ion channels (not only voltage-gated require PIP2 to function properly, confirming its crucial importance as an ion channel co-factor. This is highlighted in cases in which an altered regulation of ion channels by PIP2 leads to channelopathies, as observed for KCNQ1. This review summarizes the state of the art on the two regulatory mechanisms that are critical for KCNQ1 and other voltage-gated channels function (PIP2 and S4-S5L, and assesses their potential physiological and pathophysiological roles.

  20. A conserved motif in the linker domain of STAT1 transcription factor is required for both recognition and release from high-affinity DNA-binding sites.

    Science.gov (United States)

    Hüntelmann, Bettina; Staab, Julia; Herrmann-Lingen, Christoph; Meyer, Thomas

    2014-01-01

    Binding to specific palindromic sequences termed gamma-activated sites (GAS) is a hallmark of gene activation by members of the STAT (signal transducer and activator of transcription) family of cytokine-inducible transcription factors. However, the precise molecular mechanisms involved in the signal-dependent finding of target genes by STAT dimers have not yet been very well studied. In this study, we have characterized a sequence motif in the STAT1 linker domain which is highly conserved among the seven human STAT proteins and includes surface-exposed residues in close proximity to the bound DNA. Using site-directed mutagenesis, we have demonstrated that a lysine residue in position 567 of the full-length molecule is required for GAS recognition. The substitution of alanine for this residue completely abolished both binding to high-affinity GAS elements and transcriptional activation of endogenous target genes in cells stimulated with interferon-γ (IFNγ), while the time course of transient nuclear accumulation and tyrosine phosphorylation were virtually unchanged. In contrast, two glutamic acid residues (E559 and E563) on each monomer are important for the dissociation of dimeric STAT1 from DNA and, when mutated to alanine, result in elevated levels of tyrosine-phosphorylated STAT1 as well as prolonged IFNγ-stimulated nuclear accumulation. In conclusion, our data indicate that the kinetics of signal-dependent GAS binding is determined by an array of glutamic acid residues located at the interior surface of the STAT1 dimer. These negatively charged residues appear to align the long axis of the STAT1 dimer in a position perpendicular to the DNA, thereby facilitating the interaction between lysine 567 and the phosphodiester backbone of a bound GAS element, which is a prerequisite for transient gene induction.