DNA damage and apoptosis of endometrial cells cause loss of the early embryo in mice exposed to carbon disulfide

Energy Technology Data Exchange (ETDEWEB)

Zhang, Bingzhen [Department of Epidemiology and Health Statistics, School of Public Health, Shandong University, Jinan (China); Shen, Chunzi [Centers for Disease Control and Prevention, Zibo (China); Yang, Liu; Li, Chunhui; Yi, Anji [Department of Epidemiology and Health Statistics, School of Public Health, Shandong University, Jinan (China); Wang, Zhiping, E-mail: zhipingw@sdu.edu.cn [Department of Epidemiology and Health Statistics, School of Public Health, Shandong University, Jinan (China)

2013-12-01

Carbon disulfide (CS{sub 2}) may lead to spontaneous abortion and very early pregnancy loss in women exposed in the workplace, but the mechanism remains unclear. We designed an animal model in which gestating Kunming strain mice were exposed to CS{sub 2} via i.p. on gestational day 4 (GD4). We found that the number of implanted blastocysts on GD8 was significantly reduced by each dose of 0.1 LD{sub 50} (157.85 mg/kg), 0.2 LD{sub 50} (315.7 mg/kg) and 0.4 LD{sub 50} (631.4 mg/kg). In addition, both the level of DNA damage and apoptosis rates of endometrial cells on GD4.5 were increased, showed definite dose–response relationships, and inversely related to the number of implanted blastocysts. The expressions of mRNA and protein for the Bax and caspase-3 genes in the uterine tissues on GD4.5 were up-regulated, while the expressions of mRNA and protein for the Bcl-2 gene were dose-dependently down-regulated. Our results indicated that DNA damage and apoptosis of endometrial cells were important reasons for the loss of implanted blastocysts induced by CS{sub 2}. - Highlights: • We built an animal model of CS2 exposure during blastocyst implantation. • Endometrial cells were used in the comet assay to detect DNA damage. • CS2 exposure caused DNA damage and endometrial cell apoptosis. • DNA damage and endometrial cell apoptosis were responsible for embryo loss.

Ultraviolet differential optical absorption spectrometry: quantitative analysis of the CS2 produced by SF6 decomposition

International Nuclear Information System (INIS)

Zhang, Xiaoxing; Zhou, Hong; Cui, Zhaolun; Xiao, Song; Tang, Ju; Chen, Chuan; Li, Xin

2017-01-01

The occurrence of partial discharge or partial overthermal fault in sulfur hexafluoride (SF 6 )-insulated electrical equipment frequently causes SF 6 and solid insulation materials to decompose into various products. One of the most characteristic products of this process is carbon disulfide (CS 2 ). The internal fault type and severity of the fault in the insulation equipment can be detected through the accurate quantitative detection of CS 2 . A device for simultaneously determining and quantifying gaseous CS 2 via ultraviolet differential optical absorption spectrometry is developed in this study. A Sym14 wavelet transform and fast Fourier transform (FFT) are applied to process the spectral data of the feature regions, namely 190 nm to 210 nm. The concentration of CS 2 is determined, and the detection limit of the developed device is identified. A good linear relationship is observed between the characteristic peaks of FFT and the concentration of CS 2 after the operational parameters are optimized. Along the light path at 600 mm, the average detection limit for CS 2 is 8.65 ppb based on three times the standard deviation of the system noises. The proposed device, which exhibits high sensitivity and effective cost, addresses the urgent demand for the monitoring and diagnosis of SF 6 -insulated electrical equipment via online detection of trace CS 2 . (paper)

Symmetric pseudocapacitors based on molybdenum disulfide (MoS2)-modified carbon nanospheres: correlating physicochemistry and synergistic interaction on energy storage

CSIR Research Space (South Africa)

Khawula, TNY

2016-03-01

Full Text Available Molybdenum disulfide-modified carbon nanospheres (MoS(sub2)/CNS) with two different morphologies (spherical and flower-like) have been synthesized using hydrothermal techniques and investigated as symmetric pseudocapacitors in an aqueous electrolyte...

Structural Search for High Pressure CS2 and Xe-Cl Compounds

Science.gov (United States)

Zarifi, Niloofar; Tse, John S.

2018-04-01

The recent successful implementation of several methodologies for the prediction of crystal structures based on the first-principles electronic structure have ushered in a new area of computational chemistry. In this study, the two most popular methods, namely genetic evolution and particle swarm optimization, were applied to the investigation of stable crystalline polymorphs of solid carbon disulfide and xenon halides at high pressure. It was found that both methods have their own merits. However, there are subtleties that need to be considered for the proper execution of the methods. We found a two-dimensional (2D) layered structure that may be responsible for the superconductivity in CS2. Except for XeCl2, no thermodynamically stable crystalline Xe halides were found under 60 GPa in the halide-rich region of the phase diagram.

Insights into the coal extractive solvent N-methyl-2-pyrrolidone + carbon disulfide

Energy Technology Data Exchange (ETDEWEB)

Santiago Aparicio; Mara J. Davila; Rafael Alcalde [University of Burgos, Burgos (Spain). Department of Chemistry

2009-03-15

A wide set of experimental and computational tools were used to characterize the N-methyl-2-pyrrolidone (NMP) + carbon disulfide mixed solvent in the full composition range. The interest in this solvent rose from its very efficient use for coal extraction through a mechanism still not fully understood. Thermophysical properties at ambient pressure together with pressure-volume-temperature (PVT) behavior were measured with the objective of providing the required data for the industrial use of the mixed fluid and to get insight into the fluid structure at the molecular level. NMR, FTIR, and solvatochromic studies were performed together with microwave dielectric relaxation spectroscopy (DRS) measurements, thus providing more information on the fluid's structure and allowing one to relate the molecular level behavior with the measured macroscopic properties. Moreover, density functional theory (DFT) and classical molecular dynamics simulations (MD) were used to obtain a detailed picture of the intermolecular interactions within the fluid, at short and long ranges, and of other relevant features leading to the structure of the studied system. The whole study leads to a fluid's picture in which carbon disulfide hinders the development of NMP/NMP intermolecular dipolar interactions, thus increasing the monomer population. We should remark that some properties reported in this work are in remarkable disagreement with previously reported studies, the most important one being the positive excess molar volume in the whole pressure-temperature range studied, which contrasts with the negative values reported in the literature. Previously reported properties are hardly justified with a coherent molecular level picture, whereas the whole collection of properties reported in this work leads to a more reasonable fluid's structure. 56 refs., 17 figs., 2 tabs.

Gas chromatographic studies of the relative retention of the sulfur isotopes in carbonyl sulfide, carbon disulfide, and sulfur dioxide

International Nuclear Information System (INIS)

Fetzer, J.C.; Rogers, L.B.

1980-01-01

A precision gas chromatograph, coupled to a quadrupole mass spectrometer and an on-line computer, was used to study the fractionation on Porasil A of the 32 S/ 34 S isotopic pair in a variety of sulfur-containing molecules. Carbonyl sulfide (COS) yielded an average α value of 1.00074 +- 0.00017 (standard deviation) for the temperature range 25 0 C to 75 0 C. The carbon disulfide (CS 2 ) value was 1.00069 +- 0.00023 for the range 53 0 C to 103 0 C, and that for sulfur dioxide (SO 2 ) was 1.00090 +- 0.00018 for the range 62 0 C to 112 0 C. Differential thermodynamic data have been reported. A Porapak Q column showed no fractionation of this isotopic pair in these three molecules

Selecting core-hole localization or delocalization in CS2 by photofragmentation dynamics.

Science.gov (United States)

Guillemin, R; Decleva, P; Stener, M; Bomme, C; Marin, T; Journel, L; Marchenko, T; Kushawaha, R K; Jänkälä, K; Trcera, N; Bowen, K P; Lindle, D W; Piancastelli, M N; Simon, M

2015-01-21

Electronic core levels in molecules are highly localized around one atomic site. However, in single-photon ionization of symmetric molecules, the question of core-hole localization versus delocalization over two equivalent atoms has long been debated as the answer lies at the heart of quantum mechanics. Here, using a joint experimental and theoretical study of core-ionized carbon disulfide (CS2), we demonstrate that it is possible to experimentally select distinct molecular-fragmentation pathways in which the core hole can be considered as either localized on one sulfur atom or delocalized between two indistinguishable sulfur atoms. This feat is accomplished by measuring photoelectron angular distributions within the frame of the molecule, directly probing entanglement or disentanglement of quantum pathways as a function of how the molecule dissociates.

Biotransformation, distribution and toxicity of carbon disulfide in immature rats

International Nuclear Information System (INIS)

Green, E.C.

1984-01-01

The 24-hour LD-50 values of CS 2 in 1-, 5-, 10-, 20-, 30-, and 40-day-old rats were 583, 974, 1119, 1545, 1237, and 1183 mg/kg, respectively. Twenty-four hours after CS 2 exposure, decreases in aniline hydroxylation and cytochrome P-450 were observed in rats older than one day of age. Hepatic microsomes from rats of all ages biotransformed CS 2 to COS in vitro in the presence of NADPH. Inhibition of the hepatic mixed-function oxidase enzyme system (HMFOES) was observed after incubation of hepatic microsomes from rats as young as one day of age with CS 2 and NADPH. Studies with radiolabelled CS 2 showed that a covalently binding sulfur metabolite, free from the carbon atom of CS 2 , was formed in vitro during the metabolism of CS 2 to COS which appeared to be responsible for the inhibition of the HMFOES. Three hours after 14 C-CS 2 administration in vivo to rats, between 58 and 83% of the dose of 14 C-CS 2 was expired; 4-9% of the dose was expired as 14 C-CO 2 depending on age. One to 2% of the dose of 14 C-CS 2 , and 1 to 6% of the dose of 35 S-CS 2 remained as biotransformation products in tissues. Biotransformation products of CS 2 were identified as either acid-labile or covalently bound. The results of the study implicated CS 2 biotransformation to sulfur metabolites as an important mechanism of CS 2 toxicity, particularly to 1-day-old rats which had the lowest capacity to eliminate these metabolites

Simultaneous electrochemical determination of L-cysteine and L-cysteine disulfide at carbon ionic liquid electrode.

Science.gov (United States)

Safavi, Afsaneh; Ahmadi, Raheleh; Mahyari, Farzaneh Aghakhani

2014-04-01

A linear sweep voltammetric method is used for direct simultaneous determination of L-cysteine and L-cysteine disulfide (cystine) based on carbon ionic liquid electrode. With carbon ionic liquid electrode as a high performance electrode, two oxidation peaks for L-cysteine (0.62 V) and L-cysteine disulfide (1.3 V) were observed with a significant separation of about 680 mV (vs. Ag/AgCl) in phosphate buffer solution (pH 6.0). The linear ranges were obtained as 1.0-450 and 5.0-700 μM and detection limits were estimated to be 0.298 and 4.258 μM for L-cysteine and L-cysteine disulfide, respectively. This composite electrode was applied for simultaneous determination of L-cysteine and L-cysteine disulfide in two real samples, artificial urine and nutrient broth. Satisfactory results were obtained which clearly indicate the applicability of the proposed electrode for simultaneous determination of these compounds in complex matrices.

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

International Nuclear Information System (INIS)

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

1992-01-01

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

Properties of Cs-intercalated single wall carbon nanotubes investigated by 133Cs Nuclear Magnetic resonance

KAUST Repository

Schmid, Marc R.; Mahfouz, Remi; Bouhrara, Mohamed; Saih, Youssef; Mehring, Michael; Basset, Jean-Marie; Goze-Bac, Christophe; Abou-Hamad, Edy

2012-01-01

present within the carbon nanotube bundles. At high concentrations, the Cs (β)+ ions seem to occupy well defined positions relative to the carbon lattice. As a matter of fact, the Korringa relaxation behavior suggests a strong hyperfine coupling between Cs

Unknown plant de-construction hazard -- Toxic COS and CS2 gas from torch cutting of pipe

International Nuclear Information System (INIS)

Martin, H.L.; Nutt, A.W.; Myers, B.L.; Hightower, J.O.

1994-01-01

An employee exhibited signs of illness after apparently inhaling fumes generated from a pipe that had been cut with a cutting torch. Identification and quantification of the hazardous air emission for reduction of risk via the Department of Energy Class B Investigation are described in this case study. The old hydrogen sulfide gas flare pipe in the heavy water plant of the Savannah River Site has been abandoned with one end open to atmosphere for almost twenty years. The pipe was being removed and cut into sections for disposal during an asbestos abatement project. It contained ash like corrosion deposits that smolder after torch cutting. Investigation revealed that burning of carbon and sulfur in the oxygen deficient atmosphere in the ash generated carbonyl sulfide (COS) and carbon disulfide (CS 2 ) gas, which vented when the pipe was moved by the injured construction rigger. This is believed to be the first well documented exposure and response of a human to high concentration COS gas. Sulfur dioxide (SO 2 ) gas is also generated during the cutting. SO 2 is almost impossible to inhale and has apparently prevented a similar injury during the cutting. SO 2 is almost impossible to inhale and has apparently prevented a similar injury during the many years of US and Canadian heavy water plant de-construction experience. Immediate water quench of the smoldering ash after each cut has eliminated the hazard of residual COS and CS 2 gas. This previously unrecognized industrial hazard may be encountered by other chemical and petroleum industries during torch cutting of pipes that contain similar deposits of iron oxide, iron sulfate, sulfur and carbon

Current and historical individual data about exposure of workers in the rayon industry to carbon disulfide and their validity in calculating the cumulative dose.

Science.gov (United States)

Göen, Thomas; Schramm, Axel; Baumeister, Thomas; Uter, Wolfgang; Drexler, Hans

2014-08-01

The objective of the study was to investigate how exposure to carbon disulfide (CS2) in a rayon-manufacturing plant has changed within two decades and whether it is possible to calculate valid data for the individual cumulative exposure. The data for CS2 concentration in air and biological exposure monitoring (2-thio-1,3-thiaxolidine-4-carboxylic acid (TTCA) in urine) from two cross-sectional studies, performed in 1992 (n = 362) and 2009 (n = 212) in a German rayon-manufacturing plant, were compared to data obtained from company-internal measurements between the studies. Using the data from the cross-sectional studies and company-internal data, cumulative external exposure and the cumulative internal exposure were calculated for each worker. External and internal CS2 exposure of the employees decreased from 1992 (medians 4.0 ppm and 1.63 mgTTCA/g creatinine) to 2009 (medians 2.5 ppm and 0.86 mg/g). However, company-internal CS2 data do not show a straight trend for this period. The annual medians of the company-internal measurement of external exposure to CS2 have varied between 2.7 and 8.4 ppm, in which median values exceeded 5 ppm generally since 2000. The annual medians for the company-internal biomonitoring assessment ranged between 1.2 and 2.8 mg/g creatinine. The cumulative CS2 exposure ranged from 8.5 to 869.5 ppm years for external exposure and between 1.30 and 176.2 mg/g creatinine years for the internal exposure. Significant correlations were found between the current air pollution and the internal exposure in 2009 but also between the cumulative external and internal CS2 exposure. Current exposure data, usually collected in cross-sectional studies, rarely allow a reliable statement on the cumulative dose, because of higher exposure in the past and of fluctuating courses of exposure. On the other hand, company-internal exposure data may be affected by non-representative measurement strategies. Some verification of the reliability of

Antiradiation compounds XV: condensations of carbon disulfide with amino, chloro, cyanomethyl, and sulfonamido heterocycles

International Nuclear Information System (INIS)

Foye, W.O.; Kauffman, J.M.; Lanzillo, J.J.; LaSala, E.F.

1975-01-01

Condensations of carbon disulfide were carried out with amino, chloro, and diamino heterocycles to give condensed ring thiazoline-2-thiones and imidazoline-2-thiones, with cyanomethyl heterocycles to give dithio acid derivatives, and with heterocyclic sulfonamides to give sulfonyldithiocarbamates. Of several examples tested, pyrido[3,2-d]thiazoline-2-thione, disodium 2-(5-chloro-2-thienyl)-3,3-dimercaptoacrylonitrile, triethylammonium 4-sulfamoylphenyldithiocarbamate, ammonium β-phenethyldithiocarbamate, and methyl N-(thiophene-2-sulfonyl)dithiocarbamate, only the last-named compound showed any radiation protection for mice. Several compounds gave negative tests for antimalarial activity

Gas-phase generations and rearrangement of silathiones, R sub 2 Si=S

Energy Technology Data Exchange (ETDEWEB)

Kim, Chong Bok.

1991-01-08

Three routes are explored for the generation of silathiones: (1) the retroene elimination of propene from allythiodimethylsilane and 1-allythio-1-hydrido-1,2,2,2-tetramethylsilane; (2) the reaction of silylene, Me{sub 2}Di, with carbon disulfide which is thought to form a transient 3-membered ring with CS{sub 2} and the elimination of carbon disulfide to produce diethylsilathione; and (3) the beta-elimination of bis(trimethylsilythio)dimethylsilane. All these methods are explored in some detail. A second example of a silathione-silylene isomerization was observed in the pyrolysis of 1,1-bis(trimethylsilythio)-1,2,2,2-tetramethyldisilane. 89 refs., 5 figs., 10 tab. (BM)

Molecular structures and thermodynamic properties of 12 gaseous cesium-containing species of nuclear safety interest: Cs 2, CsH, CsO, Cs 2O, CsX, and Cs 2X 2 (X = OH, Cl, Br, and I)

Science.gov (United States)

Badawi, Michael; Xerri, Bertrand; Canneaux, Sébastien; Cantrel, Laurent; Louis, Florent

2012-01-01

Ab initio electronic structure calculations at the coupled cluster level with a correction for the triples extrapolated to the complete basis set limit have been made for the estimation of the thermochemical properties of Cs 2, CsH, CsO, Cs 2O, CsX, and Cs 2X 2 (X = OH, Cl, Br, and I). The standard enthalpies of formation and standard molar entropies at 298 K, and the temperature dependence of the heat capacities at constant pressure were evaluated. The calculated thermochemical properties are in good agreement with their literature counterparts. For Cs 2, CsH, CsOH, Cs 2(OH) 2, CsCl, Cs 2Cl 2, CsBr, CsI, and Cs 2I 2, the calculated ΔfH298K∘ values are within chemical accuracy of the most recent experimental values. Based on the excellent agreement observed between our calculated ΔfH298K∘ values and their literature counterparts, the standard enthalpies of formation at 298 K are estimated to be the following: ΔfH298K∘ (CsO) = 17.0 kJ mol -1 and ΔfH298K∘ (Cs 2Br 2) = -575.4 kJ mol -1.

Ophthalmological and angiographic findings in workers exposed to carbon disulfide (author's transl)

Energy Technology Data Exchange (ETDEWEB)

Savic, S.

1982-01-01

Microaneurysms are important in the diagnosis of vascular changes caused by carbon disulfide. They can be diagnosed by ophtholmoscopy, angiography or angioscopy. In our opinion even a careful ophthalmoscopic investigation is sufficient for diagnosis, so that angiography is not absolutely necessary for any mass survey. The incidence of microaneurysms correlates with the duration (both daily and total) as well as with the intensity of exposure to carbon disulfide. The quantity correlates closely with the intensity of exposure. The incidence of microaneurysms is not correlated to age; however it was found to be highest in 40-50-year-old men working with staple fibers, whereas in the spinning department it occurred in 50-55-old men. Microaneurysms are found equally frequently in active workers and invalids. There was no difference between the two groups with regard to degenerative changes of the macula. However, the changes found in the eyes of men from the staple fiber department were more pronounced than in those from the spinning department.

Carbon monosulfide: a useful synthetic intermediate

International Nuclear Information System (INIS)

Kramer, M.P.

1986-01-01

The physical properties of carbon monosulfide, CS, are well documented. The molecule has been observed in interstellar space and is found to be a common intermediate in the thermal decomposition of carbon disulfide and other sulfur compounds. Interestingly enough, the chemistry of carbon monosulfide, a molecule that is isovalent with carbon monoxide, has received little attention. The explosive nature of the carbon monosulfide monomer, which hindered previous workers, was overcome by the development of special handling techniques. The ability to produce carbon monosulfide in gram quantities had lead to synthesis of novel compounds and to a more direct synthetic route for certain known compounds. Specifically, the following general reaction demonstrates the capabilities of carbon monosulfide on the synthetic scale. CS + RXY → RXC(S)Y;(X = N,S), (Y = H, Cl). Note: The initial product formed in the reaction can be an unstable intermediate

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

Science.gov (United States)

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

2018-05-01

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

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

Science.gov (United States)

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

2018-01-25

Disulfide bond formation is critical for maintaining structure stability and function of many peptides and proteins. Mass spectrometry has become an important tool for the elucidation of molecular connectivity. However, the interpretation of the tandem mass spectral data of disulfide-linked peptides has been a major challenge due to the lack of appropriate tools. Developing proper data analysis software is essential to quickly characterize disulfide-linked peptides. A thorough and in-depth understanding of how disulfide-linked peptides fragment in mass spectrometer is a key in developing software to interpret the tandem mass spectra of these peptides. Two model peptides with inter- and intra-chain disulfide linkages were used to study fragmentation behavior in both collisional-activated dissociation (CAD) and electron-based dissociation (ExD) experiments. Fragments generated from CAD and ExD can be categorized into three major types, which result from different S-S and C-S bond cleavage patterns. DiSulFinder is a computer algorithm that was newly developed based on the fragmentation observed in these peptides. The software is vendor neutral and capable of quickly and accurately identifying a variety of fragments generated from disulfide-linked peptides. DiSulFinder identifies peptide backbone fragments with S-S and C-S bond cleavages and, more importantly, can also identify fragments with the S-S bond still intact to aid disulfide linkage determination. With the assistance of this software, more comprehensive disulfide connectivity characterization can be achieved. Graphical Abstract ᅟ.

Molecular CsF 5 and CsF 2 +

KAUST Repository

Rogachev, Andrey Yu.; Miao, Mao-sheng; Merino, Gabriel; Hoffmann, Roald

2015-01-01

D5h star-like CsF5, formally isoelectronic with known XeF5− ion, is computed to be a local minimum on the potential energy surface of CsF5, surrounded by reasonably large activation energies for its exothermic decomposition to CsF+2 F2, or to CsF3 (three isomeric forms)+F2, or for rearrangement to a significantly more stable isomer, a classical Cs+ complex of F5−. Similarly the CsF2+ ion is computed to be metastable in two isomeric forms. In the more symmetrical structures of these molecules there is definite involvement in bonding of the formally core 5p levels of Cs.

Molecular CsF 5 and CsF 2 +

KAUST Repository

Rogachev, Andrey Yu.

2015-06-03

D5h star-like CsF5, formally isoelectronic with known XeF5− ion, is computed to be a local minimum on the potential energy surface of CsF5, surrounded by reasonably large activation energies for its exothermic decomposition to CsF+2 F2, or to CsF3 (three isomeric forms)+F2, or for rearrangement to a significantly more stable isomer, a classical Cs+ complex of F5−. Similarly the CsF2+ ion is computed to be metastable in two isomeric forms. In the more symmetrical structures of these molecules there is definite involvement in bonding of the formally core 5p levels of Cs.

UV Photofragmentation Dynamics of Protonated Cystine: Disulfide Bond Rupture.

Science.gov (United States)

Soorkia, Satchin; Dehon, Christophe; Kumar, S Sunil; Pedrazzani, Mélanie; Frantzen, Emilie; Lucas, Bruno; Barat, Michel; Fayeton, Jacqueline A; Jouvet, Christophe

2014-04-03

Disulfide bonds (S-S) play a central role in stabilizing the native structure of proteins against denaturation. Experimentally, identification of these linkages in peptide and protein structure characterization remains challenging. UV photodissociation (UVPD) can be a valuable tool in identifying disulfide linkages. Here, the S-S bond acts as a UV chromophore and absorption of one UV photon corresponds to a σ-σ* transition. We have investigated the photodissociation dynamics of protonated cystine, which is a dimer of two cysteines linked by a disulfide bridge, at 263 nm (4.7 eV) using a multicoincidence technique in which fragments coming from the same fragmentation event are detected. Two types of bond cleavages are observed corresponding to the disulfide (S-S) and adjacent C-S bond ruptures. We show that the S-S cleavage leads to three different fragment ions via three different fragmentation mechanisms. The UVPD results are compared to collision-induced dissociation (CID) and electron-induced dissociation (EID) studies.

S center dot center dot center dot N chalcogen bonded complexes of carbon disulfide with diazines. Theoretical study

Czech Academy of Sciences Publication Activity Database

Zierkiewicz, W.; Fanfrlík, Jindřich; Michalczyk, M.; Michalska, D.; Hobza, Pavel

2018-01-01

Roč. 500, Jan 26 (2018), s. 37-44 ISSN 0301-0104 Institutional support: RVO:61388963 Keywords : chalcogen bond * carbon disulfide * diazines * DFT Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.767, year: 2016

Thermal gravimetric analysis of the CsCuCl3, Cs2CuCl4 and Cs2CuCl4x2H2O crystals

International Nuclear Information System (INIS)

Soboleva, L.V.; Vasil'eva, M.G.

1977-01-01

The thermal characteristics of crystals of Cs 2 CuCl 4 , Cs 2 CuCl 4 x2H 2 O, and CsCuCl 3 were investigated thermogravimetrically. The derivatogram of the Cs 2 CuCl 4 crystal is characterized by the presence of a single endothermal effect at 505 deg C. The derivatogram of the Cs 2 CuCl 4 x2H 2 O crystal contains three endothermal effects: at 40, 135, and 480 deg C. The derivatogram of the CsCuCl 3 crystal shows the presence of two endothermal effects at 142 and 455 deg C. The thermogravimetric data on Cs 2 CuCl 4 and CsCuCl 3 crystals reveal crystal decomposition on melting; hence, these crystals cannot be grown from melts

Ionic properties of non-aqueous liquid and PVDF-based gel electrolytes containing a cesium thiolate/disulfide redox couple

International Nuclear Information System (INIS)

Renard, Ingrid; Li Hongmei; Marsan, Benoit

2003-01-01

Liquid electrolytes containing a cesium thiolate/disulfide redox couple, prepared from 5-mercapto-1-methyltetrazole cesium salt (CsT) and di-5-(1-methyltetrazole)disulfide (T 2 ) dissolved in several aprotic solvents and solvent mixtures, have been studied using various techniques. FTIR spectroscopy reveals that relatively strong interactions occur between the reduced species T - and DMSO or DMF while Cs + ions are very weakly coordinated to the S=O or C=O bond. It is shown that the electrolyte consisting of 1.55 mol kg -1 CsT in the solvent mixture DMSO/DMF (40/60%) exhibits the highest conductivity (1.1x10 -2 and 2.3x10 -2 S cm -1 at 23 and 80 deg. C, respectively), and that the presence of the oxidized species T 2 does not affect significantly its electrical properties up to a CsT:T 2 molar ratio of 5:1. Conductivity values as a function of salt concentration are discussed in terms of the effective number of charge carriers, taking into account the level of ionic association, and of the ionic mobility. Optically transparent gel electrolytes have been prepared by incorporation of the optimal liquid electrolyte into various amounts of poly(vinylidene fluoride) (PVDF). It is shown that ionic mobility is not much affected by the polymer concentration, suggesting that migration of ions occurs mainly through the solvent mixture surrounded by the PVDF matrix

Alignment and Imaging of the CS2 Dimer Inside Helium Nanodroplets

Science.gov (United States)

Pickering, James D.; Shepperson, Benjamin; Hübschmann, Bjarke A. K.; Thorning, Frederik; Stapelfeldt, Henrik

2018-03-01

The carbon disulphide (CS2) dimer is formed inside He nanodroplets and identified using fs laser-induced Coulomb explosion, by observing the CS2+ ion recoil velocity. It is then shown that a 160 ps moderately intense laser pulse can align the dimer in advantageous spatial orientations which allow us to determine the cross-shaped structure of the dimer by analysis of the correlations between the emission angles of the nascent CS2+ and S+ ions, following the explosion process. Our method will enable fs time-resolved structural imaging of weakly bound molecular complexes during conformational isomerization, including formation of exciplexes.

40 CFR 63.500 - Back-end process provisions-carbon disulfide limitations for styrene butadiene rubber by emulsion...

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 9 2010-07-01 2010-07-01 false Back-end process provisions-carbon disulfide limitations for styrene butadiene rubber by emulsion processes. 63.500 Section 63.500 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL EMISSION STANDARDS FOR HAZARDOUS AIR POLLUTANTS FOR...

The effect of tensile stress on the conformational free energy landscape of disulfide bonds.

Directory of Open Access Journals (Sweden)

Padmesh Anjukandi

Full Text Available Disulfide bridges are no longer considered to merely stabilize protein structure, but are increasingly recognized to play a functional role in many regulatory biomolecular processes. Recent studies have uncovered that the redox activity of native disulfides depends on their C-C-S-S dihedrals, χ2 and χ'2. Moreover, the interplay of chemical reactivity and mechanical stress of disulfide switches has been recently elucidated using force-clamp spectroscopy and computer simulation. The χ2 and χ'2 angles have been found to change from conformations that are open to nucleophilic attack to sterically hindered, so-called closed states upon exerting tensile stress. In view of the growing evidence of the importance of C-C-S-S dihedrals in tuning the reactivity of disulfides, here we present a systematic study of the conformational diversity of disulfides as a function of tensile stress. With the help of force-clamp metadynamics simulations, we show that tensile stress brings about a large stabilization of the closed conformers, thereby giving rise to drastic changes in the conformational free energy landscape of disulfides. Statistical analysis shows that native TDi, DO and interchain Ig protein disulfides prefer open conformations, whereas the intrachain disulfide bridges in Ig proteins favor closed conformations. Correlating mechanical stress with the distance between the two a-carbons of the disulfide moiety reveals that the strain of intrachain Ig protein disulfides corresponds to a mechanical activation of about 100 pN. Such mechanical activation leads to a severalfold increase of the rate of the elementary redox S(N2 reaction step. All these findings constitute a step forward towards achieving a full understanding of functional disulfides.

In situ aquifer bioremediation of organics including cyanide and carbon disulfide

International Nuclear Information System (INIS)

Abou-Rizk, J.A.M.; Leavitt, M.E.; Graves, D.A.

1995-01-01

Low levels (< 1 mg/L) of acetone, cyanide, phenol, naphthalene, 2-methylnaphthalene, and carbon disulfide from an inactive industrial landfill were found above background levels in a shallow aquifer at an eastern coastal site. In situ biodegradation was evaluated for treatment of these contaminants. Two soil samples and three groundwater samples were taken from the site for a laboratory bioassessment and a biotreatability test. The positive results of the bioassessment suggested moving forward with biotreatability testing. Biotreatability test results indicated suitable site conditions for bioremediation and that all the contaminants of concern at the site could be biodegraded to nondetect or very low levels (< 50 microg/L) with oxygen only; i.e., addition of nutrients was not required. Pilot-scale testing was undertaken on site to provide information for full-scale design, including oxygen requirements and air injection well spacing. This report describes the approach, the results, and their impact on the full-scale remediation system

Functional Poly(ε-caprolactone)s via Copolymerization of ε-Caprolactone and Pyridyl Disulfide-Containing Cyclic Carbonate: Controlled Synthesis and Facile Access to Reduction-Sensitive Biodegradable Graft Copolymer Micelles

NARCIS (Netherlands)

Chen, Wei; Zou, Yan; Jia, Junna; Meng, Fenghua; Cheng, Ru; Deng, Chao; Feijen, Jan; Zhong, Zhiyuan

2013-01-01

Pyridyl disulfide-functionalized cyclic carbonate (PDSC) monomer was obtained in four straightforward steps from 3-methyl-3-oxetanemethanol and exploited for facile preparation of functional poly(ε-caprolactone) (PCL) containing pendant pyridyl disulfide (PDS) groups via ring-opening

Effect of hydrothermal treatment on the extraction of coal in the CS{sub 2}/NMP mixed solvent

Energy Technology Data Exchange (ETDEWEB)

Hengfu Shui; Zhicai Wang; Gaoqiang Wang [Anhui University of Technology, Maanshan (China). School of Chemistry and Chemical Engineering

2006-09-15

The extraction of four Chinese different rank bituminous coals with the carbon disulfide/N-2-pyrrolidinone (CS2/NMP) mixed solvent (1:1 by volume) was carried out in room temperature. It was found that one of middle bituminous raw coal of the four coals gave more than 74% (daf) extraction yield, suggesting an associative structural model for the coal. The four coals were hydrothermal treated under different conditions, and it was found that the extraction yields of the treated coals obviously increased. This will have great significance for coal liquefaction. FTIR measurements show the removal of minerals after the hydrothermal treatment of coals suggesting the dissociation of the coal aggregation structure due to ionic interactions and/or hydrogen bonds broken because of the removal of oxygen and hydroxyl oxygen proceeded through ionic pathways, resulting in the extraction yields of the treated coals increase. However, breaking of {pi}-cation interactions by hydrothermal treatment may be one of possible mechanisms for the enhancement of extraction yield of higher rank of treated coal. The mechanism of hydrothermal treatment of coal was discussed in the paper. 28 refs., 4 figs., 4 tabs.

Surface heterogeneity and ionization of Cs promoter in carbon-based ruthenium catalyst for ammonia synthesis

International Nuclear Information System (INIS)

Kotarba, Andrzej; Dmytrzyk, Jaromir; Rarog-Pilecka, Wioletta; Kowalczyk, Zbigniew

2003-01-01

Second-generation ammonia synthesis cesium-doped ruthenium catalyst supported on turbostratic carbon was investigated by the species resolved thermal alkali desorption method (SR-TAD). Energetic barriers for cesium ions (2.86 eV), ground state (1.96 eV) and electronically excited atoms (5.76 eV) desorbing from the Cs-Ru/C catalyst were determined. In the case of ruthenium-free Cs/C system, cesium desorbs as ground state atoms only, with an energy barrier of 2.87 eV. The work functions determined by the thermionic emission of electrons from Cs/C and Cs-Ru/C were of the same value (2.9 eV). It was concluded that ruthenium induces heterogeneous distribution of cesium on the catalyst surface. The promoter stability is reduced on low work function areas and its surface ionization on high work function areas opens the ionic desorption channel. The Cs desorption from the catalyst is discussed in terms of the literature data for the cesium/graphite system

CO Cleavage and CO2 Functionalization under Mild Conditions by a Multimetallic CsU2 Nitride Complex.

Science.gov (United States)

Falcone, Marta; Chatelain, Lucile; Scopelliti, Rosario; Mazzanti, Marinella

2017-04-26

Novel efficient chemical processes involving cheap and widely accessible carbon dioxide or carbon monoxide under mild conditions for the production of valuable chemical products are highly desirable in the current energetic context. Uranium nitride materials act as high activity catalysts in the Haber-Bosch process but the reactivity of molecular nitride compounds remains unexplored. Here we review recent results obtained in our group showing that a multimetallic nitride complex [Cs{[U(OSi(OtBu)3)3]2(μ-N)}] (1) with a CsUIV-N-UIV core, is able to promote N-C bond formation due to its strong nucleophile behaviour. In particular, complex 1, in the presence of excess CO2 leads to a remarkable dicarbamate product. The multimetallic CsUIV-N-UIV nitride also readily cleaves the C≡O bond under mild conditions.

Molecular CsF{sub 5} and CsF{sub 2}{sup +}

Energy Technology Data Exchange (ETDEWEB)

Rogachev, Andrey Yu. [Illinois Institute of Technology, IL (United States). Dept. of Biological and Chemical Sciences; Miao, Mao-sheng [California State Univ., Northridge, CA (United States). Dept. of Chemistry and Biochemistry; Beijing Computational Science Research Center (China); Merino, Gabriel [Centro de Investigacion y de Estudios Avanzados, Unidad Merida (Mexico). Dept. de Fisica Aplicada; Hoffmann, Roald [Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology

2015-07-06

D{sub 5h} star-like CsF{sub 5}, formally isoelectronic with known XeF{sub 5}{sup -} ion, is computed to be a local minimum on the potential energy surface of CsF{sub 5}, surrounded by reasonably large activation energies for its exothermic decomposition to CsF + 2F{sub 2}, or to CsF{sub 3} (three isomeric forms) + F{sub 2}, or for rearrangement to a significantly more stable isomer, a classical Cs{sup +} complex of F{sub 5}{sup -}. Similarly the CsF{sub 2}{sup +} ion is computed to be metastable in two isomeric forms. In the more symmetrical structures of these molecules there is definite involvement in bonding of the formally core 5p levels of Cs.

Carbon-Based CsPbBr3 Perovskite Solar Cells: All-Ambient Processes and High Thermal Stability.

Science.gov (United States)

Chang, Xiaowen; Li, Weiping; Zhu, Liqun; Liu, Huicong; Geng, Huifang; Xiang, Sisi; Liu, Jiaming; Chen, Haining

2016-12-14

The device instability has been an important issue for hybrid organic-inorganic halide perovskite solar cells (PSCs). This work intends to address this issue by exploiting inorganic perovskite (CsPbBr 3 ) as light absorber, accompanied by replacing organic hole transport materials (HTM) and the metal electrode with a carbon electrode. All the fabrication processes (including those for CsPbBr 3 and the carbon electrode) in the PSCs are conducted in ambient atmosphere. Through a systematical optimization on the fabrication processes of CsPbBr 3 film, carbon-based PSCs (C-PSCs) obtained the highest power conversion efficiency (PCE) of about 5.0%, a relatively high value for inorganic perovskite-based PSCs. More importantly, after storage for 250 h at 80 °C, only 11.7% loss in PCE is observed for CsPbBr 3 C-PSCs, significantly lower than that for popular CH 3 NH 3 PbI 3 C-PSCs (59.0%) and other reported PSCs, which indicated a promising thermal stability of CsPbBr 3 C-PSCs.

Antimony (Sb) sorption studies on zircaloy, carbon steel (CS) and magnetite coated CS (MCS) surfaces in aqueous medium at pH 10.2 and 280℃

International Nuclear Information System (INIS)

Keny, S.J.; Kumbhar, A.G.; Achary, S.N.; Basu, Saibal

2014-01-01

Antimony sorption studies on zircaloy, CS and magnetite coated carbon steel (MCS) at primary heat transport temperature (290℃) of pressurised heavy water reactor (PHWR) are of direct relevance in investigating Sb activity problem faced in Indian PHWRs. Sb impregnated PHT pump carbon bearing releases Sb to reactor core. This Sb activates, and redeposit on out-of-core surfaces and results in exposure and apparent high decontamination factors. This Sb is not amenable to normal decantation. The form and state of deposited Sb is not yet fully known. This works attempts for this

Solvent Induced Disulfide Bond Formation in 2,5-dimercapto-1,3,4-thiadiazole

OpenAIRE

Palanisamy Kalimuthu; Palraj Kalimuthu; S. Abraham John

2007-01-01

Disulfide bond formation is the decisive event in the protein folding to determine the conformation and stability of protein. To achieve this disulfide bond formation in vitro, we took 2,5-dimercapto-1,3,4-thiadiazole (DMcT) as a model compound. We found that disulfide bond formation takes place between two sulfhydryl groups of DMcT molecules in methanol. UV-Vis, FT-IR and mass spectroscopic as well as cyclic voltammetry were used to monitor the course of reaction. We proposed a mechanism for...

Highly Stretchable Supercapacitors Based on Aligned Carbon Nanotube/Molybdenum Disulfide Composites.

Science.gov (United States)

Lv, Tian; Yao, Yao; Li, Ning; Chen, Tao

2016-08-01

Stretchable supercapacitors that can sustain their performance under unpredictable tensile force are important elements for practical applications of various portable and wearable electronics. However, the stretchability of most reported supercapacitors was often lower than 100 % because of the limitation of the electrodes used. Herein we developed all-solid-state supercapacitors with a stretchability as high as 240 % by using aligned carbon nanotube composites with compact structure as electrodes. By combined with pseudocapacitive molybdenum disulfide nanosheets, the newly developed supercapacitor showed a specific capacitance of 13.16 F cm(-3) , and also showed excellent cycling retention (98 %) after 10 000 charge-discharge cycles. This work also presents a general and effective approach in developing high-performance electrodes for flexible and stretchable electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective removal of heavy metal ions by disulfide linked polymer networks

Energy Technology Data Exchange (ETDEWEB)

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

2017-06-15

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

Deactivation mechanism of the simultaneous removal of carbonyl ...

Indian Academy of Sciences (India)

KAI LI

2017-11-10

Nov 10, 2017 ... industrial processes.7–11 With the advantages of being cost-effective and having good adsorption, activated ... comes: CS2 reacted directly with the adsorbed water on the surface of the catalyst, and CS2 ..... D 2005 Adsorption-catalytic process for carbon disulfide removal from air Catal. Today 102 242. 8.

Examination of the role of CS{sub 2} in the CS{sub 2}/NMP mixed solvents to coal extraction

Energy Technology Data Exchange (ETDEWEB)

Shui, Hengfu; Wang, Zhicai [School of Chemistry and Chemical Engineering, Anhui University of Technology, 243002 Maanshan Anhui (China); Gao, Jinsheng [Department of Energy Resources and Chemical Engineering, East China University of Science & amp; Technology, 200237 Shanghai (China)

2006-02-15

The roles of CS{sub 2} in the CS{sub 2}/NMP mixed solvent to coal extraction and solubilization were investigated in this study. There was little effect of removing of CS{sub 2} from the solutions on the solubilities of UF coal extract and pyridine insoluble (PI) of the extract in the NMP/CS{sub 2} mixed solvent, suggesting that NMP has high enough solubilities to the UF coal extract and PI. Six Argonne different rank coals were extracted with the CS{sub 2}/NMP mixed solvent and NMP, respectively. It was found that the extraction yield difference between NMP and CS{sub 2}/NMP mixed solvent for UF coal is largely deviated from the curve obtained for the other 5 coals, suggesting that the pre-swelling of CS{sub 2} in the mixed solvent may be one of important roles for high extraction yield of UF coal in the CS{sub 2}/NMP mixed solvent. FTIR indicated that there was a strong interaction between CS{sub 2} and NMP in the CS{sub 2}/NMP mixed solvent of 1:1 volume ratio, which made the strong absorbance at 2156 cm{sup -1} in the FTIR spectra, and this interaction may disrupt the dipole based association of NMP thus making the CS{sub 2}/NMP mixed solvent lower viscosity, to penetrate more quickly into the network structure of coal, resulting in the larger solvent partner (NMP) to enter and break the stronger coal-coal interactions. (author)

Neutron diffraction and thermal studies of amorphous CS2 realised by low-temperature vapour deposition

International Nuclear Information System (INIS)

Yamamuro, O.; Matsuo, T.; Onoda-Yamamuro, N.; Takeda, K.; Munemura, H.; Tanaka, S.; Misawa, M.

2003-01-01

We have succeeded in preparing amorphous carbon disulphide (CS 2 ) by depositing its vapour on a cold substrate at 10 K. Complete formation of the amorphous state has been confirmed by neutron diffraction and differential thermal analysis (DTA). The amorphous sample crystallized at ca. 70 K, which is lower than the hypothetical glass transition temperature (92 K) estimated from the DTA data of the (CS 2 ) x (S 2 Cl 2 ) 1-x binary mixture. CS 2 , a symmetric linear tri-atomic molecule, is the simplest of the amorphized molecular substances whose structural and thermal information has been reported so far. Comparison of the static structure factors S(Q) has shown that the orientational correlation of CS 2 molecules may be much stronger in the amorphous state than in the liquid state at higher temperature. (authors)

Degradation of ethyl mercaptan and its major intermediate diethyl disulfide by Pseudomonas sp. strain WL2.

Science.gov (United States)

Wang, Xiangqian; Wu, Chao; Liu, Nan; Li, Sujing; Li, Wei; Chen, Jianmeng; Chen, Dongzhi

2015-04-01

A Pseudomonas sp. strain WL2 that is able to efficiently metabolize ethyl mercaptan (EM) into diethyl disulfide (DEDS) through enzymatic oxidation was isolated from the activated sludge of a pharmaceutical wastewater plant. One hundred percent removal of 113.5 mg L(-1) EM and 110.3 mg L(-1) DEDS were obtained within 14 and 32 h, respectively. A putative EM degradation pathway that involved the catabolism via DEDS was proposed, which indicated DEDS were further mineralized into carbon dioxide (CO2), bacterial cells, and sulfate (SO4 (2-)) through the transformation of element sulfur and ethyl aldehyde. Degradation kinetics for EM and DEDS with different initial concentrations by strain WL2 were evaluated using Haldane-Andrews model with maximum specific degradation rates of 3.13 and 1.33 g g(-1) h(-1), respectively, and maximum degradation rate constants of 0.522 and 0.175 h(-1) using pseudo-first-order kinetic model were obtained. Results obtained that aerobic degradation of EM by strain WL2 was more efficient than those from previous studies. Substrate range studies of strain WL2 demonstrated its ability to degrade several mercaptans, disulfides, aldehydes, and methanol. All the results obtained highlight the potential of strain WL2 for the use in the biodegradation of volatile organic sulfur compounds (VOSCs).

Cs2UPd3Se6

Directory of Open Access Journals (Sweden)

George N. Oh

2011-02-01

Full Text Available Dicaesium uranium(IV tripalladium(II hexaselenide, Cs2UPd3Se6, crystallizes in the space group Fmmm in the Ba2NaCu3O6 structure type. The asymmetric unit comprises the following atoms with site symmetries as shown: U1 (mm2, Cs1 (222, Cs2 (m2m, Pd1 (.m., Pd2 (2mm, Se1 (m.., and Se2 (1. This layered structure contains six edge-sharing square-planar [PdSe4] units that form a hexagon. These, in turn, edge-share with [USe6] trigonal–prismatic units, forming an extended layer parallel to (010. The layers are stacked along [010]. They are staggered, and are separated by the Cs atoms. The Cs atoms are either coordinated in a square antiprism of Se atoms or are ten-coordinate, with one square face and the opposite face hexagonal.

Syntheses of carbon-14 and sulfur-35 labeled 2-(Morpholinothio)-benzothiazoles and carbon-14 labeled 2-(Cyclohexylaminothio)-benzothiazoles

Energy Technology Data Exchange (ETDEWEB)

Tanaka, A.; Fukuoka, M.; Adachi, T.; Yamaha, T.

1986-04-01

Some vulcanizing accelerators, mercaptobenzothiazole derivatives labeled with carbon-14 or sulfur-35 were prepared. 2-(Morpholinothio)benzothiazole labeled with carbon-14 or sulfur-35 of the sulfhydryl group at position 2 was synthesized by oxidative condensation with sodium hypochlorite from a mixture of morpholine and 2-mercaptobenzothiazole-2-/sup 14/C or 2-mercaptobenzothiazole-2-/sup 35/S. The same method was applicable to the synthesis of 2-(morpholino-U-/sup 14/C-thio) -benzothiazole using morpholine-U-/sup 14/C as starting material. 2-(Cyclohexylaminothio)benzothiazole-2-/sup 14/C was prepared, by oxidation with a mixture of iodine and potassium iodide, from cyclohexylamine and 2-mercapto-benzothiazole-2-/sup 14/C, which was synthesized from carbon-/sup 14/C disulfide and 2-mercaptoaniline in the presence of trace sodium sulfide in dimethylformamide. 2-(Cyclohexyl-U-/sup 14/C-aminothio)benzothiazole was also obtained from cylcohexyl-amine-U-/sup 14/C and 2-mercaptobenzothiazole.

A new approach to group separation of coals

Energy Technology Data Exchange (ETDEWEB)

Zhi-Hong Qin; Zhi-Min Zong; Chun Jiang; Hao Sun; Li-Li Zhou; Xian-Yong Wei [China University of Mining and University, Jiangsu (China). School of Chemical Engineering

2005-07-01

Three coal samples were extracted with carbon disulfide/N-methyl-2-pyrrolidinone (CS{sub 2}/NMP) mixed solvent. The extraction solutions were separated to three layers: insoluble fraction (under layer), CS{sub 2} solution (middle layer) and water/NMP solution (upper layer) by water addition. Most of NMP was concentrated to the upper layer. 7 refs., 3 figs., 3 tabs.

A novel disulfide bond in the SH2 Domain of the C-terminal Src kinase controls catalytic activity.

Science.gov (United States)

Mills, Jamie E; Whitford, Paul C; Shaffer, Jennifer; Onuchic, Jose N; Adams, Joseph A; Jennings, Patricia A

2007-02-02

The SH2 domain of the C-terminal Src kinase [Csk] contains a unique disulfide bond that is not present in other known SH2 domains. To investigate whether this unusual disulfide bond serves a novel function, the effects of disulfide bond formation on catalytic activity of the full-length protein and on the structure of the SH2 domain were investigated. The kinase activity of full-length Csk decreases by an order of magnitude upon formation of the disulfide bond in the distal SH2 domain. NMR spectra of the fully oxidized and fully reduced SH2 domains exhibit similar chemical shift patterns and are indicative of similar, well-defined tertiary structures. The solvent-accessible disulfide bond in the isolated SH2 domain is highly stable and far from the small lobe of the kinase domain. However, reduction of this bond results in chemical shift changes of resonances that map to a cluster of residues that extend from the disulfide bond across the molecule to a surface that is in direct contact with the small lobe of the kinase domain in the intact molecule. Normal mode analyses and molecular dynamics calculations suggest that disulfide bond formation has large effects on residues within the kinase domain, most notably within the active-site cleft. Overall, the data indicate that reversible cross-linking of two cysteine residues in the SH2 domain greatly impacts catalytic function and interdomain communication in Csk.

Immobilized nickel hexacyanoferrate on activated carbons for efficient attenuation of radio toxic Cs(I) from aqueous solutions

International Nuclear Information System (INIS)

Lalhmunsiama; Lalhriatpuia, C.; Tiwari, Diwakar; Lee, Seung-Mok

2014-01-01

Highlights: • Rice hulls and areca nut wastes are utilized to obtain activated carbons. • Nickel hexacyanoferrate is immobilized on activated carbon samples. • Materials are characterized by SEM–EDX and XRD data. • Materials are employed in attenuation of Cs(I) under batch and column studies. • Possible mechanism is deduced at solid/solution interface. - Abstract: The aim of this study is to immobilize nickel hexacyanoferrate onto the large surface of activated carbons (ACs) precursor to rice hulls and areca nut waste materials. These nickel hexacyanoferrate immobilized materials are then assessed in the effective attenuation of radio logically important cesium ions from aqueous solutions. The solid samples are characterized by the XRD analytical method and surface morphology is obtained from the SEM images. The batch reactor experiments show that an increase in sorptive pH (2.0–10.0) apparently not affecting the high percent uptake of Cs(I). Equilibrium modeling studies suggest that the data are reasonably and relatively fitted well to the Langmuir adsorption isotherm. Kinetic studies show that sorption process is fairly rapid and the kinetic data are fitted well to the pseudo-second order rate model. Increasing the background electrolyte concentration from 0.001 to 0.1 mol/L NaCl causes insignificant decrease in Cs(I) removal which infers the higher selectivity of these materials for Cs(I) from aqueous solutions. Further, the column reactor operations enable to obtain the breakthrough data which are then fitted to the Thomas non-linear equation as to obtain the loading capacity of column for Cs(I). The results show that the modified materials show potential applicability in the attenuation of radio toxic cesium from aqueous solution

Electronic properties of Cs-intercalated single-walled carbon nanotubes derived from nuclear magnetic resonance

KAUST Repository

Abou-Hamad, E; Goze-Bac, C; Nitze, F; Schmid, M; Aznar, R; Mehring, M; Wå gberg, T

2011-01-01

We report on the electronic properties of Cs-intercalated single-walled carbon nanotubes (SWNTs). A detailed analysis of the 13C and 133Cs nuclear magnetic resonance (NMR) spectra reveals an increased metallization of the pristine SWNTs under Cs intercalation. The 'metallization' of CsxC materials where x=0–0.144 is evidenced from the increased local electronic density of states (DOS) n(EF) at the Fermi level of the SWNTs as determined from spin–lattice relaxation measurements. In particular, there are two distinct electronic phases called α and β and the transition between these occurs around x=0.05. The electronic DOS at the Fermi level increases monotonically at low intercalation levels x<0.05 (α-phase), whereas it reaches a plateau in the range 0.05≤x≤0.143 at high intercalation levels (β-phase). The new β-phase is accompanied by a hybridization of Cs(6s) orbitals with C(sp2) orbitals of the SWNTs. In both phases, two types of metallic nanotubes are found with a low and a high local n(EF), corresponding to different local electronic band structures of the SWNTs.

Electronic properties of Cs-intercalated single-walled carbon nanotubes derived from nuclear magnetic resonance

KAUST Repository

Abou-Hamad, E

2011-05-24

We report on the electronic properties of Cs-intercalated single-walled carbon nanotubes (SWNTs). A detailed analysis of the 13C and 133Cs nuclear magnetic resonance (NMR) spectra reveals an increased metallization of the pristine SWNTs under Cs intercalation. The \\'metallization\\' of CsxC materials where x=0–0.144 is evidenced from the increased local electronic density of states (DOS) n(EF) at the Fermi level of the SWNTs as determined from spin–lattice relaxation measurements. In particular, there are two distinct electronic phases called α and β and the transition between these occurs around x=0.05. The electronic DOS at the Fermi level increases monotonically at low intercalation levels x<0.05 (α-phase), whereas it reaches a plateau in the range 0.05≤x≤0.143 at high intercalation levels (β-phase). The new β-phase is accompanied by a hybridization of Cs(6s) orbitals with C(sp2) orbitals of the SWNTs. In both phases, two types of metallic nanotubes are found with a low and a high local n(EF), corresponding to different local electronic band structures of the SWNTs.

Interchange reaction of disulfides and denaturation of oxytocin by copper(II)/ascorbic acid/O2 system.

Science.gov (United States)

Inoue, H; Hirobe, M

1987-05-29

The interchange reaction of disulfides was caused by the copper(II)/ascorbic acid/O2 system. The incubation of two symmetric disulfides, L-cystinyl-bis-L-phenylalanine (PP) and L-cystinyl-bis-L-tyrosine (TT), with L-ascorbic acid and CuSO4 in potassium phosphate buffer (pH 7.2, 50 mM) resulted in the formation of an asymmetric disulfide, L-cystinyl-L-phenylalanine-L-tyrosine (PT), and the final ratio of PP:PT:TT was 1:2:1. As the reaction was inhibited by catalase and DMSO only at the initial time, hydroxyl radical generated by the copper(II)/ascorbic acid/O2 system seemed to be responsible for the initiation of the reaction. Oxytocin and insulin were denatured by this system, and catalase and DMSO similarly inhibited these denaturations. As the composition of amino acids was unchanged after the reaction, hydroxyl radical was thought to cause the cleavage and/or interchange reaction of disulfides to denature the peptides.

Neutron diffraction and thermal studies of amorphous CS{sub 2} realised by low-temperature vapour deposition

Energy Technology Data Exchange (ETDEWEB)

Yamamuro, O.; Matsuo, T. [Osaka Univ., Dept. of Chemistry, Graduate School of Sciences (Japan); Onoda-Yamamuro, N. [Tokyo Denki Univ., College of Sciences and Technology (Japan); Takeda, K. [Naruto Univ., Dept. of Chemistry, Tokushima (Japan); Munemura, H.; Tanaka, S.; Misawa, M. [Niigata Univ. (Japan). Faculty of Science

2003-08-01

We have succeeded in preparing amorphous carbon disulphide (CS{sub 2}) by depositing its vapour on a cold substrate at 10 K. Complete formation of the amorphous state has been confirmed by neutron diffraction and differential thermal analysis (DTA). The amorphous sample crystallized at ca. 70 K, which is lower than the hypothetical glass transition temperature (92 K) estimated from the DTA data of the (CS{sub 2}){sub x}(S{sub 2}Cl{sub 2}){sub 1-x} binary mixture. CS{sub 2}, a symmetric linear tri-atomic molecule, is the simplest of the amorphized molecular substances whose structural and thermal information has been reported so far. Comparison of the static structure factors S(Q) has shown that the orientational correlation of CS{sub 2} molecules may be much stronger in the amorphous state than in the liquid state at higher temperature. (authors)

Thermal, conductivity, NMR, and Raman spectroscopic measurements and phase diagram of the Cs2S2O7-CsHSO4 system

DEFF Research Database (Denmark)

Rasmussen, Søren Birk; Hama, Hind; Lapina, Olga

2003-01-01

The conductivity of the binary system CS2S2O7-CsHSO4 has been measured at 20 different molten compositions in the full composition range and in the temperature range 430-750 K. From the obtained liquidus-solidus phase transition temperatures, the phase diagram has been constructed. It is of the s......The conductivity of the binary system CS2S2O7-CsHSO4 has been measured at 20 different molten compositions in the full composition range and in the temperature range 430-750 K. From the obtained liquidus-solidus phase transition temperatures, the phase diagram has been constructed...... from the NMR measurements on CsHSO4, CS2S2O7, and Cs2S2O7-CsHSO4 mixtures. For 11 selected compositions covering the entire composition range of the CS2S2O7-CsHSO4 binary system, the conductivity of the molten state has been expressed by equations of the form k(X) = A(X) + B(X)(T - T-m) + C(X)(T - T...

Cucumber Metallothionein-Like 2 (CsMTL2 Exhibits Metal-Binding Properties

Directory of Open Access Journals (Sweden)

Yu Pan

2016-11-01

Full Text Available We identified a novel member of the metallothionein (MT family, Cucumis sativus metallothionein-like 2 (CsMTL2, by screening a young cucumber fruit complementary DNA (cDNA library. The CsMTL2 encodes a putative 77-amino acid Class II MT protein that contains two cysteine (Cys-rich domains separated by a Cys-free spacer region. We found that CsMTL2 expression was regulated by metal stress and was specifically induced by Cd2+ treatment. We investigated the metal-binding characteristics of CsMTL2 and its possible role in the homeostasis and/or detoxification of metals by heterologous overexpression in Escherichia coli cells. Furthermore, we produced a deletion mutant form of the protein, CsMTL2m, that contained the two Cys-rich clusters but lacked the spacer region, in E. coli. We compared the metal-binding properties of CsMTL2 with those of CsMTL2m, the β domain of human metallothionein-like protein 1 (HsMTXb, and phytochelatin-like (PCL heterologously expressed in E. coli using metal-binding assays. We found that E. coli cells expressing CsMTL2 accumulated the highest levels of Zn2+ and Cd2+ of the four transformed cell types, with levels being significantly higher than those of control cells containing empty vector. E. coli cells expressing CsMTL2 had a higher tolerance for cadmium than for zinc ions. These findings show that CsMTL2 improves metal tolerance when heterologously expressed in E. coli. Future studies should examine whether CsMTL2 improves metal tolerance in planta.

Synthesis and crystal structure of hydrogen phosphites RbH2PO3, CsH2PO3, and TlH2PO3

International Nuclear Information System (INIS)

Kosterina, E.V.; Troyanov, S.I.; Kemnits, Eh.; Aslanov, L.A.

2001-01-01

The crystal acid phosphites RbH 2 PO 3 , CsH 2 PO 3 and TlH 2 PO 3 were separated during reaction of Rb, Cs and Tl carbonates with phosphorous acid solution. The crystal structure of the compounds was analyzed by X-ray diffraction method at 150 K. CsH 2 PO 3 has a monoclinic system, a = 7.930(2), b = 8.929(2), c = 13.163(3) A, β = 104.84(3) Deg, V = 900.9(4) A 3 , Z 8, sp. gr. P2 1 /c, R 1 = 0.239. In the structure hydrogen bonds integrate the PHO 3 tetrahedrons in the unlimited zigzag chains [HPHO 3 ] n n- laying at the layers, which are alternate to the layers of metal cations. The layers of anion chains have a wavy form [ru

Temperature and Pressure Dependence of the Reaction S plus CS (+M) -> CS2 (+M)

DEFF Research Database (Denmark)

Glarborg, Peter; Marshall, Paul; Troe, Juergen

2015-01-01

Experimental data for the unimolecular decomposition of CS2 from the literature are analyzed by unimolecular rate theory with the goal of obtaining rate constants for the reverse reaction S + CS (+M) -> CS2 (+M) over wide temperature and pressure ranges. The results constitute an important input...

Design and introduction of a disulfide bridge in firefly luciferase: increase of thermostability and decrease of pH sensitivity.

Science.gov (United States)

Imani, Mehdi; Hosseinkhani, Saman; Ahmadian, Shahin; Nazari, Mahboobeh

2010-08-01

The thermal sensitivity and pH-sensitive spectral properties of firefly luciferase have hampered its application in a variety of fields. It is proposed that the stability of a protein can be increased by introduction of disulfide bridge that decreases the configurational entropy of unfolding. A disulfide bridge is introduced into Photinus pyralis firefly luciferase to make two separate mutant enzymes with a single bridge. Even though the A103C/S121C mutant showed remarkable thermal stability, its specific activity decreased, whereas the A296C/A326C mutant showed tremendous thermal stability, relative pH insensitivity and 7.3-fold increase of specific activity. Moreover, the bioluminescence emission spectrum of A296C/A326C was resistant against higher temperatures (37 degrees C). Far-UV CD analysis showed slight secondary structure changes for both mutants. Thermal denaturation analysis showed that conformational stabilities of A103C/S121C and A296C/A326C are more than native firefly luciferase. It is proposed that since A296 and A326 are situated in the vicinity of the enzyme active site microenvironment in comparison with A103 and S121, the formation of a disulfide bridge in this region has more impact on enzyme kinetic characteristics.

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: the case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations.

Science.gov (United States)

Cabaço, M Isabel; Besnard, Marcel; Chávez, Fabián Vaca; Pinaud, Noël; Sebastião, Pedro J; Coutinho, João A P; Danten, Yann

2014-06-28

NMR spectroscopy ((1)H, (13)C, (15)N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH3COS(-)), CO2, OCS, and trithiocarbonate (CS3 (2-)). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro](+) cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS2-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO2-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS2 reacts with the acetate anion leading to the formation of CH3COS(-), CO2, and OCS. After these reactions have proceeded the nascent CO2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO2) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO2-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO2, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim

Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}, and Cs{sub 7}[Fe{sub 4}Se{sub 8}]. Missing links of known chalcogenido ferrate series

Energy Technology Data Exchange (ETDEWEB)

Stueble, Pirmin; Roehr, Caroline [Institut fuer Anorganische und Analytische Chemie, Universitaet Freiburg (Germany)

2017-11-17

The three cesium selenido ferrate title compounds with an Se:Fe ratio of 2:1 were synthesized from stoichiometric samples reacting elemental Cs either (A) with Fe and Se in a double-crucible setup (Cs[FeSe{sub 2}], Cs{sub 3}[FeSe{sub 2}]{sub 2}) or (B) with previously prepared FeSe{sub 2} (Cs{sub 3}[FeSe{sub 2}]{sub 2}, Cs{sub 7}[Fe{sub 4}S{sub 8}]) (T{sub max} = 800-1000 C). The pure Fe{sup III} ferrate Cs[FeSe{sub 2}] crystallizes in the Tl[FeSe{sub 2}] type [monoclinic, space group C2/m, a = 1392.95(10), b = 564.43(3), c = 737.44(6) pm, β = 119.163(5) , Z = 4, R{sub 1} = 0.0550]. It is thus not isotypic to all other alkali ferrates(III) A[FeS{sub 2}] and A[FeSe{sub 2}] containing chains of edge-sharing tetrahedra, but crystallizes in a t2 subgroup of the Immm structure of Cs[FeS{sub 2}]. The mixed-valent chain compound Cs{sub 3}[FeSe{sub 2}]{sub 2} is isotypic to its sulfido analogue [orthorhombic, space group Pnma, a = 777.88(6), b = 1151.02(6), c = 1341.61(7) pm, Z = 4, R{sub 1} = 0.0470]. In contrast to the isopunctal Na{sub 3}[FeSe{sub 2}]{sub 2} type K/Rb compounds the chains are only slightly corrugated. The monoclinic, likewise mixed-valent Fe{sup II/III} selenido ferrate Cs{sub 7}[Fe{sub 4}Se{sub 8}] [monoclinic, space group C2/c, a = 1953.79(10), b = 879.71(5), c = 1717.03(10) pm, β = 117.890(2) , Z = 4, R{sub 1} = 0.0816] is isostructural both to the cesium sulfido and tellurido compound. The structure contains oligomeric moieties of four edge sharing [FeSe{sub 4}] tetrahedra forming slightly distorted tetrahedral clusters [Fe{sub 4}Se{sub 8}]{sup 7-}, which are surrounded by a cube of 26 Cs cations. Based on a structure map, the crystal chemistry of the three title compounds is discussed together with all chain/cluster ferrates of the general series A{sub 1+x}[Fe{sup III}{sub 1-x}Fe{sup II}{sub x}Q{sub 2}] (x = 0-1; A = Na, K, Rb, Cs; Q = S, Se, Te). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Quantification of thiols and disulfides

DEFF Research Database (Denmark)

Winther, Jakob R.; Thorpe, Colin

2014-01-01

lengths to regulate thiol-disulfide bond homeostasis, typically with several, apparently redundant, systems working in parallel. Dissecting the extent of oxidation and reduction of disulfides is an ongoing challenge due, in part, to the facility of thiol/disulfide exchange reactions.......Disulfide bond formation is a key posttranslational modification, with implications for structure, function and stability of numerous proteins. While disulfide bond formation is a necessary and essential process for many proteins, it is deleterious and disruptive for others. Cells go to great...

Additional disulfide bonds in insulin

DEFF Research Database (Denmark)

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

2015-01-01

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

Selective removal of heavy metal ions by disulfide linked polymer networks

DEFF Research Database (Denmark)

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

2017-01-01

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

Knudsen cell--mass spectrometer studies of cesium--urania interactions. [Cs/sub 2/CO/sub 3/ or CsOH

Energy Technology Data Exchange (ETDEWEB)

Collins, J.L.; Osborne, M.F.; Malinauskas, A.P.; Lorenz, R.A.; Manning, S.R.

1976-06-01

Limited Knudsen cell--mass spectrometer studies were made of the partial pressures of cesium-containing species (assumed to be primarily Cs(g)) over Cs/sub 2/CO/sub 3/ and over phase equilibria involving UO/sub 2/ and probable Cs-U-O compounds formed from mixtures that initially contained either Cs/sub 2/CO/sub 3/-UO/sub 2/ or CsOH-UO/sub 2/. Although additional work is required to further define the equilibria involved, the data demonstrate unambiguously a significant reduction in cesium partial pressures due to probable Cs-U-O compound formation and indicate essentially identical behavior with either CsOH or Cs/sub 2/CO/sub 3/ as the starting material with UO/sub 2/.

Combining biophysical methods to analyze the disulfide bond in SH2 domain of C-terminal Src kinase.

Science.gov (United States)

Liu, Dongsheng; Cowburn, David

2016-01-01

The Src Homology 2 (SH2) domain is a structurally conserved protein domain that typically binds to a phosphorylated tyrosine in a peptide motif from the target protein. The SH2 domain of C-terminal Src kinase (Csk) contains a single disulfide bond, which is unusual for most SH2 domains. Although the global motion of SH2 domain regulates Csk function, little is known about the relationship between the disulfide bond and binding of the ligand. In this study, we combined X-ray crystallography, solution NMR, and other biophysical methods to reveal the interaction network in Csk. Denaturation studies have shown that disulfide bond contributes significantly to the stability of SH2 domain, and crystal structures of the oxidized and C122S mutant showed minor conformational changes. We further investigated the binding of SH2 domain to a phosphorylated peptide from Csk-binding protein upon reduction and oxidation using both NMR and fluorescence approaches. This work employed NMR, X-ray cryptography, and other biophysical methods to study a disulfide bond in Csk SH2 domain. In addition, this work provides in-depth understanding of the structural dynamics of Csk SH2 domain.

Radioiodine-labeled disulfide: a novel radiotracer for evaluation of tumor uptake

Energy Technology Data Exchange (ETDEWEB)

Ryu, E. K.; Choi, Y. S.; Byun, S. S.; Baek, J. Y.; Lee, K. H.; Kim, S. E.; Choi, Y.; Kim, B. T. [Sungkyunkwan University School of Medicine, Seoul (Korea, Republic of)

2002-07-01

Diallyl disulfide found in garlic has been known to inhibit the growth of various cancer cells. In this study, iodine-substituted disulfides were synthesized and their growth inhibitory effects on cancer cells (SUN C5 and MCF-7) were investigated. Dibenzyl disulfide was labeled with {sup 123}I/{sup 125}I for evaluation of tumor uptake. Halogen-substituted disulfides were synthesized using 2,2'-dithiobis(benzothiazole) and one equivalent each of the corresponding thiols. Growth inhibition studies were performed on cancer cells that were grown at 37 .deg. C for 48 hr prior to exposure to the disulfides. Radioiodine-labeled disulfide was prepared by halogen exchange reaction on the 4-bromodibenzyl disulfide in the presence of Na{sup 123}I/{sup 125}I and CuCl at 150 .deg. C for 60 min, followed by HPLC purification. Uptake of the radioactivity to SUN C5 cells was measured as a function of time, and inhibition studies were performed in the presence of either S-methyl methanethiosulfonate (MMTS) or diallyl disulfide. Disulfides were synthesized in the high yields (90%). Tumor growth inhibition studies by the 3 iododisulfides showed the inhibition (>95%) comparable to diallyl disulfide (100%). Cu(I)-assisted radioiodination gave 4-{sup 123}I/{sup 125}I-iododibenzyl disulfide in overall 30-40% radiochemical yield and with high specific activity. Cell uptake studies of the radiolabeled disulfide showed a time-dependent increase of the uptake (4-fold increase from 15 min to 2 hr). Both MMTS, a glutathione depleting agent, and diallyl disulfide reduced the uptake of the radioactivity in a dose-dependent manner. Inhibition studies suggest that uptake of disulfide to the tumor cells could be mediated by thiol-disulfide exchange. This study demonstrates that radioiodine-labeled dibenzyl disulfide may be useful for evaluation of tumor uptake.

Structural and catalytic characterization of a thermally stable and acid-stable variant of human carbonic anhydrase II containing an engineered disulfide bond

Energy Technology Data Exchange (ETDEWEB)

Boone, Christopher D.; Habibzadegan, Andrew [University of Florida, PO Box 100245, Gainesville, FL 32610 (United States); Tu, Chingkuang; Silverman, David N. [University of Florida, PO Box 100267, Gainesville, FL 32610 (United States); McKenna, Robert, E-mail: rmckenna@ufl.edu [University of Florida, PO Box 100245, Gainesville, FL 32610 (United States)

2013-08-01

The X-ray crystallographic structure of the disulfide-containing HCAII (dsHCAII) has been solved to 1.77 Å resolution and revealed that successful oxidation of the cysteine bond was achieved while also retaining desirable active-site geometry. The carbonic anhydrases (CAs) are a family of mostly zinc metalloenzymes that catalyze the reversible hydration of CO{sub 2} to bicarbonate and a proton. Recently, there has been industrial interest in utilizing CAs as biocatalysts for carbon sequestration and biofuel production. The conditions used in these processes, however, result in high temperatures and acidic pH. This unfavorable environment results in rapid destabilization and loss of catalytic activity in CAs, ultimately resulting in cost-inefficient high-maintenance operation of the system. In order to negate these detrimental industrial conditions, cysteines at residues 23 (Ala23Cys) and 203 (Leu203Cys) were engineered into a wild-type variant of human CA II (HCAII) containing the mutation Cys206Ser. The X-ray crystallographic structure of the disulfide-containing HCAII (dsHCAII) was solved to 1.77 Å resolution and revealed that successful oxidation of the cysteine bond was achieved while also retaining desirable active-site geometry. Kinetic studies utilizing the measurement of {sup 18}O-labeled CO{sub 2} by mass spectrometry revealed that dsHCAII retained high catalytic efficiency, and differential scanning calorimetry showed acid stability and thermal stability that was enhanced by up to 14 K compared with native HCAII. Together, these studies have shown that dsHCAII has properties that could be used in an industrial setting to help to lower costs and improve the overall reaction efficiency.

The effective synthesis of Insoluble sulfur using electron beam

Energy Technology Data Exchange (ETDEWEB)

Kim, Daejin; Yu, Kookhyun [Dongguk Univ., Seoul (Korea, Republic of)

2013-07-01

Vulcanization is process that formed crosslinking by Insoluble sulfur between linear structure of rubber polymer. Recently, Synthesis of Insoluble sulfur is used Thermal polymerization using about 250 {approx} 300 .deg. C and extraction process is used carbon disulfide(CS2) for separation between soluble sulfur and insoluble sulfur. But this process isn't environmental, economical and safety. This research was focus on developing of insoluble sulfur synthesis process using electron beam. This new process is using under the 140 .deg. C. Because of that, explosion risk is decrease, environmental and economical factor is increased. The sulfur can be melt by increase temperature or made solution using carbon disulfide. And electron beam is irradiated melting sulfur or sulfur solution. After irradiation, The high purity insoluble sulfur can be obtained by separation with carbon disulfide.

Thiol-disulfide exchange in peptides derived from human growth hormone.

Science.gov (United States)

Chandrasekhar, Saradha; Epling, Daniel E; Sophocleous, Andreas M; Topp, Elizabeth M

2014-04-01

Disulfide bonds stabilize proteins by cross-linking distant regions into a compact three-dimensional structure. They can also participate in hydrolytic and oxidative pathways to form nonnative disulfide bonds and other reactive species. Such covalent modifications can contribute to protein aggregation. Here, we present experimental data for the mechanism of thiol-disulfide exchange in tryptic peptides derived from human growth hormone in aqueous solution. Reaction kinetics was monitored to investigate the effect of pH (6.0-10.0), temperature (4-50°C), oxidation suppressants [ethylenediaminetetraacetic acid (EDTA) and N2 sparging], and peptide secondary structure (amide cyclized vs. open form). The concentrations of free thiol containing peptides, scrambled disulfides, and native disulfide-linked peptides generated via thiol-disulfide exchange and oxidation reactions were determined using reverse-phase HPLC and liquid chromatography-mass spectrometry. Concentration versus time data were fitted to a mathematical model using nonlinear least squares regression analysis. At all pH values, the model was able to fit the data with R(2) ≥ 0.95. Excluding oxidation suppressants (EDTA and N2 sparging) resulted in an increase in the formation of scrambled disulfides via oxidative pathways but did not influence the intrinsic rate of thiol-disulfide exchange. In addition, peptide secondary structure was found to influence the rate of thiol-disulfide exchange. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

The Godparent Plan: A Pedagogical Strategy for CS1 Accompaniment and CS2 Pedagogical Enhancement

Directory of Open Access Journals (Sweden)

Pedro Guillermo Feijóo-García

2018-02-01

Full Text Available Courses such as CS1 and CS2 can present an interesting pedagogical challenge when it comes to the theory-practice relationship, along with aspects that involve the course's logistics, the programming language used, and the characteristics of the students involved in the process. This study presents an innovative didactic approach, oriented towards the accompaniment of CS1 students by CS2 students at Universidad El Bosque, Colombia, seeking with this Godparent Plan, to provide a personalized accompaniment to first semester students, whereby CS2 students enhance their domain over concepts and skills while accompanying, explaining and teaching younger peers. The results of this study are favorable, outlining a didactic scheme that can be adapted and replicated in other curricular scenarios.

A model with charges and polarizability for CS2 in an ionic liquid

Indian Academy of Sciences (India)

RUTH M LYNDEN-BELL

the static electrostatic distribution in the CS2 molecule with 7 charged sites and anisotropic polarizability on the carbon site and isotropic .... the charges modified to reproduce the molecular quad- ... face at 1.5 times the van der Waals radii from the nuclei ..... shows the probability distribution of induced dipoles on the C site ...

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-09-15

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

133Cs NMR investigation of 2D frustrated Heisenberg antiferromagnet, Cs2CuCl4

Science.gov (United States)

Vachon, M.-A.; Kundhikanjana, W.; Straub, A.; Mitrovic, V. F.; Reyes, A. P.; Kuhns, P.; Coldea, R.; Tylczynski, Z.

2006-10-01

We report 133Cs nuclear magnetic resonance (NMR) measurements on the 2D frustrated Heisenberg antiferromagnet Cs2CuCl4 down to 2 K and up to 15 T. We show that 133Cs NMR is a good probe of the magnetic degrees of freedom in this material. Cu spin degrees of freedom are sensed through a strong anisotropic hyperfine coupling. The spin excitation gap opens above the critical saturation field. The gap value was determined from the activation energy of the nuclear spin-lattice relaxation rate in a magnetic field applied parallel to the Cu chains (\\skew3\\hat{b} axis). The values of the g-factor and the saturation field are consistent with the neutron-scattering and magnetization results. The measurements of the spin spin relaxation time are exploited to show that no structural changes occur down to the lowest temperatures investigated.

Cesium platinide hydride 4Cs{sub 2}Pt.CsH: an intermetallic double salt featuring metal anions

Energy Technology Data Exchange (ETDEWEB)

Smetana, Volodymyr [Ames Laboratory, US Department of Energy, and Critical Materials Institute, Ames, Iowa, 50011-3020 (United States); Mudring, Anja-Verena [Ames Laboratory, US Department of Energy, and Critical Materials Institute, Ames, Iowa, 50011-3020 (United States); Department of Materials Sciences and Engineering, Iowa State University, Ames, Iowa, 50011-3111 (United States)

2016-11-14

With Cs{sub 9}Pt{sub 4}H a new representative of ionic compounds featuring metal anions can be added to this rare-membered family. Cs{sub 9}Pt{sub 4}H exhibits a complex crystal structure containing Cs{sup +} cations, Pt{sup 2-} and H{sup -} anions. Being a red, transparent compound its band gap is in the visible range of the electromagnetic spectrum and the ionic type of bonding is confirmed by quantum chemical calculations. This cesium platinide hydride can formally be considered as a double salt of the ''alloy'' cesium-platinum, or better cesium platinide, Cs{sub 2}Pt, and the salt cesium hydride CsH according to Cs{sub 9}Pt{sub 4}H≡4 Cs{sub 2}Pt.CsH. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Vibrational spectra of Cs2Cu(SO4)2·6H2O and Cs2Cu(SeO4)2·nH2O (n = 4, 6) with a crystal structure determination of the Tutton salt Cs2Cu(SeO4)2·6H2O

Science.gov (United States)

Wildner, M.; Marinova, D.; Stoilova, D.

2016-02-01

The solubility in the three-component systems Cs2SO4-CuSO4-H2O and Cs2SeO4-CuSeO4-H2O have been studied at 25 °C. The experimental results show that double salts, Cs2Cu(SO4)2·6H2O and Cs2Cu(SeO4)2·4H2O, crystallize from the ternary solutions within large concentration ranges. Crystals of Cs2Cu(SeO4)2·6H2O were synthesized at somewhat lower temperatures (7-8 °C). The thermal dehydration of the title compounds was studied by TG, DTA and DSC methods and the respective dehydration schemes are proposed. The calculated enthalpies of dehydration (ΔHdeh) have values of: 434.2 kJ mol-1 (Cs2Cu(SeO4)2·6H2O), 280.9 kJ mol-1 (Cs2Cu(SeO4)2·4H2O), and 420.2 kJ mol-1 (the phase transition of Cs2Cu(SO4)2·6H2O into Cs2Cu(SO4)2·H2O). The crystal structure of Cs2Cu(SeO4)2ṡ6H2O was determined from single crystal X-ray diffraction data. It belongs to the group of Tutton salts, crystallizing isotypic to the respective sulfate in a monoclinic structure which is characterized by isolated Cu(H2O)6 octahedra and SeO4 tetrahedra, interlinked by hydrogen bonds and [9]-coordinated Cs+ cations. Infrared spectra of the cesium copper compounds are presented and discussed with respect to both the normal modes of the tetrahedral ions and the water molecules. The analysis of the infrared spectra of the double compounds reveals that the distortion of the selenate tetrahedra in Cs2Cu(SeO4)2·4H2O is stronger than those in Cs2Cu(SeO4)2·6H2O in agreement with the structural data. Matrix-infrared spectroscopy was applied to confirm this claim - Δν3 for SO4 2 - ions matrix-isolated in Cs2Cu(SeO4)2·6H2O has a value of 35 cm-1 and that of the same ions included in Cs2Cu(SeO4)2·4H2O - 84 cm-1. This spectroscopic finding is due to the formation of strong covalent bands Cu-OSO3 on one hand, and on the other to the stronger deformation of the host SeO4 2 - tetrahedra in Cs2Cu(SeO4)2·4H2O as compared to those in Cs2Cu(SeO4)2·6H2O. The strength of the hydrogen bonds as deduced from the

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

DEFF Research Database (Denmark)

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

2016-01-01

in protein sequencing by tandem MS (MS/MS). Electrochemical (EC) reduction of disulfide bonds has recently been demonstrated to provide efficient reduction efficiencies, significantly enhancing sequence coverages in online coupling with MS characterization. In this study, the potential use of EC disulfide...... link between parent disulfide-linked fragments and free reduced peptides in an LC-EC-MS platform of nonreduced proteolytic protein digestions. Here we report the successful use of EC as a partial reduction approach in mapping of disulfide bonds of intact human insulin (HI) and lysozyme. In addition, we...... established a LC-EC-MS platform advantageous in disulfide characterization of complex and highly disulfide-bonded proteins such as human serum albumin (HSA) by online EC reduction of nonreduced proteolytic digestions....

Reactivity of the Donor-Stabilized Silylenes [iPrNC(Ph)NiPr]2 Si and [iPrNC(NiPr2 )NiPr]2 Si: Activation of CO2 and CS2.

Science.gov (United States)

Mück, Felix M; Baus, Johannes A; Nutz, Marco; Burschka, Christian; Poater, Jordi; Bickelhaupt, F Matthias; Tacke, Reinhold

2015-11-09

Activation of CO2 by the bis(amidinato)silylene 1 and the analogous bis(guanidinato)silylene 2 leads to the structurally analogous six-coordinate silicon(IV) complexes 4 (previous work) and 8, respectively, the first silicon compounds with a chelating carbonato ligand. Likewise, CS2 activation by silylene 1 affords the analogous six-coordinate silicon(IV) complex 10, the first silicon compound with a chelating trithiocarbonato ligand. CS2 activation by silylene 2, however, yields the five-coordinate silicon(IV) complex 13 with a carbon-bound CS2 (2-) ligand, which also represents an unprecedented coordination mode in silicon coordination chemistry. Treatment of the dinuclear silicon(IV) complexes 5 and 6 with CO2 also affords the six-coordinate carbonatosilicon(IV) complexes 4 and 8, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A glassy carbon electrode modified with a nanocomposite consisting of molybdenum disulfide intercalated into self-doped polyaniline for the detection of bisphenol A

International Nuclear Information System (INIS)

Yang, Tao; Chen, Huaiyin; Yang, Ruirui; Jiang, Yuhang; Jiao, Kui; Li, Weihua

2015-01-01

Thin-layered molybdenum disulfide (MoS 2 ) was intercalated, via ultrasonic exfoliation, into self-doped polyaniline (SPAN). This material, when placed on a glassy carbon electrode (GCE), exhibits excellent electrical conductivity and synergistic catalytic activity with respect to the detection of bisphenol A (BPA). The electrochemical response of the modified GCE to BPA was investigated by cyclic voltammetry and differential pulse voltammetry. Under optimal conditions, the oxidation peak current (measured best at 446 mV vs. SCE) is related to the concentration of BPA in the range from 1.0 nM to 1.0 μM, and the detection limit is 0.6 nM. (author)

Hybrid fibers made of molybdenum disulfide, reduced graphene oxide, and multi-walled carbon nanotubes for solid-state, flexible, asymmetric supercapacitors.

Science.gov (United States)

Sun, Gengzhi; Zhang, Xiao; Lin, Rongzhou; Yang, Jian; Zhang, Hua; Chen, Peng

2015-04-07

One of challenges existing in fiber-based supercapacitors is how to achieve high energy density without compromising their rate stability. Owing to their unique physical, electronic, and electrochemical properties, two-dimensional (2D) nanomaterials, e.g., molybdenum disulfide (MoS2 ) and graphene, have attracted increasing research interest and been utilized as electrode materials in energy-related applications. Herein, by incorporating MoS2 and reduced graphene oxide (rGO) nanosheets into a well-aligned multi-walled carbon nanotube (MWCNT) sheet followed by twisting, MoS2 -rGO/MWCNT and rGO/MWCNT fibers are fabricated, which can be used as the anode and cathode, respectively, for solid-state, flexible, asymmetric supercapacitors. This fiber-based asymmetric supercapacitor can operate in a wide potential window of 1.4 V with high Coulombic efficiency, good rate and cycling stability, and improved energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absorption spectra of CsNd(MoO4)2 and CsGd(MoO4)2-Nd3+ crystals in strong magnetic fields

International Nuclear Information System (INIS)

Gorban', I.S.; Kozeeva, L.P.; Slobodyanyuk, A.V.; Shevchenko, V.A.

1987-01-01

The comparison of the electronic structure of Nd 3+ in CsNd(MoO 4 ) 2 and CsGd(MoO 4 ) 2 - Nd 3+ crystals is made. It is established that in these crystals the activator centers, mainly, of the certain type with the symmetry of the local environment C 2 are formed. The absorption spectra of self-activated CsNd(MoO 4 ) 2 crystal differ from spectra of CsGd(MoO 4 ) 2 - Nd 3+ by the presence of the vibrating structure. The Stark splittings of energy levels of Nd 3+ in the investigated crystalline matrices are more sensitive to the environment effect than the Zeeman ones. The ground state of Nd 3+ ion in CsNd(MoO 4 ) 2 and CsGd(MoO 4 ) 2 molybdates is characterized by the similar values of g-factors

Theoretical study of the Cs isotope exchange reaction of CsI + Cs' → Cs + ICs' (Contract research)

International Nuclear Information System (INIS)

Kobayashi, Takanori; Hashimoto, Masashi; Yokoyama, Keiichi

2015-12-01

To discuss the exchange reaction of Cs isotope by CsI + Cs' → Cs + ICs', the structure and chemical properties of Cs 2 I intermediate and potential energy surface of the entrance reaction are calculated using M06/def2-TZVPPD density functional calculation. The calculation shows that the reaction to the intermediate has no barrier and the two Cs-I bonds of Cs 2 I are chemically equivalent. These results suggest that the rate of the Cs exchange reaction of CsI + Cs' → Cs + ICs' is as high as the collision rate. (author)

Electronic Switch in the Carbon-Centered [Re12CS17(CN6] n−Nanocluster

Directory of Open Access Journals (Sweden)

Gabuda SP

2009-01-01

Full Text Available Abstract An abrupt change in internuclear Re–Re distances between {Re6} subunits in the carbon-centered [Re12μ6-CS17(CN6] n−complexes caused by the change of the oxidation state (n = 6, 8 is first theoretically shown to be possibly controlled by an external electric field.13C NMR signal is shown to change over ~400 ppm (~37G for μ6-C atom together withn. Thereby, the metal cluster [Re12μ6-CS17(CN6] n−can be considered as a perspective model of a molecular switch.

Amino Acid Patterns around Disulfide Bonds

Directory of Open Access Journals (Sweden)

Brett Drury

2010-11-01

Full Text Available Disulfide bonds provide an inexhaustible source of information on molecular evolution and biological specificity. In this work, we described the amino acid composition around disulfide bonds in a set of disulfide-rich proteins using appropriate descriptors, based on ANOVA (for all twenty natural amino acids or classes of amino acids clustered according to their chemical similarities and Scheffé (for the disulfide-rich proteins superfamilies statistics. We found that weakly hydrophilic and aromatic amino acids are quite abundant in the regions around disulfide bonds, contrary to aliphatic and hydrophobic amino acids. The density distributions (as a function of the distance to the center of the disulfide bonds for all defined entities presented an overall unimodal behavior: the densities are null at short distances, have maxima at intermediate distances and decrease for long distances. In the end, the amino acid environment around the disulfide bonds was found to be different for different superfamilies, allowing the clustering of proteins in a biologically relevant way, suggesting that this type of chemical information might be used as a tool to assess the relationship between very divergent sets of disulfide-rich proteins.

Thermodynamic studies of (RbF + RbCl + H2O) and (CsF + CsCl + H2O) ternary systems from potentiometric measurements at T = 298.2 K

International Nuclear Information System (INIS)

Huang, Xiaoting; Li, Shu’ni; Zhai, Quanguo; Jiang, Yucheng; Hu, Mancheng

2016-01-01

Graphical abstract: Thermodynamic properties, such as mean activity coefficients, osmotic coefficients and excess Gibbs free energies, of the RbF + RbCl + H 2 O and CsF + CsCl + H 2 O ternary systems were determined from potentiometric measurement at 298.2 K. The Pitzer model and the Harned rule were used to fit the experimental data. - Highlights: • Thermodynamic properties of RbF + RbCl + H 2 O and CsF + CsCl + H 2 O ternary systems were determined. • The Pitzer model and the Harned rule were used to correlate the experimental data. • The mean activity coefficients, osmotic coefficients, and the excess Gibbs free energy were also obtained. - Abstract: Thermodynamic properties of (RbF + RbCl + H 2 O) and (CsF + CsCl + H 2 O) systems were determined by the potentiometric method for different ionic strength fractions y B of RbCl/CsCl at 298.2 K. The Pitzer model and the Harned rule were used to fit the experimental values. The Pitzer mixing parameters and the Harned coefficients were evaluated. In addition, the mean ionic activity coefficients of RbF/CsF and RbCl/CsCl, the osmotic coefficients, and the excess Gibbs energies of the systems studied were calculated.

Rietveld refinement of the orthorhombic Pbca structures of Rb2CdSi5O12, Cs2MnSiO5O12, Cs2CoSi5O12 and Cs2NiSi5O12 leucites by synchrotron X-ray powder diffraction

International Nuclear Information System (INIS)

Bell, A.M.T.; Henderson, C.M.B.

1996-01-01

Analysis of high-resolution synchrotron X-ray powder diffraction patterns for hydrothermally synthesized Rb 2 CdSi 5 O 12 and Cs 2 MnSi 5 O 12 leucite analogues, and dry-synthesized Cs 2 CoSi 5 O 12 and Cs 2 NiSi 5 O 12 leucite analogues showed that they have an orthorhombic Pbca structure. The structures have been refined by the Rietveld method, showing that the tetrahedrally coordinated atoms (Si, Cd, Mn, Co and Ni) are ordered on separate sites. The Cs 2 MnSi 5 O 12 , Cs 2 CoSi 5 O 12 and Cs 2 NiSi 5 O 12 leucite samples are unusual in containing SiO 4 tetrahedra which are more distorted, on average, than the larger MnO 4 , CoO 4 and NiO 4 tetrahedra. The JCPDS file numbers for Rb 2 CdSi 5 O 12 , Cs 2 MnSi 5 O 12 and Cs 2 CoSi 5 O 12 are 46-1491, 46-1492 and 46-1493, respectively. (orig.)

Elastic properties of Cs2HgBr4 and Cs2CdBr4 crystals

International Nuclear Information System (INIS)

Kityk, A.V.; Zadorozhna, A.V.; Shchur, Y.I.; Martynyuk-Lototska, Y.I.; Burak, Y.; Vlokh, O.G.

1998-01-01

Using ultrasonic velocity measurements, all components of the elastic constant matrix C ij , elastic compliances matrix S ij , and linear compressibility constants matrix K ij of orthorhombic Cs 2 HgBr 4 and Cs 2 CdBr 4 crystals have been determined over a wide temperature range, including the region of the phase transition from the normal to the incommensurate phase. Results obtained are considered within the framework of the phenomenological theory. Preliminary analysis of the acoustical properties at room temperature clearly indicates that both crystals are relatively important materials for acousto-optical applications. Copyright (1998) CSIRO Australia

Detection of CS in Neptune's atmosphere from ALMA observations

Science.gov (United States)

Moreno, R.; Lellouch, E.; Cavalié, T.; Moullet, A.

2017-12-01

Context. The large and vertically non-uniform abundance of CO in Neptune's atmosphere has been interpreted as the result of past cometary impact(s), either single or distributed in size and time, which could also be at the origin of Neptune's HCN. Aims: We aim to provide observational support for this scenario by searching for other comet-induced species, in particular carbon sulfide (CS) which has been observed continuously in Jupiter since the 1994 Shoemaker-Levy 9 impacts. Methods: In April 2016 we used the ALMA interferometer to search for CS(7-6) at 342.883 GHz in Neptune. Results: We report on the detection of CS in Neptune's atmosphere, the first unambiguous observation of a sulfur-bearing species in a giant planet beyond Jupiter. Carbon sulfide appears to be present only at submillibar levels, with a column density of (2.0-3.1) × 1012 cm-2, and a typical mixing ratio of (2-20) × 10-11 that depends on its precise vertical location. The favoured origin of CS is deposition by a putative large comet impact several centuries ago, and the strong depletion of CS with respect to CO - compared to the Jupiter case - is likely due to the CS sticking to aerosols or clustering to form polymers in Neptune's lower stratosphere. Conclusions: The CS detection, along with recent analyses of the CO profile, reinforces the presumption of a large comet impact into Neptune 1000 yr ago, that delivered CO, CS, and HCN at the same time.

Simple one-pot synthesis of thioureas from amine, carbon disulfide and oxidants in water

Directory of Open Access Journals (Sweden)

Milosavljević Milutin M.

2016-01-01

Full Text Available The present study reports the new facile methodology for synthesis of symmetrical and asymmetrical thioureas by an one-pot reaction of amine, carbon disulfide and oxidants: hydrogen peroxide, ethylenediamine tetraacetic acid (EDTA/sodium percarbonate system or air. The structures of the synthesized compounds were confirmed by IR, 1H and 13C NMR and MS methods. Reaction mechanism has been proposed on the basis of reaction intermediate isolation and their structure determination. The synthetic benefits of the presented methods is reflected in the operational simplicity, mild reaction conditions, short reaction times, recycling of solvent, high purity and yield of products, absence of dangerous by-products and technological applicability at industrial scale. Considering commercial importance of the thioureas, it can be emphasized that implementation of the optimal synthesis of thiourea, based on presented methods, at industrial level of production would provide concurrent alternative to existing technologies in use. [Projekat Ministarstva nauke Republike Srbije, br. 172013

Calculation of inelastic cross sections for H+ + Cs → H(n=2) + Cs+

International Nuclear Information System (INIS)

Valance, A.; Spiess, G.

1975-01-01

The cross sections for the processes H + +Cs → H(2p and 2s) +Cs + were calculated in the center of mass energy range 250--2400 eV using a simple pseudopotential formalism for the potential curves and coupling matrix elements and a perturbed stationary state (pss) formulation for the calculation of the cross sections. The results are found to be in reasonable agreement with experiment. (auth)

Synthesis of tetraalkyl thiuram disulfides using different oxidants in recycling solvent mixture

Directory of Open Access Journals (Sweden)

Milosavljević Milutin M.

2012-01-01

Full Text Available A new optimized laboratory synthesis of tetraalkyl thiuram disulfides, starting from dialkyl amines and carbon disulfide in presence of three oxidants (hydrogen peroxide, potassium peroxodisulfate and sodium hypochlorite and appropriate reaction medium: two mixtures of isopropyl alcohol - water used in two consecutive syntheses, was presented in this work. First synthesis was performed in a recycled azeotropic mixture of isopropyl alcohol - water 87.7% - 12.3%, and second in a filtrate obtained after first synthesis, which was a mixture of isopropyl alcohol - water 70.4% - 29.6%. After the second synthesis and filtration, recycled azeotropic mixture isopropyl alcohol - water 87.7% - 12.3% was regenerated from the filtrate by rectification. Considering this, the technology for beneficial use of recycling isopropyl alcohol - water mixture as reaction medium for tetraalkyl thiuram disulfides synthesis was developed. Such concept contributes to extraordinary economical benefit of implemented optimal laboratory synthesis at semi-industrial level. High yields of tetraalkyl thiuram disulfides syntheses were obtained at both laboratory and semiindustrial level. Structure and purity of synthesized compounds were confirmed by elemental analysis, as well as FTIR, 1H and 13C NMR, and MS spectral data.

Antibodies derived from an enterotoxigenic Escherichia coli (ETEC) adhesin tip MEFA (multiepitope fusion antigen) against adherence of nine ETEC adhesins: CFA/I, CS1, CS2, CS3, CS4, CS5, CS6, CS21 and EtpA.

Science.gov (United States)

Nandre, Rahul M; Ruan, Xiaosai; Duan, Qiangde; Sack, David A; Zhang, Weiping

2016-06-30

Diarrhea continues to be a leading cause of death in children younger than 5 years in developing countries. Enterotoxigenic Escherichia coli (ETEC) is a leading bacterial cause of children's diarrhea and travelers' diarrhea. ETEC bacteria initiate diarrheal disease by attaching to host receptors at epithelial cells and colonizing in small intestine. Therefore, preventing ETEC attachment has been considered the first line of defense against ETEC diarrhea. However, developing vaccines effectively against ETEC bacterial attachment encounters challenge because ETEC strains produce over 23 immunologically heterogeneous adhesins. In this study, we applied MEFA (multiepitope fusion antigen) approach to integrate epitopes from adhesin tips or adhesive subunits of CFA/I, CS1, CS2, CS3, CS4, CS5, CS6, CS21 and EtpA adhesins and to construct an adhesin tip MEFA peptide. We then examined immunogenicity of this tip MEFA in mouse immunization, and assessed potential application of this tip MEFA for ETEC vaccine development. Data showed that mice intraperitoneally immunized with this adhesin tip MEFA developed IgG antibody responses to all nine ETEC adhesins. Moreover, ETEC and E. coli bacteria expressing these nine adhesins, after incubation with serum of the immunized mice, exhibited significant reduction in attachment to Caco-2 cells. These results indicated that anti-adhesin antibodies induced by this adhesin tip MEFA blocked adherence of the most important ETEC adhesins, suggesting this multivalent tip MEFA may be useful for developing a broadly protective anti-adhesin vaccine against ETEC diarrhea. Copyright © 2016 Elsevier Ltd. All rights reserved.

Physicochemical properties of the CsNO2-CsOH-H2O ternary system at 25 deg C

International Nuclear Information System (INIS)

Protsenko, P.I.; Medvedev, B.S.; Popova, T.B.

1977-01-01

Saturated solutions of the CsNO 2 - CsOH- H 2 O system have been studied at 25 deg C by the methods of solubility, viscosity, electric conductivity, refractometry and density. It is stated that no solid phase of a new composition is formed in the system. While adding hydroxide to the saturated solution of cesium nitride, a considerable salting-out of the latter takes place

CsPb2Br5 Single Crystals: Synthesis and Characterization

KAUST Repository

Dursun, Ibrahim

2017-08-02

CsPb2Br5 is a ternary halogen-plumbate material with close characteristics to well-reported halide perovskites. Due to its unconventional two-dimensional structure, CsPb2Br5 is being looked at broadly for potential applications in optoelectronics. CsPb2Br5 investigations are currently limited to nanostructures and powder forms of the material, which present unclear and conflicting optical properties. In this study, we present the synthesis and characterization of CsPb2Br5 bulk single crystals, which enabled us to finally clarify the material\\'s optical features. Our CsPb2Br5 crystal has a two-dimensional structure with Pb2Br5- layers spaced by Cs+ cations, and exhibits a ~3.1 eV indirect bandgap with no emission in the visible spectrum.

New crystals of the CsHSO{sub 4}–CsH{sub 2}PO{sub 4}–H{sub 2}O system

Energy Technology Data Exchange (ETDEWEB)

Makarova, I. P., E-mail: makarova@crys.ras.ru; Grebenev, V. V.; Komornikov, V. A.; Selezneva, E. V. [Russian Academy of Sciences, Shubnikov Institute of Crystallography, Federal Scientific Research Centre “Crystallography and Photonics,” (Russian Federation)

2016-11-15

Cs{sub 6}H(HSO{sub 4}){sub 3}(H{sub 2}PO{sub 4}){sub 4} crystals, grown for the first time based on an analysis of the phase diagram of the CsHSO{sub 4}–CsH{sub 2}PO{sub 4}–H{sub 2}O ternary system, have been investigated by structural analysis using synchrotron radiation. The atomic structure of the crystals is determined and its specific features are analyzed.

Protein binding of N-2-mercaptoethyl-1,3-diaminopropane via mixed disulfide formation after oral administration of WR 2721

Energy Technology Data Exchange (ETDEWEB)

Tabachnik, N.F.; Blackburn, P.; Peterson, C.M.; Cerami, A.

1982-02-01

Earlier studies have shown that WR 2721 (H2N-(CH2)3-NH(CH2)2SPO3H2) is converted to its free thiol form, N-2-mercaptoethyl-1,3-diaminopropane (MDP), at the acidic pH of the stomach. MDP is a radioprotective compound and a mucolytic agent capable of decreasing sputum viscosity in the lungs of patients with cystic fibrosis. Conversion of WR 2721 and MDP to the corresponding sulfonic acid (MDP-SO3H) permits quantitative determination of these compounds in physiological fluids by use of an automatic amino acid analyzer. After oral administration of WR 2721 to human patients and rabbits it is converted to MDP and the free thiol form of the drug associates with plasma proteins by mixed disulfide linkage. The plasma proteins serve as a depot and reservoir of MDP for potential exchange at the tissues. When incubated with whole sputum or with purified mucin solutions in vitro, MDP decreased the viscosity of these solutions by reduction of the accessible disulfide bonds of the mucin molecule and was subsequently found in mixed disulfide association with the mucin molecule. The association of MDP with proteins via mixed disulfide linkage has important implications for the development of optimal dose regimens for administration of WR 2721 to patients.

Protein binding of N-2-mercaptoethyl-1,3-diaminopropane via mixed disulfide formation after oral administration of WR 2721

International Nuclear Information System (INIS)

Tabachnik, N.F.; Blackburn, P.; Peterson, C.M.; Cerami, A.

1982-01-01

Earlier studies have shown that WR 2721 [H2N-(CH2)3-NH(CH2)2SPO3H2] is converted to its free thiol form, N-2-mercaptoethyl-1,3-diaminopropane (MDP), at the acidic pH of the stomach. MDP is a radioprotective compound and a mucolytic agent capable of decreasing sputum viscosity in the lungs of patients with cystic fibrosis. Conversion of WR 2721 and MDP to the corresponding sulfonic acid (MDP-SO3H) permits quantitative determination of these compounds in physiological fluids by use of an automatic amino acid analyzer. After oral administration of WR 2721 to human patients and rabbits it is converted to MDP and the free thiol form of the drug associates with plasma proteins by mixed disulfide linkage. The plasma proteins serve as a depot and reservoir of MDP for potential exchange at the tissues. When incubated with whole sputum or with purified mucin solutions in vitro, MDP decreased the viscosity of these solutions by reduction of the accessible disulfide bonds of the mucin molecule and was subsequently found in mixed disulfide association with the mucin molecule. The association of MDP with proteins via mixed disulfide linkage has important implications for the development of optimal dose regimens for administration of WR 2721 to patients

On thermal expansion of RbD2PO4, CsH2PO4 and CsDrPO4 crystals

International Nuclear Information System (INIS)

Vlokh, O.G.; Shchur, Ya.I.; Klymiv, I.M.

1994-01-01

Thermal expansion of RbD 2 PO 4 , CsH 2 PO 4 , CsD 2 PO 4 crystals in a wide range of temperatures embracing points of phase transitions was studied. An explanation of anomalous behaviour of thermal expansion factor along directions b and c in the course of RbD 2 PO 4 transfer into intermediate phase was suggested. 10 refs., 4 figs

Steric effects in peptide and protein exchange with activated disulfides.

Science.gov (United States)

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

2013-08-12

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

CO2·- radical induced cleavage of disulfide bonds in proteins. A gamma-ray and pulse radiolysis mechanistic investigation

International Nuclear Information System (INIS)

Favaudon, V.; Tourbez, H.; Lhoste, J-M.; Houee-Levin, C.

1990-01-01

Disulfide bond reduction by the CO 2 ·- radical was investigated in aponeocarzinostatin, aporiboflavin-binding protein, and bovine immunoglobulin. Protein-bound cysteine free thiols were formed under γ-ray irradiation in the course of a pH-dependent and protein concentration dependent chain reaction. The chain efficiency increased upon acidification of the medium, with an apparent pK a around 5, and decreased abruptly below pH 3.6. It decreased also at neutral pH as cysteine accumulated. From pulse radiolysis analysis, CO 2 ·- proved able to induce rapid one-electron oxidation of thiols and of tyrosine phenolic groups in addition to one-electron donation to exposed disulfide bonds. The bulk rate constant of CO 2 ·- uptake by the native proteins was 5- to 10-fold faster at pH 3 than at pH 8, and the protonated form of the disulfide radical anion, appeared to be the major protein radical species formed under acidic conditions. Formation of the disulfide radical cation, phenoxyl radical Tyr-O · disproportionation, and phenoxyl radical induced oxidation of preformed thiol groups should also be taken into consideration to explain the fate of the oxygen-centered phenoxyl radical

Study of Cs recovery by extraction chromatography (2)

International Nuclear Information System (INIS)

Hoshi, Harutaka; Zhang, Anyun; Uchida, Hiromi; Kuraoka, Etsushu

2005-02-01

In order to apply CalixR14 extractant to extraction chromatography for Cs separation, basic characteristics of CalixR14 adsorbent were studied. CalixR14 impregnated resin and CalixR14 + TBP impregnated resin were prepared. CalixR14 extractant showed no adsorption for Cs by liquid-liquid extraction and CalixR14 impregnated resin also showed no adsorption for Cs. Therefore, it is concluded that CalixR14 itself has no affinity for Cs. On the other hand, Cs was adsorbed onto CalixR14-TBP impregnated resin from a concentrated nitric acid solution. The distribution coefficients of Cs were more than 10 cm 3 /g from 2 to 6 M nitric acid. While Rb showed week adsorption, Na, K, Sr and La showed no adsorption and separation factor was over 100. A slight amount of CalixR14 and TBP was leaked from impregnated resin into the aqueous phase. Separation from simulated liquid waste was carried out by using a column packed with CalixR14-TBP adsorbent. Na, K, Sr and La were not adsorbed onto the column, however, Cs and Rb were adsorbed onto the column. Cs and Rb were eluted from the column by water. Cs and Rb were quantitatively recovered. (author)

Is 137Cs Dating Becoming Obsolete in North America?

Science.gov (United States)

Drexler, J. Z.; Fuller, C.; Salas, A.

2016-12-01

Dating of wetland sediments and peat is routinely carried out using 137Cs and 210Pb analysis. Unlike 210Pb, 137Cs is an anthropogenic radionuclide with a history of fallout from nuclear weapons testing. 137Cs is used as a single time marker; its peak is coincident with the height of atmospheric nuclear testing in 1963/4. During its use in the 1970s-90s, 137Cs peaks were usually highly distinct in wetland sediments (e.g., see 137Cs peaks from Louisiana marshes in Feijtel et al., 1988). This enabled its use as a check for dates assigned to a profile by 210Pb and other methods. However, recently, the efficacy of 137Cs dating in North America has deteriorated. In this presentation, we will provide specific examples of 137Cs as well as 210Pb dating in wetland sediments/peats we collected between 2005 and 2015 in Maine, California, Virginia, North Carolina, South Carolina, and Washington. Two main reasons exist for this decline. First, 137Cs activities in our recent cores are 30-40 % of the original activities in 1963/4 due to decay of the original 137Cs in situ (half-life = 30.17 years) and no major new sources. This manifests in lower signal to noise ratio, with some peaks barely recognizable above the noise. Second, 137Cs peaks are much less distinct due to 137Cs migration through time independent of substrate (or sediment) particles. Migration of peaks has resulted in estimated accretion rates being systematically lower or higher than those derived from 210Pb dating. These issues with 137Cs dating have important implications because 137Cs is used with 210Pb dating or even alone to determine rates of recent wetland carbon accumulation. Such rates are required to enter wetland restoration projects into carbon markets and to document IPCC mandated reductions in carbon pollution. Our analysis shows that, although dating by 137Cs alone has always been highly tenuous, now it is especially contraindicated and should be disallowed for the purposes of carbon accounting.

Large area synthesis, characterization, and anisotropic etching of two dimensional tungsten disulfide films

International Nuclear Information System (INIS)

Mutlu, Zafer; Ozkan, Mihrimah; Ozkan, Cengiz S.

2016-01-01

Emergent properties of tungsten disulfide at the quantum confinement limit hold promise for electronic and optoelectronic applications. Here we report on the large area synthesis of atomically thin tungsten disulfide films with strong photoluminescence properties via sulfurization of the pre-deposited tungsten films. Detailed characterization of the pre-deposited tungsten films and tungsten disulfide films are performed using microscopy and spectroscopy methods. By directly heating tungsten disulfide films in air, we have shown that the films tend to be etched into a series of triangular shaped pits with the same orientations, revealing the anisotropic etching behavior of tungsten disulfide edges. Moreover, the dimensions of the triangular pits increase with the number of layers, suggesting a thickness dependent behavior of etching in tungsten disulfide films. This method offers a promising new avenue for engineering the edge structures of tungsten disulfide films. - Highlights: • Large-scale synthesis of WS_2 films is achieved via sulfurization of W films. • Annealing of W films leads to a substantial improvement in the quality of WS_2 films. • WS_2 films show laser power dependent photoluminescence characteristics. • WS_2 films are etched with well-oriented triangular pits upon annealing in air. • Anisotropic oxidative etching is greatly affected by the thickness of WS_2 films.

Systems of Rb2I2-CdI2-PbI2 and Cs2I2-CdI2-PbI2

International Nuclear Information System (INIS)

Volchanskaya, V.V.; Il'yasov, I.I.

1979-01-01

The Rb 2 I 2 -CdI 2 -PbI 2 and Cs 2 I 2 -CdI 2 -PbI 2 triple systems have been studied, using the visual-polythermal method. The liquidus of the systems researched consists of the components and compounds crystallization fields: 2RbIxCdI 2 , 2RbIxRbI 2 , RbIxPbI 2 and 2CsIxCdI 2 , 4CsIxPbI 2 , CsIxPbI 2 , respectively. The crystallization fields converge in four non-variant points at 360, 280, 205 and 192 deg C in the Rb 2 I 2 -CdI 2 -PbI 2 system and at 375, 368, 208 and 190 deg C in the CsI 2 -CdI 2 -PbI 2 system

The TiO2 Refraction Film for CsI Scintillator

OpenAIRE

C. C. Chen; C. W. Hun; C. J. Wang; C. Y. Chen; J. S. Lin; K. J. Huang

2015-01-01

Cesium iodide (CsI) melt was injected into anodic aluminum oxide (AAO) template and was solidified to CsI column. The controllable AAO channel size (10~500 nm) can makes CsI column size from 10 to 500 nm in diameter. In order to have a shorter light irradiate from each singe CsI column top to bottom the AAO template was coated a TiO2 nano-film. The TiO2 film acts a refraction film and makes X-ray has a shorter irradiation path in the CsI crystal making a stronger the photo-electron signal. Wh...

Thiol-Disulfide Exchange between Glutaredoxin and Glutathione

DEFF Research Database (Denmark)

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

2010-01-01

Glutaredoxins are ubiquitous thiol-disulfide oxidoreductases which catalyze the reduction of glutathione-protein mixed disulfides. Belonging to the thioredoxin family, they contain a conserved active site CXXC motif. The N-proximal active site cysteine can form a mixed disulfide with glutathione ...... has been replaced with serine. The exchange reaction between the reduced protein and oxidized glutathione leading to formation of the mixed disulfide could readily be monitored by isothermal titration calorimetry (ITC) due to the enthalpic contributions from the noncovalent interactions...

Multiple ways to make disulfides

DEFF Research Database (Denmark)

Bulleid, Neil J; Ellgaard, Lars

2011-01-01

Our concept of how disulfides form in proteins entering the secretory pathway has changed dramatically in recent years. The discovery of endoplasmic reticulum (ER) oxidoreductin 1 (ERO1) was followed by the demonstration that this enzyme couples oxygen reduction to de novo formation of disulfides...

Hexa-histidin tag position influences disulfide structure but not binding behavior of in vitro folded N-terminal domain of rat corticotropin-releasing factor receptor type 2a

OpenAIRE

Klose, Jana; Wendt, Norbert; Kubald, Sybille; Krause, Eberhard; Fechner, Klaus; Beyermann, Michael; Bienert, Michael; Rudolph, Rainer; Rothemund, Sven

2004-01-01

The oxidative folding, particularly the arrangement of disulfide bonds of recombinant extracellular N-terminal domains of the corticotropin-releasing factor receptor type 2a bearing five cysteines (C2 to C6), was investigated. Depending on the position of a His-tag, two types of disulfide patterns were found. In the case of an N-terminal His-tag, the disulfide bonds C2–C3 and C4–C6 were found, leaving C5 free, whereas the C-terminal position of the His-tag led to the disulfide pattern C2–C5 a...

Environmental sciences: general. 2. Water Adsorption/Absorption by CsOH Particles

International Nuclear Information System (INIS)

Riggs, C.A.; Ghosh, T.K.; Tompson, R.V.; Loyalka, S.K.; Viswanath, D.S.

2001-01-01

Cesium hydroxide in aerosol form is likely to be a significant source of radio-cesium released during a reactor transient. Cesium hydroxide particles are hydrophilic and absorb/adsorb water rapidly. The result is a rapid growth of cesium hydroxide wetted agglomerates that can deposit on surfaces by gravitational settling. However, they can also react with iodine gas to form CsI according to Eq. (1). The rapid absorption/adsorption of water by CsOH may increase the rate of absorption of iodine by CsOH. Iodine may attach itself to adsorbed water molecules on CsOH and facilitate the reaction by bringing iodine to CsOH. Thus, the iodine removal mechanism from the pressurized water reactor containment atmosphere may change: I 2(g) + 4CsOH (s) ↔ 2CsI (s) + 2CsO (s) + 2H 2 O (l) . (1) Despite the importance of CsOH as an aerosol material released during a reactor transient, we have been unable to find any isotherm data of water on cesium hydroxide in the literature. The significant hydrophilic nature of CsOH, together with its being the strongest base currently known, present challenges to collection of water adsorption data. The objective in this research was to experimentally obtain isotherm data of water vapor on CsOH for a range of temperatures and pressures on macroscopic samples using an electro-balance. These data then may be used to predict the amount of water vapor adsorbed on CsOH at other temperatures and pressures by existing models. The adsorption apparatus using a Cahn 2000 electro-balance is shown in Fig. 1. The water adsorption/absorption data on CsOH at different relative pressures of water vapor were obtained gravimetrically. A detailed description of the experimental system is given in Hassan et al. An∼70-mg sample of CsOH.H 2 O (s) was placed onto a platinum weighing dish in the hang-down tube of the balance. The sample was regenerated by heating it at 100 deg. C under a vacuum of 3.5x10 -2 mm Hg for 24 h to remove adsorbed water and other gases

Knudsen cell mass spectrometric study of the Cs2IOH(g) molecule thermodynamics

International Nuclear Information System (INIS)

Roki, F-Z.; Ohnet, M-N.; Fillet, S.; Chatillon, C.; Nuta, I.

2013-01-01

Highlights: • The pronounced ionic character leads to only dissociative ionization processes. • Ions formed are same as those coming from pure dimmers. • De-convolution of the ions origin needs accurate thermodynamic values for the pure gas phase. • Mass spectrometric interpretation has to be performed gradually and as a function of suitable condensed compositions. • Thermal functions have to be fully estimated. -- Abstract: The gas phase of the CsI + CsOH system is analyzed by high temperature Knudsen cell mass spectrometry in order to confirm the existence of the Cs 2 IOH(g) complex molecule. The mass spectrometric analysis is quite complex since such molecules undergo dissociative ionization into fragment ions that mix with the same ions from dimers of the pure compounds in the same vapor phase. Varying the chemical conditions for vaporization by using different CsI + CsOH mixture contents showed that the ionization of the Cs 2 IOH(g) molecule led to five different fragment ions, Cs 2 OH + , Cs 2 I + , Cs + , CsOH + and CsI + . This complex ionization pattern was studied in relation with previous assessed values for the vaporization of CsOH and CsI pure compounds in which monomer and dimer molecules are predominant. The equilibrium constant for the reaction CsI(g) + CsOH(g) = Cs 2 IOH(g) was determined and, after modeling the structure of the Cs 2 IOH molecule, the enthalpy of formation was determined using the third law of thermodynamics, as follows: Δ f H°(Cs 2 IOH, g, 298.15 K) = −578 ± 14.7 kJ · mole −1

Insights into the chemistry of the Claus reaction furnace and waste heat boiler

International Nuclear Information System (INIS)

Clark, P.D.; Dowling, N.I.; Huang, M.

1997-01-01

Methods to deal with the unwanted by-product of acid-gas combustion in the Claus reaction furnace were presented. The by-product, carbon disulfide (CS 2 ), is disturbing because if it is not converted to H 2 S in the first catalytic converter, it will appear as a sulfur emission in the tail gas of plants not using reductive clean-up technology. To address this issue, Claus catalysts have been designed specifically for CS 2 hydrolysis. Studies have been conducted to determine what type of hydrocarbons lead to CS 2 formation. It was concluded that all hydrocarbons result in CS 2 production, but that benzene is particularly difficult. Data for a wide range of acid gas compositions and contaminant hydrocarbons at different process conditions was presented. Methods to destroy CS 2 in the furnace were also identified

Widespread Disulfide Bonding in Proteins from Thermophilic Archaea

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Julien Jorda

2011-01-01

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

Widespread disulfide bonding in proteins from thermophilic archaea.

Science.gov (United States)

Jorda, Julien; Yeates, Todd O

2011-01-01

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

Enthalpy-increment measurements for CsI(s) and Cs2CrO4(s) by high-temperature Calvet calorimetry

International Nuclear Information System (INIS)

Venugopal, V.; Agarwal, R.; Roy, K.N.; Prasad, R.; Sood, D.D.

1987-01-01

Molar thermodynamic properties of CsI(s) and Cs 2 Cr O 4 (s) have been evaluated by enthalpy-increment measurements, using a Calvet high-temperature calorimeter. Least squares analyses were performed on the enthalpy increment results. Data is presented in tabular form for the dependence of enthalpy increments on temperature, in the range 333 to 822 K, for both caesium compounds, along with the thermal properties of the compounds. Good agreement is found between the present data and previously reported results on reduced enthalpy increments of CsI(s) and Cs 2 CrO 4 (s). (U.K.)

CS Informativeness Governs CS-US Associability

Science.gov (United States)

Ward, Ryan D.; Gallistel, C. R.; Jensen, Greg; Richards, Vanessa L.; Fairhurst, Stephen; Balsam, Peter D

2012-01-01

In a conditioning protocol, the onset of the conditioned stimulus (CS) provides information about when to expect reinforcement (the US). There are two sources of information from the CS in a delay conditioning paradigm in which the CS-US interval is fixed. The first depends on the informativeness, the degree to which CS onset reduces the average expected time to onset of the next US. The second depends only on how precisely a subject can represent a fixed-duration interval (the temporal Weber fraction). In three experiments with mice, we tested the differential impact of these two sources of information on rate of acquisition of conditioned responding (CS-US associability). In Experiment 1, we show that associability (the inverse of trials to acquisition) increases in proportion to informativeness. In Experiment 2, we show that fixing the duration of the US-US interval or the CS-US interval or both has no effect on associability. In Experiment 3, we equated the increase in information produced by varying the C̅/T̅ ratio with the increase produced by fixing the duration of the CS-US interval. Associability increased with increased informativeness, but, as in Experiment 2, fixing the CS-US duration had no effect on associability. These results are consistent with the view that CS-US associability depends on the increased rate of reward signaled by CS onset. The results also provide further evidence that conditioned responding is temporally controlled when it emerges. PMID:22468633

All-Ambient Processed Binary CsPbBr3-CsPb2Br5 Perovskites with Synergistic Enhancement for High-Efficiency Cs-Pb-Br-Based Solar Cells.

Science.gov (United States)

Zhang, Xisheng; Jin, Zhiwen; Zhang, Jingru; Bai, Dongliang; Bian, Hui; Wang, Kang; Sun, Jie; Wang, Qian; Liu, Shengzhong Frank

2018-02-28

All-inorganic CsPbBr 3 perovskite solar cells display outstanding stability toward moisture, light soaking, and thermal stressing, demonstrating great potential in tandem solar cells and toward commercialization. Unfortunately, it is still challenging to prepare high-performance CsPbBr 3 films at moderate temperatures. Herein, a uniform, compact CsPbBr 3 film was fabricated using its quantum dot (QD)-based ink precursor. The film was then treated using thiocyanate ethyl acetate (EA) solution in all-ambient conditions to produce a superior CsPbBr 3 -CsPb 2 Br 5 composite film with a larger grain size and minimal defects. The achievement was attributed to the surface dissolution and recrystallization of the existing SCN - and EA. More specifically, the SCN - ions were first absorbed on the Pb atoms, leading to the dissolution and stripping of Cs + and Br - ions from the CsPbBr 3 QDs. On the other hand, the EA solution enhances the diffusion dynamics of surface atoms and the surfactant species. It is found that a small amount of CsPb 2 Br 5 in the composite film gives the best surface passivation, while the Br-rich surface decreases Br vacancies (V Br ) for a prolonged carrier lifetime. As a result, the fabricated device gives a higher solar cell efficiency of 6.81% with an outstanding long-term stability.

Synthesis and structural characterization of inorganic luminescent materials of Cs2NaErBr6 and Cs2NaHoBr6

International Nuclear Information System (INIS)

Poblete, V.H; Fack, G

2003-01-01

The synthesis and structural characterization is described of two luminescent materials, with technological [1] and spectroscopic [2] interest, whose crystallographic charts have not been published in the literature. The synthesis of both systems: Cs 2 NaErBr 6 and CS 2 NaHoBr 6 , was done using solid state reactions in a controlled environment. The thermal analyses DTA/TGA, applied with a temperature gradient of 10 o C/min., established crystallization ranges of 490,4 o C to 545,4 o C, for the elpasolite CS 2 NaHoBr 6 and 501 o C to 556 o C, for the structure CS 2 NaErBr 6 .. The heat vacuum treatments were carried out at 505 o C and 526 o C respectively, obtaining optimum crystallization. The structural characterization was performed with powdered X-ray diffraction (XRD). The range between 12 o and 80 o (2θ), was analyzed for 3352 points, measured steps of 0.02 o (2θ using the Rietveld profile refining program. The following crystallographic parameters were established: a 0 = 11,279(1), and 11,293(4) Angstroms, for the two structures analyzed, respectively. The relationship R exp wp in both cases is highly accurate for the 32 test lines that were analyzed. The structures present cubic closed packing Cs 1+ 3 Cl 1- , with Ho 3+ and Er 3+ atoms, filling the octahedral holes. The test data obtained will be very useful for completing the mass of experimental data needed to develop the design engineering, with specific applications for luminescent devices (au)

Probing molecules on a surface by Cs+ reactive ion scattering: identification of C2Hx (x≤4) hydrocarbons

International Nuclear Information System (INIS)

Kang, H.; Lee, C.W.; Hwang, C.H.; Kim, C.M.

2003-01-01

We studied molecular species appearing in the reactions of ethylene on a Pt(1 1 1) surface by the technique of Cs + reactive ion scattering (Cs + RIS). Dehydrogenation reaction of ethylene was examined for a surface temperature range of 100-800 K, and the RIS result verified the well-known sequence of forming di-σ-bonded ethylene (-CH 2 -CH 2 -), ethylidyne (≡C-CH 3 ), CH, and then surface carbons, as the temperature increased. In particular, the intermediate species in the conversion of ethylene to ethylidyne was closely investigated, which showed the presence of an ethylidene intermediate (≡CH-CH 3 ). In a study of H/D exchange reactions between surface C 2 D 4 and H, we successfully identified the ethylenes in which several deuterium atoms were substituted by hydrogen (C 2 D 4-x H x ,x=0-4), and quantitatively determined their relative populations. These examples demonstrate the ability of the Cs + RIS method to identify small hydrocarbons and their isotope-exchanged species on surfaces

Synthesis and crystallographic study of the compounds in the system Cs{sub 2}O - Al{sub 2}O{sub 3} - SiO{sub 2}; Synthese et etude cristallographique des composes du systeme Cs{sub 2}O - Al{sub 2}O{sub 3} - SiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

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

1969-05-01

A study has been made on the preparation, structure and thermal evolution of some definite compounds in the system: Cs{sub 2}O - Al{sub 2}O{sub 3} - SiO{sub 2}. Precise details are given about the structure of the following compounds: CsAlO{sub 2}, RbAlO{sub 2}, KAlO{sub 2} and NaAlO{sub 2}; CsAlO{sub 2}, 2 H{sub 2}O; Cs{sub 2}O, 11 Al{sub 2}O{sub 3}; Cs{sub 2}O, 2 SiO{sub 2}; Cs{sub 2}O, 4 SiO{sub 2} and Rb{sub 2}O, 4 SiO{sub 2}; CsAlSiO{sub 4}; CsAlSi{sub 2}O{sub 6}; Cs{sub 4}Ge{sub 11}O{sub 24} and Rb{sub 4}Ge{sub 11}O{sub 24}. The long term purpose of this work was to find a compound which would be insoluble, refractory and at the same time able to contain radioactive isotopes of cesium and thus suitable as radiation sources. The knowledge of the properties and structure of aluminates, silicates and aluminosilicates is a necessary stage before the elaboration of ceramic caesium sources. The compound which seems quite convenient for this use, Cs{sub 2}AlSi{sub 2}O{sub 6}, is closely related to the natural mineral 'pollucite', and offers interesting properties. (author) [French] Ce travail constitue une etude de la preparation, de la structure et de l'evolution thermique des composes definis du systeme: Cs{sub 2}O - Al{sub 2}O{sub 3} - SiO{sub 2} et de quelques homologues. Des precisions sont donnees sur la structure des composes suivants: CsAlO{sub 2}, RbAlO{sub 2}, KAlO{sub 2} et NaAlO{sub 2}; CsAlO{sub 2}, 2 H{sub 2}O; Cs{sub 2}O, 11 Al{sub 2}O{sub 3}; Cs{sub 2}O, 2 SiO{sub 2}; Cs{sub 2}O, 4 SiO{sub 2} et Rb{sub 2}O, 4 SiO{sub 2}; CsAlSiO{sub 4}; CsAlSi{sub 2}O{sub 6}; Cs{sub 4}Ge{sub 11}O{sub 24} et Rb{sub 4}Ge{sub 11}O{sub 24}. Le but a long terme de cette etude consistait a obtenir un compose a la fois refractaire et insoluble, susceptible de contenir un isotope radioactif du caesium, et d'etre utilise comme source de rayonnement. La connaissance des proprietes et de la structure des aluminates, silicates et aluminosilicates represente une etape necessaire

Physicochemical properties of the CsNO/sub 2/-CsOH-H/sub 2/O ternary system at 25/sup 0/C

Energy Technology Data Exchange (ETDEWEB)

Protsenko, P I; Medvedev, B S; Popova, T B [Rostovskii-na-Donu Gosudarstvennyj Univ. (USSR); Kalmytskij Gosudarstvennyj Univ., Ehlista (USSR))

1977-01-01

Saturated solutions of the CsNO/sub 2/ - CsOH- H/sub 2/O system have been studied at 25 deg C by the methods of solubility, viscosity, electric conductivity, refractometry and density. It is stated that no solid phase of a new composition is formed in the system. While adding hydroxide to the saturated solution of cesium nitride, a considerable salting-out of the latter takes place.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-05-10

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

Structures and related properties of helical, disulfide-stabilized peptides

Energy Technology Data Exchange (ETDEWEB)

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

1993-11-01

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

Electrostatic influence of local cysteine environments on disulfide exchange kinetics.

Science.gov (United States)

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

1981-11-10

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

The Approaching Obsolescence of 137Cs as a Means of Dating Wetland Soils and Sediments in North America

Science.gov (United States)

Drexler, J. Z.; Fuller, C.

2017-12-01

137Cesium is an anthropogenic radionuclide whose maximum fallout occurred in 1963/4 at the height of above-ground nuclear weapons testing. The presence of this fallout peak in core profiles has been used widely to estimate vertical accretion and carbon accumulation rates in wetlands. 137Cs dating has long been applied with little attention to uncertainty of peak position or measurement error. Initially, this caused few problems as activities were high and peaks were generally clear; however recently the clarity of peaks has deteriorated, raising questions of method efficacy. We quantified uncertainty in 137Cs dating in 52 wetland sediment/peat cores collected from 2005 - 2015 in Maine, California, Virginia, North Carolina, South Carolina, and Washington and compared the position of each peak to the date obtained with 210Pb. We found that the two dating methods matched within 5 years for only 20% of cores with a distinct 137Cs peak. We attribute this to a decline in 137Cs efficacy for three main reasons: (1) mobility of 137Cs resulting from diffusion independent of sediments, downwashing, and/or physical/biotic perturbation, (2) on-going decay of the original 137Cs in situ (half-life = 30.17 years), which manifests in lower signal to noise ratios, and (3) 137Cs inputs from watershed/tidal sources, which have confounded the 137Cs pattern in sediments. Such reduced efficacy is of concern because carbon accumulation rates determined with 137Cs are used for informing national-scale carbon assessments and for determining the carbon storage potential of wetlands restored as offsets for the carbon market. We conclude that 137Cs dating alone has sufficient uncertainty that it should be disallowed for carbon accounting and that any use of 137Cs should be accompanied by an uncertainty analysis of peak position. Our results suggest that soon the common practice of using 137Cs to corroborate 210Pb dating will likely be obsolete in much of North America.

Effect of minerals on accumulation of Cs by fungus Saccaromyces cerevisiae.

Science.gov (United States)

Ohnuki, Toshihiko; Sakamoto, Fuminori; Yamasaki, Shinya; Kozai, Naofumi; Shiotsu, Hiroyuki; Utsunomiya, Satoshi; Watanabe, Naoko; Kozaki, Tamotsu

2015-06-01

The accumulation of Cs by unicellular fungus of Saccharomyces cerevisiae in the presence of minerals has been studied to elucidate the role of microorganisms in the migration of radioactive Cs in the environment. Two different types of experiments were employed: experiments using stable Cs to examine the effect of a carbon source on the accumulation of Cs, and accumulation experiments of radioactive Cs from agar medium containing (137)Cs and zeolite, vermiculite, phlogopite, smectite, mica, or illite as mineral supplements. In the former type of experiments, the Cs-accumulated cells were analyzed by scanning electron microscopy equipped with energy dispersive X-ray analysis (SEM-EDS). In the latter type, the radioactivity in the yeast cells was measured by an autoradiography technique. When a carbon source was present, higher amounts of Cs accumulated in the cells than in the resting condition without a carbon source. Analyses with SEM-EDS showed that no mineral formed on the cell surface. These results indicate that the yeast cells accumulate Cs by adsorption on the cell surface and intracellular accumulation. In the presence of minerals in the agar medium, the radioactivity in the yeast cells was in the order of mica > smectite, illite > vermiculite, phlogopite, zeolite. This order is inversely correlated to the ratio of the concentration of radioactive Cs between the minerals and the medium solution. These results strongly suggest that the yeast accumulates radioactive Cs competitively with minerals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

Science.gov (United States)

Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

2016-01-01

Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

How thioredoxin dissociates its mixed disulfide.

Directory of Open Access Journals (Sweden)

Goedele Roos

2009-08-01

Full Text Available The dissociation mechanism of the thioredoxin (Trx mixed disulfide complexes is unknown and has been debated for more than twenty years. Specifically, opposing arguments for the activation of the nucleophilic cysteine as a thiolate during the dissociation of the complex have been put forward. As a key model, the complex between Trx and its endogenous substrate, arsenate reductase (ArsC, was used. In this structure, a Cys29(Trx-Cys89(ArsC intermediate disulfide is formed by the nucleophilic attack of Cys29(Trx on the exposed Cys82(ArsC-Cys89(ArsC in oxidized ArsC. With theoretical reactivity analysis, molecular dynamics simulations, and biochemical complex formation experiments with Cys-mutants, Trx mixed disulfide dissociation was studied. We observed that the conformational changes around the intermediate disulfide bring Cys32(Trx in contact with Cys29(Trx. Cys32(Trx is activated for its nucleophilic attack by hydrogen bonds, and Cys32(Trx is found to be more reactive than Cys82(ArsC. Additionally, Cys32(Trx directs its nucleophilic attack on the more susceptible Cys29(Trx and not on Cys89(ArsC. This multidisciplinary approach provides fresh insights into a universal thiol/disulfide exchange reaction mechanism that results in reduced substrate and oxidized Trx.

The two-dimensional thiophosphate CsCrP2S7

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Kyounghee Kim

2010-09-01

Full Text Available The quaternary title compound, caesium chromium(III heptathiodiphosphate(V, CsCrP2S7, has been synthesized using the reactive halide flux method. It is isotypic with other AMP2S7 (A = alkali metal; M = Cr, V or In structures and consists of two-dimensional ∞2[CrP2S7]− layers extending parallel to (001 which are separated from each other by Cs+ ions (symmetry 2. The layer is built up from slightly distorted octahedral [CrS6] units (symmetry 2 and bent [P2S7] units consisting of two corner-sharing [PS4] tetrahedra. The [CrS6] octahedra share two edges and two corners with the [PS4] tetrahedra. There are only van der Waals interactions present between the layers. The Cs+ ions are located in this van der Waals gap and stabilize the structure through weak ionic interactions. The classical charge balance of the title compound can be expressed as [Cs+][Cr3+][P5+]2[S2−]7.

The human protein disulfide isomerase gene family

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Galligan James J

2012-07-01

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

The Two Translationally Controlled Tumor Protein Genes, CsTCTP1 and CsTCTP2, Are Negative Modulators in the Cucumis sativus Defense Response to Sphaerotheca fuliginea

Directory of Open Access Journals (Sweden)

Xiangnan Meng

2018-04-01

Full Text Available Pathogen stress often significantly decreases cucumber production. However, knowledge regarding the molecular mechanism and signals of cucumber disease resistance is far from complete. Here, we report two translationally controlled tumor protein genes, CsTCTP1 and CsTCTP2, that are both negative modulators in the Cucumis sativus defense response to Sphaerotheca fuliginea. Subcellular localization analysis showed that CsTCTP1 and CsTCTP2 were both localized in the cytoplasm. Expression analysis indicated that the transcript levels of CsTCTP1 and CsTCTP2 were linked to the degree of cucumber resistance to S. fuliginea. Transient overexpression of either CsTCTP1 or CsTCTP2 in cucumber cotyledons impaired resistance to S. fuliginea, whereas silencing of either CsTCTP1 or CsTCTP2 enhanced cucumber resistance to S. fuliginea. The relationship of several defense-related genes and ABA and target of rapamycin (TOR signaling pathway-related genes to the overexpressing and silencing of CsTCTP1/CsTCTP2 in non-infested cucumber plants was investigated. The results indicated that CsTCTP1 participates in the defense response to S. fuliginea by regulating the expression of certain defense-associated genes and/or ABA signaling pathway-associated genes, and CsTCTP2 participates through regulating the expression of TOR signaling pathway-associated genes. Our findings will guide enhancing the resistance of cucumber to powdery mildew.

Precipitation behaviors of Cs and Re(/Tc) by NaTPB and TPPCl from a simulated fission products-(Na2CO3-NaHCO3)-H2O2 solution

International Nuclear Information System (INIS)

Lee, Eil Hee; Lim, Jae Gwan; Chung, Dong Yong; Yang, Han Beum; Kim, Kwang Wook

2010-01-01

In this study, the removal of Cs and Tc from a simulated fission products (FP) solution which were co-dissolved with U during the oxidative-dissolution of spent fuel in a mixed carbonate solution of (Na 2 CO 3 -NaHCO 3 )-H 2 O 2 was investigated by using a selective precipitation method. As Cs and Tc might cause an unstable behavior due to the high decay heat emission of Cs as well as the fast migration of Tc when disposed of underground, it is one of the important issues to removal them in views of the increase of disposal safety. The precipitation of Cs and Re (as a surrogate for Tc) was examined by introducing sodium tetraphenylborate (NaTPB) and tetraphenylphosponium chloride (TPPCl), respectively. Precipitation of Cs by NaTPB and that of Re by TPPCl were completed within 5 minutes. Their precipitation rates were not influenced so much by the temperature and stirring speed even if they were increased by up to 50 .deg. C and 1,000 rpm. However, the pH of the solution was found to have a great influence on the precipitation with NaTPB and TPPCl. Since Mo tends to co-precipitate with Re at a lower pH, especially, it was effective that a selective precipitation of Re by TPPCl was carried out at pH of above 9 without co-precipitation of Mo and Re. Over 99% of Cs was precipitated when the ratio of [NaTPB]/[Cs]>1 and more than 99% of Re, likewise, was precipitated when the ratio of [TPPCl]/[Re]>1.

Characterization of aromatic organosulfur model compounds relevant to fossil fuels by using atmospheric pressure chemical ionization with CS2 and high-resolution tandem mass spectrometry.

Science.gov (United States)

Tang, Weijuan; Sheng, Huaming; Jin, Chunfen; Riedeman, James S; Kenttämaa, Hilkka I

2016-04-15

The chemistry of desulfurization involved in processing crude oil is greatly dependent on the forms of sulfur in the oil. Sulfur exists in different chemical bonding environments in fossil fuels, including those in thiophenes and benzothiophenes, thiols, sulfides, and disulfides. In this study, the fragmentation behavior of the molecular ions of 17 aromatic organosulfur compounds with various functionalities was systematically investigated by using high-resolution tandem mass spectrometry. Multiple-stage tandem mass spectrometric experiments were carried out using a linear quadrupole ion trap (LQIT) equipped with an atmospheric pressure chemical ionization (APCI) source. (+)APCI/CS2 was used to generate stable dominant molecular ions for all the compounds studied except for three sulfides that also showed abundant fragment ions. The LQIT coupled with an orbitrap mass spectrometer was used for elemental composition analysis, which facilitated the identification of the neutral molecules lost during fragmentation. The characteristic fragment ions generated in MS(2) and MS(3) experiments provide clues for the chemical bonding environment of sulfur atoms in the examined compounds. Upon collision-induced dissociation (CID), the molecular ions can lose the sulfur atom in a variety of ways, including as S (32 Da), HS(•) (33 Da), H2 S (34 Da), CS (44 Da), (•) CHS (45 Da) and CH2 S (46 Da). These neutral fragments are not only indicative of the presence of sulfur, but also of the type of sulfur present in the compound. Generally, losses of HS(•) and H2 S were found to be associated with compounds containing saturated sulfur functionalities, while losses of S, CS and (•) CHS were more common for heteroaromatic sulfur compounds. High-resolution tandem mass spectrometry with APCI/CS2 ionization is a viable approach to determining the types of organosulfur compounds. It can potentially be applied to analysis of complex mixtures, which is beneficial to improving the

137Cs tracing dynamics of soil erosion, organic carbon and nitrogen in sloping farmland converted from original grassland in Tibetan plateau

International Nuclear Information System (INIS)

Nie Xiaojun; Wang Xiaodan; Liu Suzhen; Gu Shixian; Liu Haijun

2010-01-01

There is a shortage of research concerning the relationships between land-use change, soil erosion, and soil organic carbon (SOC) and nitrogen (N) dynamics in alpine environments such as those found in the Tibetan plateau. In this paper, typical sloping farmlands converted from grassland 50 years ago in eastern Tibet were selected to determine dynamics of soil erosion, SOC, and total N associated with land-use change. Soil samples were collected from sloping farmland and control fields (grassland). The 137 Cs, SOC, total N contents, and soil particle size fractions were analyzed in these samples. As compared with the control fields, 137 Cs, SOC, and total N inventories in the sloping farmlands decreased by 30%, 27%, and 33%, respectively. Meanwhile variations in the three parameters were enhanced in the sloping farmlands, with coefficients of variation (CVs) of 38%, 23%, and 20%, respectively, for 37 Cs, SOC, and total N. In addition, SOC and total N inventories significantly decreased with increasing soil erosion in the sloping farmland. In a sloping farmland with a steep 24 o gradient, the 137 Cs inventory gradually increased along a downslope transect with its lowest value at 0 Bq m -2 in the top-slope position (0 m). The soil clay ( 137 Cs and clay (r=0.92, p=0.003), SOC (r=0.96, p=0.001), or total N (r=0.95, p=0.001) were also found in the farmland. These results showed that converting alpine grassland to sloping farmland accelerates soil erosion, losses in SOC and N, and increases the soil's spatial variability. The combined impacts of tillage and water erosion contributed a significant decrease in the soil's organic carbon and N storages. Particularly in steep sloping farmlands, tillage erosion contributed for severe soil loss, but the soil redistribution pattern was dominated by water erosion, not tillage erosion, due to the lack of boundaries across the field patches. It was also found that 137 Cs, SOC, and total N moved along the same pathway within these

Ammonothermal synthesis and characterization of Cs{sub 2}[Zn(NH{sub 2}){sub 4}

Energy Technology Data Exchange (ETDEWEB)

Richter, Theresia M.M.; Niewa, Rainer [Institut fuer Anorganische Chemie, Universitaet Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart (Germany); Alt, Nicolas S.A.; Schluecker, Eberhard [Lehrstuhl fuer Prozessmaschinen und Anlagentechnik, Friedrich-Alexander-Universitaet Erlangen-Nuernberg, Cauerstrasse 4, 91058, Erlangen (Germany)

2016-10-15

Cs{sub 2}[Zn(NH{sub 2}){sub 4}] was synthesized under ammonothermal conditions (sc-NH{sub 3}, 523 K, 155 MPa) from CsNH{sub 2} and Zn. Growth of cm-sized crystals succeeded upon application of a temperature gradient. The crystal structure is based on the motif of a hexagonal closed packing of [Zn(NH{sub 2}){sub 4}]{sup 2-} ions with occurrence of no significant hydrogen bridges according to distances and vibrational spectroscopy. Cs{sup +} ions are located within octahedral and tetrahedral holes of the packing. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

Science.gov (United States)

Langford, Troy F; Deen, William M; Sikes, Hadley D

2018-03-22

Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

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

Science.gov (United States)

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

2008-09-01

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

High Temperature NMR Studies of the Glass-Crystal Transition in the Cs2S2O7-V2O5 System

DEFF Research Database (Denmark)

Lapina, Olga B.; Terskikh, Viktor V.; Shubin, Aleksander A.

1997-01-01

133Cs and 51V NMR spectra have been recorded of Cs2S2O7 and the catalytically important Cs2S2O7-V2O5 mixtures in the temperature range 20 - 550 C. A high mobility of Cs+ in the solid Cs2S2O7 was observed. The transformation from glassy state to crystalline state was investigated for the compositi...

Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa; Engelhard, Mark H.; Polzin, Bryant; Wang, Chong M.; Zhang, Jiguang; Xu, Wu

2016-02-10

Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.

Selective removal of Cs and Re by precipitation in a Na2CO3-H2O2 solution

International Nuclear Information System (INIS)

Eil-Hee Lee; Jae-Gwan Lim; Dong-Yong Chung; Han-Beom Yang; Kwang-Wook Kim

2010-01-01

The removal of Cs and Re (as a surrogate for Tc) by selective precipitation from the simulated fission products which were co-dissolved with uranium during the oxidative dissolution of spent fuel in a Na 2 CO 3 -H 2 O 2 solution was investigated in this study. The precipitations of Cs and Re were examined by introducing sodium tetraphenylborate (NaTPB) and tetraphenylohosponium chloride (TPPCl), respectively. The precipitation of Cs by NaTPB and that of Re by TPPCl each took place within 5 min, and an increase in temperature up to 50 deg C and a stirring speed up to 1000 rpm hardly affected their precipitation rates. The most important factor in the precipitation with NaTPB and TPPCl was found to be a pH of the solution after precipitation. Since Mo tends to co-precipitate with Cs or Re at a lower pH, an effective precipitation with NaTPB and TPPCl was done at pH of above 9 without the co-precipitation of Mo. More than 99% of Cs and Re were precipitated when the initial concentration ratio of NaTPB to Cs was above 1 and when that of TPPCl to Re was above 1. The precipitation of Cs and Re was never affected by the concentration of Na 2 CO 3 and H 2 O 2 , even though they were raised up to 1.5 and 1.0 M, respectively. Precipitation yields of Cs and Re in a Na 2 CO 3 -H 2 O 2 solution were found to be dependent on the concentration ratios of [NaTBP]/[Cs] and [TPPCl]/[Re]. (author)

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

DEFF Research Database (Denmark)

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

2006-01-01

reduction/rearrangement of non-native disulfides is poorly understood. We analyzed the role of individual PDI domains in disulfide bond formation in a reaction driven by their natural oxidant, Ero1p. We found that Ero1p oxidizes the isolated PDI catalytic thioredoxin domains, A and A' at the same rate......Native disulfide bond formation in eukaryotes is dependent on protein-disulfide isomerase (PDI) and its homologs, which contain varying combinations of catalytically active and inactive thioredoxin domains. However, the specific contribution of PDI to the formation of new disulfides versus...... catalytic (A) domain. The specific order of thioredoxin domains in PDI is important in establishing the asymmetry in the rate of oxidation of the two active sites thus allowing A and A', two thioredoxin domains that are similar in sequence and structure, to serve opposing functional roles as a disulfide...

Effect of He pressure on the superconducting transition temperatures of Na2CsC60 and (NH3)4Na2CsC60

International Nuclear Information System (INIS)

Schirber, J.E.; Bayless, W.R.; Rosseinsky, M.J.; Zhou, O.; Fleming, R.M.; Murphy, D.; Fischer, J.E.

1994-01-01

The Na based mixed alkali doped C 60 superconductors show anomalous behavior with respect to the ''universal'' superconducting transition temperature T c vs lattice constant a 0 relation followed by most of the fcc A 3 C 60 superconductors. We have measured dt c /dP for Na 2 CsC 60 and (NH 3 ) 4 Na 2 CsC 60 using solid He as the pressure medium to ∼ 6 kbar finding dT c /dP equal to -0.8±(0.01) K/kbar and -1.0(±0.1)K/kbar for Na 2 CsC 60 and Na 2 (NH 3 ) 4 C 60 respectively. Our value for Na 2 CsC 60 differs markedly from that obtained by Mizuki et al of about -1.3 K/kbar. However, using N 2 or Ar, we obtain values for dT c /dP in substantial agreement with Mizuki et al who used fluorinert to generate their pressure. This work emphasizes the need for compressibility measurements with the same pressure medium in the appropriate temperature range so that meaningful comparisons can be made between various pressure measurements and models which are based on lattic spacing

CsPb2Br5 Single Crystals: Synthesis and Characterization

KAUST Repository

Dursun, Ibrahim; de Bastiani, Michele; Turedi, Bekir; Alamer, Badriah Jaber; Shkurenko, Aleksander; Yin, Jun; Gereige, Issam; Alsaggaf, Ahmed; Mohammed, Omar F.; Eddaoudi, Mohamed; Bakr, Osman

2017-01-01

, which enabled us to finally clarify the material's optical features. Our CsPb2Br5 crystal has a two-dimensional structure with Pb2Br5- layers spaced by Cs+ cations, and exhibits a ~3.1 eV indirect bandgap with no emission in the visible spectrum.

Dynamic combinatorial chemistry with diselenides and disulfides in water

DEFF Research Database (Denmark)

Rasmussen, Brian; Sørensen, Anne; Gotfredsen, Henrik

2014-01-01

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

One step gold (bio)functionalisation based on CS{sub 2}-amine reaction

Energy Technology Data Exchange (ETDEWEB)

Almeida, Ines [Centro de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Ed. C8, Campo Grande, 1749-016 Lisboa (Portugal); Cascalheira, Antonio C. [Lumisense, Lda, Campus Faculdade de Ciencias da Universidade de Lisboa, Ed. ICAT, Campo Grande, 1749-016 Lisboa (Portugal); Viana, Ana S., E-mail: anaviana@fc.ul.p [Centro de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Ed. C8, Campo Grande, 1749-016 Lisboa (Portugal)

2010-12-01

Dithiocarbamates have been regarded as alternative anchor groups to thiols on gold surfaces, and claimed to be formed in situ through the reaction between secondary amines and carbon disulphide. In this paper, we further exploit this methodology for a convenient one step biomolecule immobilisation onto gold surfaces. First, the reactivity between CS{sub 2} and electroactive compounds containing amines, primary (dopamine), secondary (epinephrine), and an amino acid (tryptophan) has been investigated by electrochemical methods. Cyclic voltammetric characterisation of the modified electrodes confirmed the immobilisation of all the target compounds, allowing the estimation of their surface concentration. The best result was obtained with epinephrine, a secondary amine, for which a typical quasi-reversible behaviour of surface confined electroactive species could be clearly depicted. Electrochemical reductive desorption studies enabled to infer on the extent of the reaction and on the relative stability of the generated monolayers. Bio-functionalisation studies have been accomplished through the reaction of CS{sub 2} with glucose oxidase in aqueous medium, and the catalytic activity of the immobilised enzyme was evaluated towards glucose, by electrochemical methods in the presence of a redox mediator. Scanning tunnelling microscopy (STM) and Atomic force microscopy (AFM) were used respectively, to characterize the gold electrodes and Glucose Oxidase coverage and distribution on the modified surfaces.

Determination of disulfide bridges of two spider toxins: hainantoxin-III and hainantoxin-IV

Directory of Open Access Journals (Sweden)

W Wang

2009-01-01

Full Text Available Peptide toxins are usually highly bridged proteins with multipairs of intrachain disulfide bonds. Analysis of disulfide connectivity is an important facet of protein structure determination. In this paper, we successfully assigned the disulfide linkage of two novel peptide toxins, called HNTX-III and HNTX-IV, isolated from the venom of Ornithoctonus hainana spider. Both peptides are useful inhibitors of TTX-sensitive voltage-gated sodium channels and are composed of six cysteine residues that form three disulfide bonds, respectively. Firstly, the peptides were partially reduced by tris(2-carboxyethyl-phosphine (TCEP in 0.1 M citrate buffer containing 6 M guanidine-HCl at 40° C for ten minutes. Subsequently, the partially reduced intermediates containing free thiols were separated by reversed-phase high-performance liquid chromatography (RP-HPLC and alkylated by rapid carboxamidomethylation. Then, the disulfide bonds of the intermediates were analyzed by Edman degradation. By using the strategy above, disulfide linkages of HNTX-III and HNTX-IV were determined as I-IV, II-V and III-VI pattern. In addition, this study also showed that this method may have a great potential for determining the disulfide bonds of spider peptide toxins.

Conformational analysis by quantitative NOE measurements of the β-proton pairs across individual disulfide bonds in proteins

International Nuclear Information System (INIS)

Takeda, Mitsuhiro; Terauchi, Tsutomu; Kainosho, Masatsune

2012-01-01

NOEs between the β-protons of cysteine residues across disulfide bonds in proteins provide direct information on the connectivities and conformations of these important cross-links, which are otherwise difficult to investigate. With conventional [U- 13 C, 15 N]-proteins, however, fast spin diffusion processes mediated by strong dipolar interactions between geminal β-protons prohibit the quantitative measurements and thus the analyses of long-range NOEs across disulfide bonds. We describe a robust approach for alleviating such difficulties, by using proteins selectively labeled with an equimolar mixture of (2R, 3S)-[β- 13 C; α,β- 2 H 2 ] Cys and (2R, 3R)-[β- 13 C; α,β- 2 H 2 ] Cys, but otherwise fully deuterated. Since either one of the prochiral methylene protons, namely β2 (proS) or β3 (proR), is always replaced with a deuteron and no other protons remain in proteins prepared by this labeling scheme, all four of the expected NOEs for the β-protons across disulfide bonds could be measured without any spin diffusion interference, even with long mixing times. Therefore, the NOEs for the β2 and β3 pairs across each of the disulfide bonds could be observed at high sensitivity, even though they are 25% of the theoretical maximum for each pair. With the NOE information, the disulfide bond connectivities can be unambiguously established for proteins with multiple disulfide bonds. In addition, the conformations around disulfide bonds, namely χ 2 and χ 3 , can be determined based on the precise proton distances of the four β-proton pairs, by quantitative measurements of the NOEs across the disulfide bonds. The feasibility of this method is demonstrated for bovine pancreatic trypsin inhibitor, which has three disulfide bonds.

Synthesis and structural characterization of luminescent inorganic materials of the type CS2NaErBr6 and CS2NaHoBr6

International Nuclear Information System (INIS)

Poblete, V.H.; Fack, G.

2001-01-01

The synthesis and structural characterization is described of two luminescent materials, with technological [1] and spectroscopic [2] interest, whose crystallographic charts have not been published in the literature. The synthesis of both systems: Cs 2 NaErBr 6 and CS 2 NaHoBr 6 , was done using solid state reactions in a controlled environment. The thermal analyses DTA/TGA, applied with a temperature gradient of 10 o C/min., established crystallization ranges of 490,4 o C to 545,4 o C, for the elpasolite CS 2 NaHoBr 6 and 501 o C to 556 o C, for the structure CS 2 NaErBr 6 .. The heat vacuum treatments were carried out at 505 o C and 526 o C respectively, obtaining optimum crystallization. The structural characterization was performed with powdered X-ray diffraction (XRD). The range between 12 o and 80 o (2θ), was analyzed for 3352 points, measured steps of 0.02 o (2θ using the Rietveld profile refining program. The following crystallographic parameters were established: a 0 = 11,279(1), and 11,293(4) Angstroms, for the two structures analyzed, respectively. The relationship R exp wp in both cases is highly accurate for the 32 test lines that were analyzed. The structures present cubic closed packing Cs 1+ 3 Cl 1- , with Ho 3+ and Er 3+ atoms, filling the octahedral holes. The test data obtained will be very useful for completing the mass of experimental data needed to develop the design engineering, with specific applications for luminescent devices

Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

International Nuclear Information System (INIS)

Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T.; Kefalidis, Christos E.; Maron, Laurent; Tuna, Floriana; McInnes, Eric J.L.; Lewis, William

2017-01-01

The reactivity of terminal uranium(V/VI) nitrides with CE 2 (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren TIPS )(N)][K(B15C5) 2 ] (1, Tren TIPS =N(CH 2 CH 2 NSiiPr 3 ) 3 ; B15C5=benzo-15-crown-5) reacts with CO 2 to give [U(Tren TIPS )(O)(NCO)][K(B15C5) 2 ] (3), whereas the uranium(VI) nitride [U(Tren TIPS )(N)] (2) reacts with CO 2 to give isolable [U(Tren TIPS )(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren TIPS )(O)] (5) with concomitant formation of N 2 and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS 2 to give [U(Tren TIPS )(κ 2 -CS 3 )][K(B15C5) 2 ] (6), 2, and [K(B15C5) 2 ][NCS] (7), whereas 2 reacts with CS 2 to give [U(Tren TIPS )(NCS)] (8) and ''S'', with the latter trapped as Ph 3 PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE 2 follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS 2 as a reactivity surrogate for CO 2 . (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

DEFF Research Database (Denmark)

Maeda, Kenji; Hägglund, Per; Finnie, Christine

2006-01-01

Thioredoxin is ubiquitous and regulates various target proteins through disulfide bond reduction. We report the structure of thioredoxin (HvTrxh2 from barley) in a reaction intermediate complex with a protein substrate, barley alpha-amylase/subtilisin inhibitor (BASI). The crystal structure...... of this mixed disulfide shows a conserved hydrophobic motif in thioredoxin interacting with a sequence of residues from BASI through van der Waals contacts and backbone-backbone hydrogen bonds. The observed structural complementarity suggests that the recognition of features around protein disulfides plays...... a major role in the specificity and protein disulfide reductase activity of thioredoxin. This novel insight into the function of thioredoxin constitutes a basis for comprehensive understanding of its biological role. Moreover, comparison with structurally related proteins shows that thioredoxin shares...

Soft Computing Methods for Disulfide Connectivity Prediction.

Science.gov (United States)

Márquez-Chamorro, Alfonso E; Aguilar-Ruiz, Jesús S

2015-01-01

The problem of protein structure prediction (PSP) is one of the main challenges in structural bioinformatics. To tackle this problem, PSP can be divided into several subproblems. One of these subproblems is the prediction of disulfide bonds. The disulfide connectivity prediction problem consists in identifying which nonadjacent cysteines would be cross-linked from all possible candidates. Determining the disulfide bond connectivity between the cysteines of a protein is desirable as a previous step of the 3D PSP, as the protein conformational search space is highly reduced. The most representative soft computing approaches for the disulfide bonds connectivity prediction problem of the last decade are summarized in this paper. Certain aspects, such as the different methodologies based on soft computing approaches (artificial neural network or support vector machine) or features of the algorithms, are used for the classification of these methods.

The synthesis of unsymmetric disulfides for use as radio-protectives

International Nuclear Information System (INIS)

Chang, S.H.H.

1988-01-01

Unsymmetric disulfides with radioprotective potential were synthesized by linking biomolecules, and related substances, to known radio-protective aminothiols via a disulfide bond. The biomolecules used in this research include mercaptoalcohols, mercaptopyridines and mercaptophenothiazines. Unsymmetric disulfides were synthesized by reacting two thiols with diethyl azodicarboxylate sequentially at low temperature. The reactions of thiols with thiosulfinate were studied as an alternative for synthesizing disulfides. A cross-linked polystyrene was thiolated by different reagents. The thiolation of polymers is part of a methodological study using solid phase synthesis to synthesize unsymmetric disulfides

Liquid hydrogen production via hydrogen sulfide methane reformation

Science.gov (United States)

Huang, Cunping; T-Raissi, Ali

Hydrogen sulfide (H 2S) methane (CH 4) reformation (H 2SMR) (2H 2S + CH 4 = CS 2 + 4H 2) is a potentially viable process for the removal of H 2S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H 2SMR produces carbon disulfide (CS 2), a liquid under ambient temperature and pressure-a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H 2SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH 4 to H 2S ratios are needed. In this paper, we analyze H 2SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H 2SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively.

A single disulfide bond disruption in the β3 integrin subunit promotes thiol/disulfide exchange, a molecular dynamics study.

Directory of Open Access Journals (Sweden)

Lihie Levin

Full Text Available The integrins are a family of membrane receptors that attach a cell to its surrounding and play a crucial function in cell signaling. The combination of internal and external stimuli alters a folded non-active state of these proteins to an extended active configuration. The β3 subunit of the platelet αIIbβ3 integrin is made of well-structured domains rich in disulfide bonds. During the activation process some of the disulfides are re-shuffled by a mechanism requiring partial reduction of some of these bonds; any disruption in this mechanism can lead to inherent blood clotting diseases. In the present study we employed Molecular Dynamics simulations for tracing the sequence of structural fluctuations initiated by a single cysteine mutation in the β3 subunit of the receptor. These simulations showed that in-silico protein mutants exhibit major conformational deformations leading to possible disulfide exchange reactions. We suggest that any mutation that prevents Cys560 from reacting with one of the Cys(567-Cys(581 bonded pair, thus disrupting its ability to participate in a disulfide exchange reaction, will damage the activation mechanism of the integrin. This suggestion is in full agreement with previously published experiments. Furthermore, we suggest that rearrangement of disulfide bonds could be a part of a natural cascade of thiol/disulfide exchange reactions in the αIIbβ3 integrin, which are essential for the native activation process.

Electrical behaviour of heterobimetallic [MM'(EtCS2)4] (MM'=NiPd, NiPt, PdPt) and MM'X-chain polymers [PtM(EtCS2)4I] (M=Ni, Pd).

Science.gov (United States)

Givaja, Gonzalo; Castillo, Oscar; Mateo, Eva; Gallego, Almudena; Gómez-García, Carlos J; Calzolari, Arrigo; di Felice, Rosa; Zamora, Félix

2012-11-26

Herein, we report the isolation of new heterobimetallic complexes [Ni(0.6)Pd(1.4)(EtCS(2))(4)] (1), [NiPt(EtCS(2))(4)] (2) and [Pd(0.4)Pt(1.6)(EtCS(2))(4)] (3), which were constructed by using transmetallation procedures. Subsequent oxidation with iodine furnished the MM'X monodimensional chains [Ni(0.6)Pt(1.4)(EtCS(2))(4)I] (4) and [Ni(0.1)Pd(0.3)Pt(1.6)(EtCS(2))(4)I] (5). The physical properties of these systems were investigated and the chain structures 4 and 5 were found to be reminiscent of the parent [Pt(2)(EtCS(2))(4)I] species. However, they were more sensitively dependent on the localised nature of the charge on the Ni ion, which caused spontaneous breaking of the conduction bands. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All-Inorganic Perovskite CsPb2Br5 Microsheets for Photodetector Application

Directory of Open Access Journals (Sweden)

Xiaosheng Tang

2018-01-01

Full Text Available Lead-halide perovskites have emerged as one kind of important optoelectronic materials with excellent performance in photovoltaic and light-emitting diode applications. Herein, we reported all-inorganic perovskite CsPb2Br5 microsheets prepared by a facile injection method. Through the X-ray diffraction (XRD and Scanning Electron Microscope (SEM, it could be seen that the CsPb2Br5 microsheets showed single tetragonal crystalline phase and kept uniform square shape. Moreover, the as-synthesized CsPb2Br5 microsheets exhibited photoluminescence emission at 513 nm, and the UV–vis absorption spectrum further indicated the band gap of CsPb2Br5 microsheets was ≈2.50 eV. Additionally, the as-fabricated CsPb2Br5 microsheets based photodetector exhibited faster photoresponse characteristics of short rise time (0.71 s and decay time (0.60 s, which demonstrated its promising application as high performance electronic and optoelectronic devices.

Widespread Disulfide Bonding in Proteins from Thermophilic Archaea

OpenAIRE

Jorda, Julien; Yeates, Todd O.

2011-01-01

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

Effect of minerals on accumulation of Cs by fungus Saccaromyces cerevisiae

International Nuclear Information System (INIS)

Ohnuki, Toshihiko; Sakamoto, Fuminori; Yamasaki, Shinya; Kozai, Naofumi; Shiotsu, Hiroyuki; Utsunomiya, Satoshi; Watanabe, Naoko; Kozaki, Tamotsu

2015-01-01

The accumulation of Cs by unicellular fungus of Saccharomyces cerevisiae in the presence of minerals has been studied to elucidate the role of microorganisms in the migration of radioactive Cs in the environment. Two different types of experiments were employed: experiments using stable Cs to examine the effect of a carbon source on the accumulation of Cs, and accumulation experiments of radioactive Cs from agar medium containing 137 Cs and zeolite, vermiculite, phlogopite, smectite, mica, or illite as mineral supplements. In the former type of experiments, the Cs-accumulated cells were analyzed by scanning electron microscopy equipped with energy dispersive X-ray analysis (SEM-EDS). In the latter type, the radioactivity in the yeast cells was measured by an autoradiography technique. When a carbon source was present, higher amounts of Cs accumulated in the cells than in the resting condition without a carbon source. Analyses with SEM-EDS showed that no mineral formed on the cell surface. These results indicate that the yeast cells accumulate Cs by adsorption on the cell surface and intracellular accumulation. In the presence of minerals in the agar medium, the radioactivity in the yeast cells was in the order of mica > smectite, illite >> vermiculite, phlogopite, zeolite. This order is inversely correlated to the ratio of the concentration of radioactive Cs between the minerals and the medium solution. These results strongly suggest that the yeast accumulates radioactive Cs competitively with minerals. - Graphical abstract: Autoradiography analysis showed that presence of larger amounts of mineral of vermiculite collected in South Africa induced less accumulation of radioactive Cs in yeast cells from the medium. - Highlights: • Effect of minerals on the accumulation of radioactive Cs by yeast was studied. • Presence of minerals reduced accumulation of radioactive Cs by yeast. • The order of reduction is mica>smectite, illite>>vermiculite, phlogopite

A novel reduced graphene oxide/molybdenum disulfide/polyaniline nanocomposite-based electrochemical aptasensor for detection of aflatoxin B1.

Science.gov (United States)

Geleta, Girma Selale; Zhao, Zhen; Wang, Zhenxin

2018-03-26

In this study, we developed a novel reduced graphene oxide/molybdenum disulfide/polyaniline@gold nanoparticles-based electrochemical aptasensor (termed as RGO/MoS2/PANI@AuNPs/Apt) for detection of aflatoxin B1 (AFB1). The RGO/MoS2/PANI nanocomposites were synthesized and characterized by multiple techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (FTIR), UV-visible spectroscopy, and X-ray photoelectron spectroscopy (XPS). A glassy carbon electrode (GCE) was then modified by the RGO/MoS2/PANI nanocomposites, coated with a chitosan (Cs) film, and followed by AuNPs attachment for immobilizing the AFB1 aptamers. In the presence of AFB1, the AFB1 binding-induced conformation change of the immobilized aptamer on the electrode surface results in the reduction of the electron transfer from a [Fe(CN)6]3-/4- redox couple in the solution to the GCE surface. Therefore, the aptamer-AFB1 binding event can be easily monitored by the peak current change of the RGO/MoS2/PANI@AuNPs/Apt through differential pulse voltammetry (DPV) measurement. Under the optimized conditions, the as-developed RGO/MoS2/PANI@AuNPs/Apt exhibits a wide linear range from 0.01 fg mL-1 to 1.0 fg mL-1 and a remarkably low detection limit (3σ) of 0.002 fg mL-1. The aptasensor also has good reproducibility as well as shows high selectivity against other fungal toxins, such as OTA and FB1. Moreover, the practicability of the RGO/MoS2/PANI@AuNPs/Apt was demonstrated by the analysis of AFB1 in the spiked wine samples.

Alpha-gamma pulse shape discrimination in CsI:Tl, CsI:Na and BaF sub 2 scintillators

CERN Document Server

Dinca, L E; Haas, J; Bom, V R; Eijk, C W E

2002-01-01

Some scintillating materials offer the possibility of measuring well separated alpha and gamma scintillation response using a single crystal. Eventually aiming at thermal neutron detection using sup 6 Li or sup 1 sup 0 B admixture, pulse shape discrimination measurements were made on three scintillators: CsI:Tl, CsI:Na and pure BaF sub 2 crystals. A very good alpha/gamma discrimination was obtained using sup 2 sup 2 Na, sup 2 sup 4 sup 1 Am (gamma) and sup 2 sup 4 sup 4 Cm (alpha) radioactive sources.

An investigation of the thermal conductivity of Cs2MoO4

International Nuclear Information System (INIS)

Ishii, T.; Mizuno, T.

1997-01-01

The thermal diffusivity of 82.6% TD and 89.3% TD Cs 2 MoO 4 was measured by the laser flash method and the thermal conductivity was calculated. The thermal conductivity of these Cs 2 MoO 4 ranged from 0.3 to 0.5 W m -1 K -1 . The density dependence of the thermal conductivity was correlated based on the experimental values of these two densities and on the 94.3% TD specimen from the preceding study. The correlation of the thermal conductivity of Cs 2 MoO 4 is k=(1.0-1.848 x P)/(1.0-1.848 x P ref ) x k ref , where k ref =132.56/T+0.03+3.2 x 10 -10 x T 3 , P ref =1.0-0.943=0.057 and k and k ref are the thermal conductivities (Wm -1 K -1 ) of Cs 2 MoO 4 with the porosities P and P ref , respectively, where P ref is the porosity for the 94.3% TD Cs 2 MoO 4 . T is the temperature (K). This correlation is applicable for 82.6 to 94.3% TD Cs 2 MoO 4 from 873 to 1023 K. (orig.)

Integrated basic treatment of activated carbon for enhanced CO{sub 2} selectivity

Energy Technology Data Exchange (ETDEWEB)

Adelodun, Adedeji Adebukola; Jo, Young-Min, E-mail: ymjo@khu.ac.kr

2013-12-01

We attempted the use of three chemical agents viz nitric acid (HN), calcium nitrate (CaN) and calcium ethanoate (CaEt) to achieve enhanced CO{sub 2} selective adsorption by activated carbon (AC). In dry phase treatment, microporous coconut shell-based carbon (CS) exhibits higher CO{sub 2} capacity than coal-based. However, upon wet-phase pre-treatment, modified CS samples showed lesser CO{sub 2} adsorption efficiency. Surface characterization with X-ray photoelectron spectroscopy confirms the presence of calcium and amine species on the samples with integrated treatment (A-CaN). These samples recorded the highest low-level CO{sub 2} capture despite calcinated CaEt-doped samples (C-CaEt) showing the highest value for pure and high level CO{sub 2} adsorption capacities. The slope and linearity values of isobaric desorption were used to estimate the proportion of CO{sub 2} chemisorbed and heterogeneity of the adsorbents’ surfaces respectively. Consequently, integrated basic impregnation provides the most efficient adsorbents for selective adsorption of both indoor and outdoor CO{sub 2} levels.

Kinetic and Thermodynamic Aspects of Cellular Thiol-Disulfide Redox Regulation

DEFF Research Database (Denmark)

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

2009-01-01

. In the cytosol regulatory disulfide bonds are typically formed in spite of the prevailing reducing conditions and may thereby function as redox switches. Such disulfide bonds are protected from enzymatic reduction by kinetic barriers and are thus allowed to exist long enough to elicit the signal. Factors......Regulation of intracellular thiol-disulfide redox status is an essential part of cellular homeostasis. This involves the regulation of both oxidative and reductive pathways, production of oxidant scavengers and, importantly, the ability of cells to respond to changes in the redox environment...... that affect the rate of thiol-disulfide exchange and stability of disulfide bonds are discussed within the framework of the underlying chemical foundations. This includes the effect of thiol acidity (pKa), the local electrostatic environment, molecular strain and entropy. Even though a thiol-disulfide...

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

International Nuclear Information System (INIS)

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

2012-01-01

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

Absorption spectra and Faraday effect in Cs2NaNdCl6 and Cs2NaPrCl6 crystals

International Nuclear Information System (INIS)

Ehdel'man, I.S.; Galanov, E.K.; Kokov, I.T.; Malakhovskij, A.V.; Anistratov, A.T.

1985-01-01

The paper is devoted to studying absorption spectra and the Faraday effect in Cs 2 NaNdCl 6 and Cs 2 NaPrCl 6 crystals. The absorption spectra and Faraday effect were measured at room temperature in the range of 9000-30000 cmsup(-1) (0.33-1.2 μm) in 0-10 kOe magnetic fields. The absorption spectra produced contain several groups of intense absorption bands resulted from intraconfiguration electron transitions in rare-earth cations. The Faraday spectra in the whole range studied for both crystals have the form of smoothly dipping curves when increasing wavelength. The form of these curves testifies to prevailing contribution of strong electron transitions lying in a nearer UV region to the Faraday effect

Kinetic analysis of the mechanism and specificity of protein-disulfide isomerase using fluorescence-quenched peptides

DEFF Research Database (Denmark)

Westphal, V; Spetzler, J C; Meldal, M

1998-01-01

Protein-disulfide isomerase (PDI) is an abundant folding catalyst in the endoplasmic reticulum of eukaryotic cells. PDI introduces disulfide bonds into newly synthesized proteins and catalyzes disulfide bond isomerizations. We have synthesized a library of disulfide-linked fluorescence......-quenched peptides, individually linked to resin beads, for two purposes: 1) to probe PDI specificity, and 2) to identify simple, sensitive peptide substrates of PDI. Using this library, beads that became rapidly fluorescent by reduction by human PDI were selected. Amino acid sequencing of the bead-linked peptides...

Structural and thermodynamic study of dicesium molybdate Cs2Mo2O7: Implications for fast neutron reactors

Science.gov (United States)

Smith, A. L.; Kauric, G.; van Eijck, L.; Goubitz, K.; Wallez, G.; Griveau, J.-C.; Colineau, E.; Clavier, N.; Konings, R. J. M.

2017-09-01

The structure of α-Cs2Mo2O7 (monoclinic in space group P21 / c), which can form during irradiation in fast breeder reactors in the space between nuclear fuel and cladding, has been refined in this work at room temperature from neutron diffraction data. Furthermore, the compounds' thermal expansion and polymorphism have been investigated using high temperature X-ray diffraction combined with high temperature Raman spectroscopy. A phase transition has been observed at Ttr(α → β)=(621.9±0.8) K using Differential Scanning Calorimetry, and the structure of the β-Cs2Mo2O7 phase, orthorhombic in space group Pbcm, has been solved ab initio from the high temperature X-ray diffraction data. Furthermore, the low temperature heat capacity of α-Cs2Mo2O7 has been measured in the temperature range T=(1.9-313.2) K using a Quantum Design PPMS (Physical Property Measurement System) calorimeter. The heat capacity and entropy values at T=298.15 K have been derived as Cp,mo (Cs2Mo2O7 , cr , 298.15 K) = (211.9 ± 2.1) J K-1mol-1 and Smo (Cs2Mo2O7 , cr , 298.15 K) = (317.4 ± 4.3) J K-1mol-1 . When combined with the enthalpy of formation reported in the literature, these data yield standard entropy and Gibbs energy of formation as Δf Smo (Cs2Mo2O7 , cr , 298.15 K) = - (628.2 ± 4.4) J K-1mol-1 and Δf Gmo (Cs2Mo2O7 , cr , 298.15 K) = - (2115.1 ± 2.5) kJmol-1 . Finally, the cesium partial pressure expected in the gap between fuel and cladding following the disproportionation reaction 2Cs2MoO4=Cs2Mo2O7+2Cs(g)+ 1/2 O2(g) has been calculated from the newly determined thermodynamic functions.

Superacid univalent metal phosphites (MH2PO3)2·H3PO3 (M Rb, Tl+) and MH2PO3·H3PO3 (M = K, Cs): synthesis and structure

International Nuclear Information System (INIS)

Kosterina, E.V.; Troyanov, S.I.; Aslanov, L.A.; Kemnits, Eh.

2001-01-01

Crystal superacid phosphites α-CsH 2 PO 3 ·H 3 PO 3 (1) and β-CsH 2 PO 3 ·H 3 PO 3 (2) were prepared by means of interaction between cesium carbonate and phosphoric acid excess. The structure of the compounds, i.e.: 1-rhombic crystal system, sp.gr. P2 1 2 1 2 1 , a = 6.033 (1), b = 6.444 (1), c = 18.345 (4) A: 2-monoclinic crystal system, sp.gr. C2/c, a = 9.990 (3), b = 12.197 (4), c = 6.866 (2) A, β = 118.14 (3) deg, was determined by the method of X-ray diffraction analysis of monocrystals at 150 K. Comparative analysis of the crystal structure and hydrogen bond systems in acid phosphites of different composition was conducted [ru

Lattice dynamics of cubic Cs2NaLnX6 and CsNaLn1-xLn'xX6 elpasolites

International Nuclear Information System (INIS)

Acevedo, R.; Poblete, V.; Alzamora, R.; Venegas, R.; Navarro, G.; Henriquez, C.

1999-01-01

Crystal lattice dynamics of stoichiometric Cs 2 NaLnX 6 and nonstoichiometric CsNaLn 1-x Ln' x X 6 , 0.01 ≤ x ≤ 0.10, Ln and Ln' are trivalent positive lanthanide ions and X is chlorine or bromine, were studied.. Phonon dispersion relations were computed for similar compound, Cs 2 UBr 6 , and vibronic absorption spectra with reduced number of required input parameters are considered on the basis of proposed model. (author)

The effects of morphology re-arrangements on the pseudocapacitive properties of mesoporous molybdenum disulfide (MoS2) nanoflakes

CSIR Research Space (South Africa)

Khawula, TNY

2016-07-01

Full Text Available Mesoporous molybdenum disulfide (MoS(sub2)) with different morphologies have been prepared via hydrothermal method using different solvents, water or water/acetone mixture. The MoS(sub2) obtained with water alone gave a graphene-like nanoflakes (g...

The high temperature synthesis of CsAlSiO 4-ANA, a new polymorph in the system Cs 2OAl 2O 3SiO 2. I. The end member of ANA type of zeolite framework

Science.gov (United States)

Dimitrijevic, R.; Dondur, V.; Petranovic, N.

1991-12-01

High temperature phase transformations of Cs + exchanged zeolites were investigated. Above 1000°C, CsX, CsY (FAU), and Cs, ZK-4 (LTA) frameworks recrystallized in a pollucite phase. A Cs + loaded mordenite recrystallized at 1300°C in the orthorhombic CsAlSi 5O 12 phase. A Cs + exchanged zeolite A at 960°C recrystallized in a mixture of two polymorphic CsAlSiO 4 phases having different (Al,Si)O 4 frameworks. The unstable orthorhombic CsAlSiO 4ABW phase has a topotactic transition at 1150°C into an ordered low CsAlSiO 4-ANA framework. Further calcination produces, at 1200°C, transformation of the low CsAlSiO 4-ANA phase to the more stable high CsAlSiO 4-ANA polymorph having cubic ( a 0 = 13.6595 (5) Å) symmetry and an ordered SiAl distribution. The crystal structure of high CsAlSiO 4ANA, a new polymorph in the system Cs 2OAl 2O 3SiO 2, was determined using X-ray Rietveld analyses and 29Si MAS NMR spectroscopy.

Growth and characterization of tin disulfide (SnS2) thin film deposited by successive ionic layer adsorption and reaction (SILAR) technique

International Nuclear Information System (INIS)

Deshpande, N.G.; Sagade, A.A.; Gudage, Y.G.; Lokhande, C.D.; Sharma, Ramphal

2007-01-01

Thin films of tin disulfide (SnS 2 ) have been deposited by using low cost successive ionic layer adsorption and reaction (SILAR) technique. The deposition parameters such as SILAR cycles (60), immersion time (20 s), rinsing time (10 s) and deposition temperature (27 o C) were optimized to obtain good quality of films. Physical investigations were made to study the structural, optical and electrical properties. X-ray diffraction (XRD) patterns reveal that the deposited SnS 2 thin films have hexagonal crystal structure. Energy dispersive X-ray analysis (EDAX) indicated elemental ratio close to those for tin disulfide (SnS (2.02) ). Uniform deposition of the material over the entire glass substrate was revealed by scanning electron microscopy (SEM). Atomic force microscopy (AFM) showed the film is uniform and the substrate surface is well covered with small spherical grains merged in each other. A direct band gap of 2.22 eV was obtained. Photoluminescence (PL) showed two strong peaks corresponding to green and red emission. Ag/SnS 2 junction showed Schottky diode like I-V characteristics. The barrier height calculated was 0.22 eV. Thermoelectric power (TEP) properties showed that tin disulfide exhibits n-type conductivity

Shape and phase evolution from CsPbBr3 perovskite nanocubes to tetragonal CsPb2Br5 nanosheets with an indirect bandgap.

Science.gov (United States)

Li, Guopeng; Wang, Hui; Zhu, Zhifeng; Chang, Yajing; Zhang, Ting; Song, Zihang; Jiang, Yang

2016-09-13

Tetragonal CsPb 2 Br 5 nanosheets were obtained by an oriented attachment of orthorhombic CsPbBr 3 nanocubes, involving a lateral shape evolution from octagonal to square. Meanwhile, the experimental results, together with DFT simulation results, indicated that the tetragonal CsPb 2 Br 5 is an indirect bandgap semiconductor that is PL-inactive with a bandgap of 2.979 eV.

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

Directory of Open Access Journals (Sweden)

O. A. Gromova

2017-01-01

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

Room temperature humidity sensor based on polyaniline-tungsten disulfide composite

Science.gov (United States)

Manjunatha, S.; Chethan, B.; Ravikiran, Y. T.; Machappa, T.

2018-05-01

Polyaniline-tungsten disulfide (PANI-WS2) composite was synthesized using in situ polymerization technique by adding finely grinded powder of WS2 during the polymerization of aniline. Field emission scanning electron microscopy (FESEM) images showed the granular morphology with porous nature. Energy dispersive X-ray spectroscopy (EDX) confirmed the presence of carbon, nitrogen, chlorine of PANI, tungsten and sulfur elements of WS2. Humidity sensing property of the composite was investigated by plotting change in its resistance with different relative humidity environments ranging from 10 to 97% RH. Decrease in resistance of the composite was observed with increase in relative humidity. Maximum sensing response of the composite was found to be 88.46%. Response and recovery times of the composite at 97%RH were fair enough to fabricate a sensor based on it. Stability of the composite with respect to the humidity sensing behavior was observed to be unchanged even after two months.

Impaired Thiol-Disulfide Balance in Acute Brucellosis.

Science.gov (United States)

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

2017-05-24

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

Infrared Spectroscopy of Two Isomers of the OCS-CS_{2} Complex

Science.gov (United States)

Oliaee, J. N.; Dehghany, M.; Afshari, Mahin; Moazzen-Ahmadi, N.; McKellar, A. R. W.

2009-06-01

A second isomer of OCS-CS_{2} complex, with a nonplanar cross-shaped structure, has been studied for the first time by analysing an infrared band in the region of the OCS stretching vibration (2062 cm^{-1}). This isomer has C_{s} symmetry and the observed band consists of purely c-type rotational transitions. The ground state rotational parameters are found to be A=0.07306 cm^{-1}, B=0.03325 cm^{-1} and C=0.02879 cm^{-1}, in good agreement with a previous semi-empirical calculation. In addition, a hybrid band with a- and b-type rotational transitions has been assigned to be due to the known planar form of OCS-CS_{2}, as previously studied by microwave spectroscopy. The spectra were recorded using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. Calculations indicate that the planar isomer of OCS-CS_{2} is the lowest in energy, in contrast to CO_{2}-CS_{2} where the crossed form is believed to be the lowest. J. J. Newby, M. M. Serafin, R. A. Peebles and S. A. Peebles, Phys. Chem. Chem. Phys. 7, 487 (2005). C. C. Dutton, D. A. Dows, R. Eikey, S. Evans and R. A. Beaudet, J. Phys. Chem. A 102, 6904 (1998).

Terminal uranium(V/VI) nitride activation of carbon dioxide and carbon disulfide. Factors governing diverse and well-defined cleavage and redox reactions

Energy Technology Data Exchange (ETDEWEB)

Cleaves, Peter A.; Gardner, Benedict M.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Kefalidis, Christos E.; Maron, Laurent [LPCNO, CNRS and INSA, Universite Paul Sabatier, Toulouse (France); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom); Lewis, William [School of Chemistry, The University of Nottingham (United Kingdom)

2017-02-24

The reactivity of terminal uranium(V/VI) nitrides with CE{sub 2} (E=O, S) is presented. Well-defined C=E cleavage followed by zero-, one-, and two-electron redox events is observed. The uranium(V) nitride [U(Tren{sup TIPS})(N)][K(B15C5){sub 2}] (1, Tren{sup TIPS}=N(CH{sub 2}CH{sub 2}NSiiPr{sub 3}){sub 3}; B15C5=benzo-15-crown-5) reacts with CO{sub 2} to give [U(Tren{sup TIPS})(O)(NCO)][K(B15C5){sub 2}] (3), whereas the uranium(VI) nitride [U(Tren{sup TIPS})(N)] (2) reacts with CO{sub 2} to give isolable [U(Tren{sup TIPS})(O)(NCO)] (4); complex 4 rapidly decomposes to known [U(Tren{sup TIPS})(O)] (5) with concomitant formation of N{sub 2} and CO proposed, with the latter trapped as a vanadocene adduct. In contrast, 1 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(κ{sup 2}-CS{sub 3})][K(B15C5){sub 2}] (6), 2, and [K(B15C5){sub 2}][NCS] (7), whereas 2 reacts with CS{sub 2} to give [U(Tren{sup TIPS})(NCS)] (8) and ''S'', with the latter trapped as Ph{sub 3}PS. Calculated reaction profiles reveal outer-sphere reactivity for uranium(V) but inner-sphere mechanisms for uranium(VI); despite the wide divergence of products the initial activation of CE{sub 2} follows mechanistically related pathways, providing insight into the factors of uranium oxidation state, chalcogen, and NCE groups that govern the subsequent divergent redox reactions that include common one-electron reactions and a less-common two-electron redox event. Caution, we suggest, is warranted when utilising CS{sub 2} as a reactivity surrogate for CO{sub 2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Elastic properties of Cs{sub 2}HgBr{sub 4} and Cs{sub 2}CdBr{sub 4} crystals

Energy Technology Data Exchange (ETDEWEB)

Kityk, A.V.; Zadorozhna, A.V.; Shchur, Y.I.; Martynyuk-Lototska, Y.I.; Burak, Y.; Vlokh, O.G. [Institute of Physical Optics, Lvov (Ukraine)

1998-12-31

Using ultrasonic velocity measurements, all components of the elastic constant matrix C{sub ij} , elastic compliances matrix S{sub ij}, and linear compressibility constants matrix K{sub ij} of orthorhombic Cs{sub 2}HgBr{sub 4} and Cs{sub 2}CdBr{sub 4} crystals have been determined over a wide temperature range, including the region of the phase transition from the normal to the incommensurate phase. Results obtained are considered within the framework of the phenomenological theory. Preliminary analysis of the acoustical properties at room temperature clearly indicates that both crystals are relatively important materials for acousto-optical applications. Copyright (1998) CSIRO Australia 16 refs., 1 tab. 8 figs. The URL for the electronic version of this article is http://www.publish.csiro.au/journals/ajp/electronic.html

Water-resistant, monodispersed and stably luminescent CsPbBr3/CsPb2Br5 core-shell-like structure lead halide perovskite nanocrystals

Science.gov (United States)

Qiao, Bo; Song, Pengjie; Cao, Jingyue; Zhao, Suling; Shen, Zhaohui; Gao, Di; Liang, Zhiqin; Xu, Zheng; Song, Dandan; Xu, Xurong

2017-11-01

Lead halide perovskite materials are thriving in optoelectronic applications due to their excellent properties, while their instability due to the fact that they are easily hydrolyzed is still a bottleneck for their potential application. In this work, water-resistant, monodispersed and stably luminescent cesium lead bromine perovskite nanocrystals coated with CsPb2Br5 were obtained using a modified non-stoichiometric solution-phase method. CsPb2Br5 2D layers were coated on the surface of CsPbBr3 nanocrystals and formed a core-shell-like structure in the synthetic processes. The stability of the luminescence of the CsPbBr3 nanocrystals in water and ethanol atmosphere was greatly enhanced by the photoluminescence-inactive CsPb2Br5 coating with a wide bandgap. The water-stable enhanced nanocrystals are suitable for long-term stable optoelectronic applications in the atmosphere.

Cs2SeO4-UO2SeO4-H2O system at 25 deg C

International Nuclear Information System (INIS)

Serezhkina, L.B.; Serezhkin, V.N.

1987-01-01

Using the method of isothermal solubility at 25 deg C the interaction of cesium and uranyl selenates in aqueous solution is studied. Formation of congruently soluble Cs 2 UO 2 (SeO 4 ) 2 x2H 2 O and Cs 2 (UO 2 ) 2 x(SeO 4 ) 3 is ascertained, their crystallographic characteristics being determined

Mineral capacity of peat soils organic matter and entry of Cs137 into perennial grasses

International Nuclear Information System (INIS)

Tsybulko, N.N.; Shapsheeva, T.P.; Arastovich, T.V.; Zajtsev, A.A.

2010-01-01

The results of the study of peat soils organic substance structure with various peat ash content are given. Contents of active organic substance and carbon of microbial biomass in peat and boggy soil with 20% peat ash content is 3.0-3.5 and 1.6-1.8 times higher correspondingly, than thus in peaty-gley soil with 70% peat ash content. At peat and boggy soil with low peat ash content Cs137 transition into hay is minimal. 14 times higher than at peaty-gley soil with 70% peat ash content. Application of fertilizers at peat and boggy soil reduces Cs137 transition factor 4.7-6.4 times if compared to peaty-gley soil (2.1-4.7 times). Close positive interconnection between Cs137 transition factors from soil into the plants and organic carbon soil contents, absolute contents of potentially mineralized carbon and mineralization degree

On the photostability of the disulfide bond

DEFF Research Database (Denmark)

Stephansen, Anne Boutrup; Larsen, Martin Alex Bjørn; Klein, Liv Bærenholdt

2014-01-01

Photostability is an essential property of molecular building blocks of nature. Disulfides are central in the structure determination of proteins, which is in striking contradiction to the result that the S-S bond is a photochemically labile structural entity that cleaves to form free radicals upon...... on a sub 50 fs timescale without further ado. In a cyclic motif resembling the cysteine-disulfide bond in proteins, light can perturb the S-S bond to generate short-lived diradicaloid species, but the sulfur atoms are conformationally restricted by the ring that prevents the sulfur atoms from flying apart...... the photostability of disulfide-bonds must be ascribed a cyclic structural arrangement....

Selective disulfide reduction for labeling and enhancement of Fab antibody fragments

International Nuclear Information System (INIS)

Kirley, Terence L.; Greis, Kenneth D.; Norman, Andrew B.

2016-01-01

Many methods have been developed for chemical labeling and enhancement of the properties of antibodies and their common fragments, including the Fab and F(ab’) 2 fragments. Somewhat selective reduction of some antibody disulfide bonds has been previously achieved, yielding antibodies and antibody fragments that can be labeled at defined sites, enhancing their utility and properties. Selective reduction of the two hinge disulfide bonds present in F(ab’) 2 fragments using mild reduction has been useful. However, such reduction is often not quantitative and results in the reduction of multiple disulfide bonds, and therefore subsequent multiple labeling or conjugation sites are neither homogenous nor stoichiometric. Here, a simple and efficient selective reduction of the single disulfide bond linking the partial heavy chain and the intact light chain which compose the Fab fragment is accomplished utilizing tris(2-carboxyethyl)phosphine (TCEP) immobilized on agarose beads. The resultant reduced cysteine residues were labeled with several cysteine-selective fluorescent reagents, as well as by cysteine-directed PEGylation. These two cysteine residues can also be re-ligated by means of a bifunctional cysteine cross-linking agent, dibromobimane, thereby both restoring a covalent linkage between the heavy and light chains at this site, far removed from the antigen binding site, and also introducing a fluorescent probe. There are many other research and clinical uses for these selectively partially reduced Fab fragments, including biotinylation, toxin and drug conjugation, and incorporation of radioisotopes, and this technique enables simple generation of very useful Fab fragment derivatives with many potential applications. - Highlights: • TCEP agarose is effective for selective reduction of a single Fab disulfide bond. • This disulfide is solvent accessible and distant from the antigen binding site. • A variety of buffers of varying pHs can be used, simplifying

Cytoplasmic glutathione redox status determines survival upon exposure to the thiol-oxidant 4,4'-dipyridyl disulfide

DEFF Research Database (Denmark)

López-Mirabal, H Reynaldo; Thorsen, Michael; Kielland-Brandt, Morten C

2007-01-01

Dipyridyl disulfide (DPS) is a highly reactive thiol oxidant that functions as electron acceptor in thiol-disulfide exchange reactions. DPS is very toxic to yeasts, impairing growth at low micromolar concentrations. The genes TRX2 (thioredoxin), SOD1 (superoxide dismutase), GSH1 (gamma-glutamyl-c......Dipyridyl disulfide (DPS) is a highly reactive thiol oxidant that functions as electron acceptor in thiol-disulfide exchange reactions. DPS is very toxic to yeasts, impairing growth at low micromolar concentrations. The genes TRX2 (thioredoxin), SOD1 (superoxide dismutase), GSH1 (gamma...... antioxidant pools of glutathione (GSH) and thioredoxin are required for resistance to DPS. We found that DPS-sensitive mutants display increases in the disulfide form of GSH (GSSG) during DPS exposure that roughly correlate with their more oxidizing GSH redox potential in the cytosol and their degree of DPS...

Atomic force microscopy studies on molybdenum disulfide flakes as sodium-ion anodes.

Science.gov (United States)

Lacey, Steven D; Wan, Jiayu; von Wald Cresce, Arthur; Russell, Selena M; Dai, Jiaqi; Bao, Wenzhong; Xu, Kang; Hu, Liangbing

2015-02-11

A microscale battery comprised of mechanically exfoliated molybdenum disulfide (MoS2) flakes with copper connections and a sodium metal reference was created and investigated as an intercalation model using in situ atomic force microscopy in a dry room environment. While an ethylene carbonate-based electrolyte with a low vapor pressure allowed topographical observations in an open cell configuration, the planar microbattery was used to conduct in situ measurements to understand the structural changes and the concomitant solid electrolyte interphase (SEI) formation at the nanoscale. Topographical observations demonstrated permanent wrinkling behavior of MoS2 electrodes upon sodiation at 0.4 V. SEI formation occurred quickly on both flake edges and planes at voltages before sodium intercalation. Force spectroscopy measurements provided quantitative data on the SEI thickness for MoS2 electrodes in sodium-ion batteries for the first time.

Electron Dynamics in the Core-Excited CS 2 Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy

OpenAIRE

Marchenko , T; Carniato , S; Journel , L; Guillemin , R; Kawerk , E; Žitnik , M; Kavčič , M; Bučar , K; Bohinc , R; Petric , M; Vaz Da Cruz , V; Gel 'mukhanov , F; Simon , Marielle

2015-01-01

International audience; We present an experimental and theoretical study of resonant inelastic x-ray scattering (RIXS) in the carbon disulphide CS 2 molecule near the sulfur K-absorption edge. We observe a strong evolution of the RIXS spectral profile with the excitation energy tuned below the lowest unoccupied molecular orbital (LUMO) absorption resonance. The reason for this is twofold. Reducing the photon energy in the vicinity of the LUMO absorption resonance leads to a relative suppressi...

In vitro controlled release of cisplatin from gold-carbon nanobottles via cleavable linkages

Directory of Open Access Journals (Sweden)

Li J

2015-12-01

Full Text Available Jian Li,1 Sia Lee Yoong,2 Wei Jiang Goh,2 Bertrand Czarny,1 Zhi Yang,1 Kingshuk Poddar,2,3 Michal M Dykas,2,3 Abhijeet Patra,2,3 T Venkatesan,2,3 Tomasz Panczyk,4 Chengkuo Lee,5 Giorgia Pastorin1–3 1Department of Pharmacy, National University of Singapore, 2NUS Graduate School for Integrative Sciences and Engineering, Centre for Life Sciences (CeLS, 3NUSNNI-NanoCore, National University of Singapore, Singapore; 4Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Cracow, Poland; 5Department of Electrical and Computer Engineering, National University of Singapore, Singapore Abstract: Carbon nanotubes’ (CNTs hollow interior space has been explored for biomedical applications, such as drug repository against undesirable inactivation. To further devise CNTs as smart material for controlled release of cargo molecules, we propose the concept of “gold-carbon nanobottles”. After encapsulating cis-diammineplatinum(II dichloride (cisplatin, CDDP in CNTs, we covalently attached gold nanoparticles (AuNPs at the open-tips of CNTs via different cleavable linkages, namely hydrazine, ester, and disulfide-containing linkages. Compared with our previous study in which more than 80% of CDDP leaked from CNTs in 2 hours, AuNPs were found to significantly decrease such spontaneous release to <40%. In addition, CDDP release from AuNP-capped CNTs via disulfide linkage was selectively enhanced by twofolds in reducing conditions (namely with 1 mM dithiothreitol [DTT], which mimic the intracellular environment. We treated human colon adenocarcinoma cells HCT116 with our CDDP-loaded gold-carbon nanobottles and examined the cell viability using lactate dehydrogenase assay. Interestingly, we found that our nanobottles with cleavable disulfide linkage exerted stronger cytotoxic effect in HCT116 compared with normal human fetal lung fibroblast cells IMR-90. Therefore, we infer that our nanobottles strategy with inbuilt disulfide linkage could

Regulation of interleukin-4 signaling by extracellular reduction of intramolecular disulfides

International Nuclear Information System (INIS)

Curbo, Sophie; Gaudin, Raphael; Carlsten, Mattias; Malmberg, Karl-Johan; Troye-Blomberg, Marita; Ahlborg, Niklas; Karlsson, Anna; Johansson, Magnus; Lundberg, Mathias

2009-01-01

Interleukin-4 (IL-4) contains three structurally important intramolecular disulfides that are required for the bioactivity of the cytokine. We show that the cell surface of HeLa cells and endotoxin-activated monocytes can reduce IL-4 intramolecular disulfides in the extracellular space and inhibit binding of IL-4 to the IL-4Rα receptor. IL-4 disulfides were in vitro reduced by thioredoxin 1 (Trx1) and protein disulfide isomerase (PDI). Reduction of IL-4 disulfides by the cell surface of HeLa cells was inhibited by auranofin, an inhibitor of thioredoxin reductase that is an electron donor to both Trx1 and PDI. Both Trx1 and PDI have been shown to be located at the cell surface and our data suggests that these enzymes are involved in catalyzing reduction of IL-4 disulfides. The pro-drug N-acetylcysteine (NAC) that promotes T-helper type 1 responses was also shown to mediate the reduction of IL-4 disulfides. Our data provides evidence for a novel redox dependent pathway for regulation of cytokine activity by extracellular reduction of intramolecular disulfides at the cell surface by members of the thioredoxin enzyme family.

Facile synthesis and characterization of CsPbBr3 and CsPb2Br5 ...

Indian Academy of Sciences (India)

2018-03-23

Mar 23, 2018 ... All-inorganic caesium lead-halide perovskite CsPbBr3 and ... optoelectronic materials owing to their stabilities and highly efficient photoluminescence (PL). ... chemical tenability [2], hybrid organic–inorganic lead halide-.

{sup 137}Cs tracing dynamics of soil erosion, organic carbon and nitrogen in sloping farmland converted from original grassland in Tibetan plateau

Energy Technology Data Exchange (ETDEWEB)

Nie Xiaojun, E-mail: niexj2005@126.co [School of Surveying and Land Information Engineering, Henan Polytechnic University, Jiaozuo 454000 (China); Wang Xiaodan; Liu Suzhen; Gu Shixian [Institute of Mountain Hazards and Environment, Chinese Academy of Sciences and Ministry of Water Conservation, Chengdu 610041 (China); Liu Haijun [Institute of Water Resources Planning, Surveying, Design, and Research, Lhasa 850000 (China)

2010-09-15

There is a shortage of research concerning the relationships between land-use change, soil erosion, and soil organic carbon (SOC) and nitrogen (N) dynamics in alpine environments such as those found in the Tibetan plateau. In this paper, typical sloping farmlands converted from grassland 50 years ago in eastern Tibet were selected to determine dynamics of soil erosion, SOC, and total N associated with land-use change. Soil samples were collected from sloping farmland and control fields (grassland). The {sup 137}Cs, SOC, total N contents, and soil particle size fractions were analyzed in these samples. As compared with the control fields, {sup 137}Cs, SOC, and total N inventories in the sloping farmlands decreased by 30%, 27%, and 33%, respectively. Meanwhile variations in the three parameters were enhanced in the sloping farmlands, with coefficients of variation (CVs) of 38%, 23%, and 20%, respectively, for {sup 37}Cs, SOC, and total N. In addition, SOC and total N inventories significantly decreased with increasing soil erosion in the sloping farmland. In a sloping farmland with a steep 24{sup o} gradient, the {sup 137}Cs inventory gradually increased along a downslope transect with its lowest value at 0 Bq m{sup -2} in the top-slope position (0 m). The soil clay (<0.002 mm) content in such an area increased with decreasing elevation (r=-0.95, p=0.001). Significant correlations between {sup 137}Cs and clay (r=0.92, p=0.003), SOC (r=0.96, p=0.001), or total N (r=0.95, p=0.001) were also found in the farmland. These results showed that converting alpine grassland to sloping farmland accelerates soil erosion, losses in SOC and N, and increases the soil's spatial variability. The combined impacts of tillage and water erosion contributed a significant decrease in the soil's organic carbon and N storages. Particularly in steep sloping farmlands, tillage erosion contributed for severe soil loss, but the soil redistribution pattern was dominated by water erosion

Sulfur-doped graphene via thermal exfoliation of graphite oxide in H2S, SO2, or CS2 gas.

Science.gov (United States)

Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

2013-06-25

Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

Gasoline from natural gas by sulfur processing

Energy Technology Data Exchange (ETDEWEB)

Erekson, E.J.; Miao, F.Q. [Institute of Gas Technology, Des Plaines, IL (United States)

1995-12-31

The overall objective of this research project is to develop a catalytic process to convert natural gas to liquid transportation fuels. The process, called the HSM (Hydrogen Sulfide-Methane) Process, consists of two steps that each utilize a catalyst and sulfur-containing intermediates: (1) converting natural gas to CS{sub 2} and (2) converting CS{sub 2} to gasoline range liquids. Catalysts have been found that convert methane to carbon disulfide in yields up to 98%. This exceeds the target of 40% yields for the first step. The best rate for CS{sub 2} formation was 132 g CS{sub 2}/kg-cat-h. The best rate for hydrogen production is 220 L H{sub 2} /kg-cat-h. A preliminary economic study shows that in a refinery application hydrogen made by the HSM technology would cost $0.25-R1.00/1000 SCF. Experimental data will be generated to facilitate evaluation of the overall commercial viability of the process.

The Cs2SO4-Ce2(SO4)3-H2SO4-H2O system at 150 and 200 deg C

International Nuclear Information System (INIS)

Bondar', S.A.; Belokoskov, V.I.; Trofimov, G.V.

1982-01-01

Solubility in the system Cs 2 SO 4 -Ce 2 (SO 4 ) 3 -H 2 SO 4 -H 2 O using the isothermal method at 150 and 200 deg C at molar ratios Cs 2 SO 4 :Ce 2 (SO 4 ) 3 =1:5 and conditions of sulfate crystallization Cs 2 SO 4 xCe 2 (SO 4 ) 3 , Ce 2 (SO 4 ) 3 x0.5H 2 SO 4 xnH 2 O (n=2-3) and Ce 2 (SO 4 ) 3 x3H 2 SO 4 are determined. Double sulfate Cs 2 SO 4 xCe 2 (SO 4 ) 3 is studied using the methods of crystallooptical, thermal, X-ray phase analyses and IR spectroscopy

Recent mass spectrometry-based techniques and considerations for disulfide bond characterization in proteins.

Science.gov (United States)

Lakbub, Jude C; Shipman, Joshua T; Desaire, Heather

2018-04-01

Disulfide bonds are important structural moieties of proteins: they ensure proper folding, provide stability, and ensure proper function. With the increasing use of proteins for biotherapeutics, particularly monoclonal antibodies, which are highly disulfide bonded, it is now important to confirm the correct disulfide bond connectivity and to verify the presence, or absence, of disulfide bond variants in the protein therapeutics. These studies help to ensure safety and efficacy. Hence, disulfide bonds are among the critical quality attributes of proteins that have to be monitored closely during the development of biotherapeutics. However, disulfide bond analysis is challenging because of the complexity of the biomolecules. Mass spectrometry (MS) has been the go-to analytical tool for the characterization of such complex biomolecules, and several methods have been reported to meet the challenging task of mapping disulfide bonds in proteins. In this review, we describe the relevant, recent MS-based techniques and provide important considerations needed for efficient disulfide bond analysis in proteins. The review focuses on methods for proper sample preparation, fragmentation techniques for disulfide bond analysis, recent disulfide bond mapping methods based on the fragmentation techniques, and automated algorithms designed for rapid analysis of disulfide bonds from liquid chromatography-MS/MS data. Researchers involved in method development for protein characterization can use the information herein to facilitate development of new MS-based methods for protein disulfide bond analysis. In addition, individuals characterizing biotherapeutics, especially by disulfide bond mapping in antibodies, can use this review to choose the best strategies for disulfide bond assignment of their biologic products. Graphical Abstract This review, describing characterization methods for disulfide bonds in proteins, focuses on three critical components: sample preparation, mass

Sedimentation rates measurements in former channels of the upper Rhone river using Chernobyl 137Cs and 134Cs as tracers

International Nuclear Information System (INIS)

Rostan, J.C.; Juget, J.; Brun, A.M.

1997-01-01

Former river channels are aquatic ecosystems with a different geomorphology generated by fluvial dynamics more or less linked to the main channel. They present different ecological successions to become terrestrial ecosystems and are thus supposed to have different sedimentation rates. The aim of this paper is to assess this sedimentation rate using radioactive tracer methodology commonly used in lake studies. Chernobyl impacts, expressed in 137 Cs concentration and 137 Cs/ 134 Cs ratio, were determined in sediment cores. Sites (21) were sampled in the alluvial plain of the Upper Rhone River from 1989 to 1994. The contamination presented a high spatial heterogeneity. The maximum values encountered by site ranged between 34 and 541 Bq/kg of dry matter. The method generally gave good core profiles. Sedimentation rate ranged between 0.14 and 0.70 cm/year for the former meanders and between 0.14 and 2.86 cm/year for the braided channels. The sediment accumulation rates ranged from 0.03 to 0.25 g/cm 2 per year and 0.03 to 2.26 g/cm 2 per year, respectively. These values are similar to those found for Lake Geneva. The importance of the former channels in relation to the main channel is enhanced by the higher contamination and radionuclides retention. The sediment accumulation rate is related to the organic carbon content in the sediment. A comparison between two former channels with different productivity showed that the the allogeneous driven system presents a high organic sediment accumulation rate with a low organic content in the sediment and inversely, a low organic sediment accumulation rate with a high organic carbon content was found for the autogeneous driven system

Chemical vapor deposition based tungsten disulfide (WS2) thin film transistor

KAUST Repository

Hussain, Aftab M.

2013-04-01

Tungsten disulfide (WS2) is a layered transition metal dichalcogenide with a reported band gap of 1.8 eV in bulk and 1.32-1.4 eV in its thin film form. 2D atomic layers of metal dichalcogenides have shown changes in conductivity with applied electric field. This makes them an interesting option for channel material in field effect transistors (FETs). Therefore, we show a highly manufacturable chemical vapor deposition (CVD) based simple process to grow WS2 directly on silicon oxide in a furnace and then its transistor action with back gated device with room temperature field effect mobility of 0.1003 cm2/V-s using the Schottky barrier contact model. We also show the semiconducting behavior of this WS2 thin film which is more promising than thermally unstable organic materials for thin film transistor application. Our direct growth method on silicon oxide also holds interesting opportunities for macro-electronics applications. © 2013 IEEE.

Reversible light-mediated compositional and structural transitions between CsPbBr3 and CsPb2Br5 nanosheets.

Science.gov (United States)

Shen, Wei; Ruan, Longfei; Shen, Zhitao; Deng, Zhengtao

2018-03-13

This communication describes a new method to achieve reversible light-induced chemical composition and phase structural transitions from polyvinylpyrrolidone-capped orthorhombic CsPbBr 3 to tetragonal CsPb 2 Br 5 nanosheets or vice versa. This work will deepen our understanding of the controlled synthesis, post-processing, and decomposition pathway of cesium lead halide perovskite nanocrystals.

Crystal structures of LiCsTiF6 and Cs2TiF6 and interval mobility of complex anions

International Nuclear Information System (INIS)

Popov, D.Yu.; Kavun, V.Ya.; Gerasimenko, A.V.; Sergienko, V.I.; Antokhina, T.F.

2002-01-01

The structure of LiCsTiF 6 (1) and Cs 2 TiF 6 (2) monocrystals was studied by the method of X-ray diffraction analysis. Crystal lattice parameters for compound 1 are: a = 9.251 (1), b = 11.920 (1), c = 10.271 (1), sp.gr. Pbcn, Z = 8; for compound 2: a = 6.213 (1), c = 5.004 (1), sp.gr. P3-bar m1, Z = 1. Three-dimensional frame of bound titanium octahedrons and slightly distorted lithium tetragonal pyramids with Li-F distance ranging from 1.86 to 2.24 A is the crystal structure base of compound 1. The structure of compound 2 is made of dose-packed CsF 3 layers and TiF 6 2- octahedrons located between the layers. The types of internal motion of the complex anions were determined by 10 F NMR method, their activation energy in crystals 1 and 2 in the temperature range of 200-500 K being estimated [ru

Enhanced photoresponse of monolayer molybdenum disulfide (MoS2) based on microcavity structure

Science.gov (United States)

Lu, Yanan; Yang, Guofeng; Wang, Fuxue; Lu, Naiyan

2018-05-01

There is an increasing interest in using monolayer molybdenum disulfide (MoS2) for optoelectronic devices because of its inherent direct band gap characteristics. However, the weak absorption of monolayer MoS2 restricts its applications, novel concepts need to be developed to address the weakness. In this work, monolayer MoS2 monolithically integrates with plane microcavity structure, which is formed by the top and bottom chirped distributed Bragg reflector (DBR), is demonstrated to improve the absorption of MoS2. The optical absorption is 17-fold enhanced, reaching values over 70% at work wavelength. Moreover, the monolayer MoS2-based photodetector device with microcavity presents a significantly increased photoresponse, demonstrating its promising prospects in MoS2-based optoelectronic devices.

Sorption of Cs onto γ-Al2O3 using batch technique

International Nuclear Information System (INIS)

Wang Xiangke

2004-01-01

The sorption of Cs onto γ-Al 2 O 3 is studied by using batch technique, ultra-filtration method and UV vis spectrophotometer at room temperature, pH 4.0, 6.0 and 8.0, the ionic strength of NaClO 4 is from 0.001 mol/L to 0.1 mol/L. The concentration of humic acid in the solution is determined at wavelength of 254 nm. The sorption of humic acid on the γ-Al 2 O 3 is strong (≅98% HA is sorbed on the surface of alumina at pH zpc =9.2)) and strongly dependent on pH values. At pH>9.2, the sorption of HA is decreased markedly with the increasing of pH. Humic acid has a little negative effect on the sorption of Cs onto alumina, this may be attributed to the formation of HA-Cs complexation in the solution. The sorption of Cs onto γ-Al 2 O 3 is weakly dependent on the pH and independent on the ionic strength. Freundlich isotherm can fit the sorption isotherms very well. The sorption of Cs onto γ-Al 2 O 3 may be contributed to cation exchange and surface complexation mechanisms. (authors)

Alkali/TX[sub 2] catalysts for CO/H[sub 2] conversion to C[sub 1]-C[sub 4] alcohols

Energy Technology Data Exchange (ETDEWEB)

Klier, K.; Herman, R.G.; Bastian, R.D.; Flanagan, K.L.

1989-01-01

Ruthenium disulfide catalysts have been synthesized, tested, and characterized during this period of research. It was observed that both the undoped and Cs-doped RuS[sub 2] catalysts produced alcohols and lower amounts of hydrocarbons from H[sub 2]/CO = 1.0 synthesis gas at temperatures above 300[degree]C. Calcination and catalytic testing resulted in partial reduction of the RuS[sub 2] to Ru[sup o]. Calcination under H[sub 2]S prevented the partial reduction of the RuS[sub 2] catalyst, but subsequent catalytic testing again resulted in the formation of a quantity of Ru[sup o]. A Cs-doped RuS[sub 2] catalyst was prepared, but it might have had too high of a loading of Cs. Upon testing, a lower activity was observed for the doped catalyst compared with the undoped catalyst, but the alcohol selectivity was the same for the two catalysts.

Role of Conserved Disulfide Bridges and Aromatic Residues in Extracellular Loop 2 of Chemokine Receptor CCR8 for Chemokine and Small Molecule Binding

DEFF Research Database (Denmark)

Barington, Line; Rummel, Pia C; Lückmann, Michael

2016-01-01

and aromatic residues in extracellular loop 2 (ECL2) for ligand binding and activation in the chemokine receptor CCR8. We used IP3 accumulation and radioligand binding experiments to determine the impact of receptor mutagenesis on both chemokine and small molecule agonist and antagonist binding and action...... in CCR8. We find that the 7 transmembrane (7TM) receptor conserved disulfide bridge (7TM bridge) linking transmembrane helix (TM)III and ECL2 is crucial for chemokine and small molecule action, whereas the chemokine receptor conserved disulfide bridge between the N terminus and TMVII is needed only...

Alpha-cyclodextrins reversibly capped with disulfide bonds

Czech Academy of Sciences Publication Activity Database

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

2010-01-01

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

Metallic molybdenum disulfide nanosheet-based electrochemical actuators

Science.gov (United States)

Acerce, Muharrem; Akdoğan, E. Koray; Chhowalla, Manish

2017-09-01

Actuators that convert electrical energy to mechanical energy are useful in a wide variety of electromechanical systems and in robotics, with applications such as steerable catheters, adaptive wings for aircraft and drag-reducing wind turbines. Actuation systems can be based on various stimuli, such as heat, solvent adsorption/desorption, or electrochemical action (in systems such as carbon nanotube electrodes, graphite electrodes, polymer electrodes and metals). Here we demonstrate that the dynamic expansion and contraction of electrode films formed by restacking chemically exfoliated nanosheets of two-dimensional metallic molybdenum disulfide (MoS2) on thin plastic substrates can generate substantial mechanical forces. These films are capable of lifting masses that are more than 150 times that of the electrode over several millimetres and for hundreds of cycles. Specifically, the MoS2 films are able to generate mechanical stresses of about 17 megapascals—higher than mammalian muscle (about 0.3 megapascals) and comparable to ceramic piezoelectric actuators (about 40 megapascals)—and strains of about 0.6 per cent, operating at frequencies up to 1 hertz. The actuation performance is attributed to the high electrical conductivity of the metallic 1T phase of MoS2 nanosheets, the elastic modulus of restacked MoS2 layers (2 to 4 gigapascals) and fast proton diffusion between the nanosheets. These results could lead to new electrochemical actuators for high-strain and high-frequency applications.

Carbonate hydrates of the heavy alkali metals: preparation and structure of Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O und Cs{sub 2}CO{sub 3} . 3 H{sub 2}O; Carbonat-Hydrate der schweren Alkalimetalle: Darstellung und Struktur von Rb{sub 2}CO{sub 3} . 1,5 H{sub 2}O und Cs{sub 2}CO{sub 3} . 3 H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Cirpus, V.; Wittrock, J.; Adam, A. [Koeln Univ. (Germany). Inst. fuer Anorganische Chemie

2001-03-01

Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O and Cs{sub 2}CO{sub 3} . 3 H{sub 2}O were prepared from aqueous solution and by means of the reaction of dialkylcarbonates with RbOH and CsOH resp. in hydrous alcoholes. Based on four-circle diffractometer data, the crystal structures were determined (Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O: C2/c (no. 15), Z = 8, a = 1237.7(2) pm, b = 1385.94(7) pm, c = 747.7(4) pm, {beta} = 120.133(8) , V{sub EZ} = 1109.3(6) . 10{sup 6} pm{sup 3}; Cs{sub 2}CO{sub 3} . 3 H{sub 2}O: P2/c (no. 13), Z = 2, a = 654.5(2) pm, b = 679.06(6) pm, c = 886.4(2) pm, {beta} = 90.708(14) , V{sub EZ} = 393.9(2) . 10{sup 6} pm{sup 3}). Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O is isostructural with K{sub 2}CO{sub 3} . 1.5 H{sub 2}O. In case of Cs{sub 2}CO{sub 3} . 3 H{sub 2}O no comparable structure is known. Both structures show {sub {infinity}}{sup 1}[(CO{sub 3}{sup 2-})(H{sub 2}O)]-chains, being connected via additional H{sub 2}O forming columns (Rb{sub 2}CO{sub 3} . 1.5 H{sub 2}O) and layers (Cs{sub 2}CO{sub 3} . 3 H{sub 2}O), respectively. (orig.)

Oxathiiranes 8 On the OCS2 Singlet Potential Energy Surface

DEFF Research Database (Denmark)

Carlsen, Lars

1982-01-01

The reaction between atomic oxygen and carbon disulfide is predicted to lead to at least two primary products, which are the dithiiranone (1) and the oxathiirane-thione (2) and/or the carbon disulfide S-oxide (4). The possible intramolecular equilibria 1 ⇄ 2, 1 ⇄ 3, 2 ⇄ 4, and 2 ⇄ 5 as well...... as the fragmentations of the possible intermediates 1–5 have been studied theoretically within the semiempirical cndo/B framework as conceivable ground-state reactions. On the basis of mo correlations and potential energy changes along the reaction paths, supplementary with previously reported experimental data...

[Using 137Cs and 210Pb(ex) to trace the impact of soil erosion on soil organic carbon at a slope farmland in the black soil region].

Science.gov (United States)

Fang, Hai-Yan; Sheng, Mei-Ling; Sun, Li-Ying; Cai, Qiang-Guo

2013-07-01

Soil cores were collected from a 28.5 hm2 slope farmland in the black soil region of Northeast China. Based on the sampled data of 137Cs, 210Pb(ex) and SOC, the potentials of applying 137Cs and 210Pb(ex) for assessing SOC redistribution were evaluated, aimed to approach the impact of soil erosion on soil organic carbon (SOC) in black soil region. At both planar and vertical directions, the 137Cs, 210Pb(ex) and SOC in the farmland had similar distribution patterns. Although there were large planar variations in the 137Cs and 210Pb(ex) areal activities and the SOC stock as affected by soil erosion and deposition, the 137Cs, 210Pb(ex) and SOC had similar changing trends over the landscape. Two depth distribution profiles were also used to study the relations of 137Cs and 210Pb(ex) with SOC. At eroded site, the radioactivities of 137Cs and 210Pb(ex) and the SOC mass fraction did not show large variations in 0-25 cm soil layer, but decreased sharply below 25 cm. For the deposition sample, the radioactivities of 137Cs and 210Pb(ex) in 0-100 cm soil increased firstly and then decreased. The SOC mass fraction also had similar depth distribution pattern in this soil layer. The 137Cs and 210Pb(ex) presented positive linear correlations with the SOC, indicating that 137Cs, 210Pb(ex) and SOC moved with the same physical mechanism in the farmland, and fallout 137Cs and 210Pb(ex) could be used to study spatio-temporal distribution characteristics of SOC in the black soil region under the condition of soil erosion.

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

DEFF Research Database (Denmark)

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

2005-01-01

K(a) value of Cys149, as well as favorable electrostatic interactions with the negatively charged reagents. The results presented here show that the electrostatic milieu of cysteine thiols in proteins can have substantial effects on the rates of the thiol-disulfide exchange reactions.......The thiol-disulfide exchange reaction plays a central role in the formation of disulfide bonds in newly synthesized proteins and is involved in many aspects of cellular metabolism. Because the thiolate form of the cysteine residue is the key reactive species, its electrostatic milieu is thought...... surface. We have studied properties of vicinal cysteine residues in proteins using a model system based on redox-sensitive yellow fluorescent protein (rxYFP). In this system, the formation of a disulfide bond between two cysteines Cys149 and Cys202 is accompanied by a 2.2-fold decrease in fluorescence...

Functional differences in yeast protein disulfide isomerases

DEFF Research Database (Denmark)

Nørgaard, P; Westphal, V; Tachibana, C

2001-01-01

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

Development of sensitive amperometric hydrogen peroxide sensor using a CuNPs/MB/MWCNT-C_6_0-Cs-IL nanocomposite modified glassy carbon electrode

International Nuclear Information System (INIS)

Roushani, Mahmoud; Bakyas, Kobra; Zare Dizajdizi, Behruz

2016-01-01

A sensitive hydrogen peroxide (H_2O_2) sensor was constructed based on copper nanoparticles/methylene blue/multiwall carbon nanotubes–fullerene–chitosan–ionic liquid (CuNPs/MB/MWCNTs–C_6_0–Cs–IL) nanocomposites. The MB/MWCNTs–C_6_0–Cs–IL and CuNPs were modified glassy carbon electrode (GCE) by the physical adsorption and electrodeposition of copper nitrate solution, respectively. The physical morphology and chemical composition of the surface of modified electrode was investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. The electrochemical properties of CuNPs/MB/MWCNTs–C_6_0–Cs–IL/GCE were investigated by cyclic voltammetry (CV) and amperometry techniques and the sensor exhibited remarkably strong electrocatalytic activities toward the reduction of hydrogen peroxide. The peak currents possess a linear relationship with the concentration of H_2O_2 in the range of 0.2 μM to 2.0 mM, and the detection limit is 55.0 nM (S/N = 3). In addition, the modified electrode was used to determine H_2O_2 concentration in human blood serum sample with satisfactory results. - Highlights: • CuNPs/MB/MWCNT-C_6_0-Cs-IL/GC electrode was constructed by layer-by-layer method. • The catalytic performance of the sensor was studied with the use of amperometric technique. • The constructed sensor showed enhanced electrocatalytic activity toward the reduction of H_2O_2. • The CuNPs/MB/MWCNT-C_6_0-Cs-IL/GC electrode demonstrated high stability for the detection of H_2O_2.

Development of sensitive amperometric hydrogen peroxide sensor using a CuNPs/MB/MWCNT-C{sub 60}-Cs-IL nanocomposite modified glassy carbon electrode

Energy Technology Data Exchange (ETDEWEB)

Roushani, Mahmoud, E-mail: mahmoudroushani@yahoo.com; Bakyas, Kobra; Zare Dizajdizi, Behruz

2016-07-01

A sensitive hydrogen peroxide (H{sub 2}O{sub 2}) sensor was constructed based on copper nanoparticles/methylene blue/multiwall carbon nanotubes–fullerene–chitosan–ionic liquid (CuNPs/MB/MWCNTs–C{sub 60}–Cs–IL) nanocomposites. The MB/MWCNTs–C{sub 60}–Cs–IL and CuNPs were modified glassy carbon electrode (GCE) by the physical adsorption and electrodeposition of copper nitrate solution, respectively. The physical morphology and chemical composition of the surface of modified electrode was investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. The electrochemical properties of CuNPs/MB/MWCNTs–C{sub 60}–Cs–IL/GCE were investigated by cyclic voltammetry (CV) and amperometry techniques and the sensor exhibited remarkably strong electrocatalytic activities toward the reduction of hydrogen peroxide. The peak currents possess a linear relationship with the concentration of H{sub 2}O{sub 2} in the range of 0.2 μM to 2.0 mM, and the detection limit is 55.0 nM (S/N = 3). In addition, the modified electrode was used to determine H{sub 2}O{sub 2} concentration in human blood serum sample with satisfactory results. - Highlights: • CuNPs/MB/MWCNT-C{sub 60}-Cs-IL/GC electrode was constructed by layer-by-layer method. • The catalytic performance of the sensor was studied with the use of amperometric technique. • The constructed sensor showed enhanced electrocatalytic activity toward the reduction of H{sub 2}O{sub 2}. • The CuNPs/MB/MWCNT-C{sub 60}-Cs-IL/GC electrode demonstrated high stability for the detection of H{sub 2}O{sub 2}.

Liquid hydrogen production via hydrogen sulfide methane reformation

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [University of Central Florida, Florida Solar Energy Center, 1769 Clearlake Road, Cocoa, FL 32922 (United States)

2008-01-03

Hydrogen sulfide (H{sub 2}S) methane (CH{sub 4}) reformation (H{sub 2}SMR) (2H{sub 2}S + CH{sub 4} = CS{sub 2} + 4H{sub 2}) is a potentially viable process for the removal of H{sub 2}S from sour natural gas resources or other methane containing gases. Unlike steam methane reformation that generates carbon dioxide as a by-product, H{sub 2}SMR produces carbon disulfide (CS{sub 2}), a liquid under ambient temperature and pressure - a commodity chemical that is also a feedstock for the synthesis of sulfuric acid. Pinch point analyses for H{sub 2}SMR were conducted to determine the reaction conditions necessary for no carbon lay down to occur. Calculations showed that to prevent solid carbon formation, low inlet CH{sub 4} to H{sub 2}S ratios are needed. In this paper, we analyze H{sub 2}SMR with either a cryogenic process or a membrane separation operation for production of either liquid or gaseous hydrogen. Of the three H{sub 2}SMR hydrogen production flowsheets analyzed, direct liquid hydrogen generation has higher first and second law efficiencies of exceeding 80% and 50%, respectively. (author)

1.42 A crystal structure of mini-IGF-1(2): an analysis of the disulfide isomerization property and receptor binding property of IGF-1 based on the three-dimensional structure

International Nuclear Information System (INIS)

Yun Caihong; Tang Yuehua; Feng Youmin; An Xiaomin; Chang Wenrui; Liang Dongcai

2004-01-01

Insulin and insulin-like growth factor 1 (IGF-1) share a homologous sequence, a similar three-dimensional structure and weakly overlapping biological activity, but IGF-1 folds into two thermodynamically stable disulfide isomers, while insulin folds into one unique stable tertiary structure. This is a very interesting phenomenon in which one amino acid sequence encodes two three-dimensional structures, and its molecular mechanism has remained unclear for a long time. In this study, the crystal structure of mini-IGF-1(2), a disulfide isomer of an artificial analog of IGF-1, was solved by the SAD/SIRAS method using our in-house X-ray source. Evidence was found in the structure showing that the intra-A-chain/domain disulfide bond of some molecules was broken; thus, it was proposed that disulfide isomerization begins with the breakdown of this disulfide bond. Furthermore, based on the structural comparison of IGF-1 and insulin, a new assumption was made that in insulin the several hydrogen bonds formed between the N-terminal region of the B-chain and the intra-A-chain disulfide region of the A-chain are the main reason for the stability of the intra-A-chain disulfide bond and for the prevention of disulfide isomerization, while Phe B1 and His B5 are very important for the formation of these hydrogen bonds. Moreover, the receptor binding property of IGF-1 was analyzed in detail based on the structural comparison of mini-IGF-1(2), native IGF-1, and small mini-IGF-1

Crystal structure and thermal behaviour of boro-pollucite CsBSi2O6

International Nuclear Information System (INIS)

Bubnova, R.S.; Stepanov, N.K.; Filatov, S.K.; Levin, A.A.; Paufler, P.; Meyer, D.C.

2004-01-01

The crystal structure of Cs 0.82 B 1.09 Si 1.98 O 6 boro-pollucite at room temperature was determined by direct methods and refined in the l a 3-bar d space group using an anisotropic approximation of atomic thermal displacements (a = 13.009 (1) angstrom, Z = 16, R w = 0.027, R F = 0.037 for 141 independent observed (IFI ≥4σ F ) reflections). The occupancy factors have been refined for Cs and tetrahedral positions assuming the oxygen sites being fully occupied. The compound is isostructural to leucite pollucite high-temperature modification. Thermal behaviour of CsBSi 2 O 6 was investigated by DTA and TG, annealing at different temperatures with following wet chemical analysis and high-temperature X-ray powder diffraction methods. The CsBSi 2 O 6 cubic phase loses mass before melting and decomposes to form a new crystalline phase with close to CsBSi 3 O 8 stoichiometry in the temperature range of 1303 353 K. Thermal expansion of two boro-pollucite samples, which differed in the number of Cs + and/or B 3+ ions of a nominal composition CsBSi 2 O 6 was investigated in air as well as in vacuum. Temperature ranges of negative thermal expansion were found. (authors)

Measurement of glutathione-protein mixed disulfides

International Nuclear Information System (INIS)

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

1984-01-01

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

Trapping and interactions of an ultracold gas of Cs2 molecules

International Nuclear Information System (INIS)

Mark, M.; Kraemer, T.; Herbig, J.; Waldburger, P.; Naegerl, H.C.; Chin, C.; Grimm, R.

2005-01-01

Full text: We investigate dynamics and interactions of Cs 2 dimers in a CO2-laser dipole trap. Starting with a Bose-Einstein condensate (BEC) of 2.2 x 10 5 Cs atoms, we create ultracold molecules in a single, weakly bound quantum state by sweeping the magnetic field across a narrow Feshbach resonance. When the molecules are created in free space, the conversion efficiency exceeds 30 %, yielding up to 50000 molecules. In our trapping experiments, about 6000 ultracold Cs 2 dimers are prepared in the optical trap at a temperature of 200 nK. We transfer the trapped molecules from the initial molecular state to other molecular states by following avoided crossings. We find two magnetically tunable resonances in collisions between the molecules for one of the molecular states. We interpret these Feshbach-liKEX resonances as being induced by Cs 4 bound states near the molecular scattering continuum. Further, we have discovered a new molecular state with very large orbital angular momentum of l = 8. This state is very weakly coupled to one of the initial molecular states. We use the associated avoided crossing as a molecular beam splitter to realize a molecular Ramsey-type interferometer. Refs. 2 (author)

The crystal structure of Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O

Energy Technology Data Exchange (ETDEWEB)

Winkler, Verena; Schlosser, Marc; Pfitzner, Arno [Regensburg Univ. (Germany). Inst. fuer Anorganische Chemie

2016-08-01

A reinvestigation of the alkali metal thiosulfates has led to the new phase Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O. At first cesium thiosulfate monohydrate was obtained as a byproduct of the synthesis of Cs{sub 4}In{sub 2}S{sub 5}. Further investigations were carried out using the traditional synthesis reported by J. Meyer and H. Eggeling. Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O crystallizes in transparent, colorless needles. The crystal structure of the title compound was determined by single crystal X-ray diffraction at room temperature: space group C2/m (No. 12), unit cell dimensions: a = 11.229(4), b = 5.851(2), c = 11.260(5) Aa, β = 95.89(2) , with Z = 4 and a cell volume of V = 735.9(5) Aa{sup 3}. The positions of all atoms including the hydrogen atoms were located in the structure refinement. Cs{sub 2}S{sub 2}O{sub 3}.H{sub 2}O is isotypic with Rb{sub 2}S{sub 2}O{sub 3}.H{sub 2}O. Isolated tetrahedra [S{sub 2}O{sub 3}]{sup 2-} are coordinated by the alkali metal cations, and in addition they serve as acceptors for hydrogen bonding. For both Cs atoms the shortest distances are observed to oxygen atoms of the S{sub 2}O{sub 3}{sup 2-} anions whereas the terminating sulfur atom has its shortest contacts to the water hydrogen atoms. Thus, an extended hydrogen bonding network is formed. The title compound has also been characterized by IR spectroscopy. IR spectroscopy reveals the vibrational bands of the water molecules at 3385 cm{sup -1}. They show a red shift in the OH stretching and bending modes as compared to free water. This is due both to the S..H hydrogen bonding and to the coordination of H{sub 2}O molecules to the cesium atoms.

Comparative mode of action of novel hybrid peptide CS-1a and its rearranged amphipathic analogue CS-2a.

Science.gov (United States)

Joshi, Seema; Bisht, Gopal S; Rawat, Diwan S; Maiti, Souvik; Pasha, Santosh

2012-10-01

Cell selective, naturally occurring, host defence cationic peptides present a good template for the design of novel peptides with the aim of achieving a short length with improved antimicrobial potency and selectivity. A novel, short peptide CS-1a (14 residues) was derived using a sequence hybridization approach on sarcotoxin I (39 residues) and cecropin B (35 residues). The sequence of CS-1a was rearranged to enhance amphipathicity with the help of a Schiffer-Edmundson diagram to obtain CS-2a. Both peptides showed good antibacterial activity in the concentration range 4-16 μg·mL(-1) against susceptible as well as drug-resistant bacterial strains, including the clinically relevant pathogens Acenatobacter sp. and methicillin-resistant Staphylococcus aureus. The major thrust of these peptides is their nonhaemolytic activity against human red blood cells up to a high concentration of 512 μg·mL(-1). Compared to CS-1a, amphipathic peptide CS-2a showed a more pronounced α-helical conformation, along with a better membrane insertion depth in bacterial mimic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) small unilamellar vesicles. With equivalent lipid-binding affinity, the two peptides assumed different pathways of membrane disruption, as demonstrated by calcein leakage and the results of transmission electron microscopy on model bacterial mimic large unilamellar vesicles. Extending the work from model membranes to intact Escherichia coli cells, differences in membrane perturbation were visible in microscopic images of peptide-treated E. coli. The present study describes two novel short peptides with potent activity, cell selectivity and divergent modes of action that will aid in the future design of peptides with better therapeutic potential. © 2012 The Authors Journal compilation © 2012 FEBS.

Conductivity And Thermal Stability of Solid Acid Composites CsH2PO4 /NaH2PO4/ SiO2

International Nuclear Information System (INIS)

Norsyahida Mohammad; Abu Bakar Mohamad; Abu Bakar Mohamad; Abdul Amir Hassan Kadhum

2016-01-01

Solid acid composites CsH 2 PO 4 / NaH 2 PO 4 / SiO 2 with different mole ratios of CsH 2 PO 4 and NaH 2 PO 4 to SiO 2 were synthesized and characterized. Preliminary infrared measurements of CsH 2 PO 4 and its composites indicated that hydrogen bonds breaking and formation were detected between 1710 to 2710 cm -1 , while the rotation of phosphate tetrahedral anions occurred between 900 and 1200 cm -1 . The superprotonic transition of CsH 2 PO 4 / NaH 2 PO 4 / SiO 2 composite was identified at superprotonic temperatures between 230 and 260 degree Celcius, under atmospheric pressure. This study reveals higher conductivity values for composites with higher CsH 2 PO 4 (CDP) content. Solid acid composite CDP 613 appeared as the composite with the highest conductivity that is 7.2x10 -3 S cm -1 at 230 degree Celcius. Thermal stability of the solid acid composites such as temperature of dehydration, melting and decomposition were investigated. The addition of NaH 2 PO 4 lowers the dehydration temperature of the solid acid composites. (author)

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

DEFF Research Database (Denmark)

Mysling, Simon; Salbo, Rune; Ploug, Michael

2014-01-01

Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically...... of TCEP. In the present study, we explore the feasibility of using electrochemical reduction as a substitute for TCEP in HDX-MS analyses. Our results demonstrate that efficient disulfide bond reduction is readily achieved by implementing an electrochemical cell into the HDX-MS workflow. We also identify...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

Generation of a Multicomponent Library of Disulfide Donor-Acceptor Architectures Using Dynamic Combinatorial Chemistry.

Science.gov (United States)

Drożdż, Wojciech; Kołodziejski, Michał; Markiewicz, Grzegorz; Jenczak, Anna; Stefankiewicz, Artur R

2015-07-17

We describe here the generation of new donor-acceptor disulfide architectures obtained in aqueous solution at physiological pH. The application of a dynamic combinatorial chemistry approach allowed us to generate a large number of new disulfide macrocyclic architectures together with a new type of [2]catenanes consisting of four distinct components. Up to fifteen types of structurally-distinct dynamic architectures have been generated through one-pot disulfide exchange reactions between four thiol-functionalized aqueous components. The distribution of disulfide products formed was found to be strongly dependent on the structural features of the thiol components employed. This work not only constitutes a success in the synthesis of topologically- and morphologically-complex targets, but it may also open new horizons for the use of this methodology in the construction of molecular machines.

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

Czech Academy of Sciences Publication Activity Database

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

2017-01-01

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

Luminescent properties of BaCl2-Eu microcrystals embedded in a CsI matrix

International Nuclear Information System (INIS)

Pushak, A.; Vistovskyy, V.; Voloshinovskii, A.; Savchyn, P.; Antonyak, O.; Demkiv, T.; Dacyuk, Yu.; Myagkota, S.; Gektin, A.

2013-01-01

The spectral-luminescent properties of CsI-BaCl 2 (1 mol%)-Eu(0.02 mol%) crystalline system are studied. Europium ion doped BaCl 2 microcrystals embedded in a CsI matrix are revealed on CsI-BaCl 2 (1 mol%)-Eu(0.02 mol%) freshly cleaved surface by the scanning electron microscopy. The size of microcrystals is shown to be within 0.5–5 microns. The luminescent parameters of the BaCl 2 -Eu 2+ microcrystals are shown to be similar to ones of a single crystal analogue. The 4f → 5d absorption transitions in europium ions and the reabsorption of the intrinsic emission of the CsI host are the main excitation mechanisms of europium luminescence in the BaCl 2 microcrystals. -- Highlights: ► The formation of chloride BaCl 2 :Eu microcrystals in the case of BaCl 2 doped CsI crystal has been revealed. ► The observed size of microcrystals at BaCl 2 concentration of 1% is about 0.5–5 μm. ► Majority of Eu 2+ ions in CsI-BaCl 2 -EuCl 3 crystalline system enters into BaCl 2 microcrystals. ► The luminescent parameters of the BaCl 2 :Eu 2+ microcrystals and its bulk analogue are similar

Single crystal growth, electronic structure and optical properties of Cs2HgBr4

Science.gov (United States)

Lavrentyev, A. A.; Gabrelian, B. V.; Vu, V. T.; Shkumat, P. N.; Parasyuk, O. V.; Fedorchuk, A. O.; Khyzhun, O. Y.

2015-10-01

We report on successful synthesis of high-quality single crystal of cesium mercury tetrabromide, Cs2HgBr4, by using the vertical Bridgman-Stockbarger method as well as on studies of its electronic structure. For the Cs2HgBr4 crystal, we have recorded X-ray photoelectron spectra for both pristine and Ar+ ion-bombarded surfaces. Our data indicate that the Cs2HgBr4 single crystal surface is rather sensitive with respect to Ar+ ion-bombardment. In particular, such a treatment of the Cs2HgBr4 single crystal surface alters its elemental stoichiometry. To explore peculiarities of the energy distribution of total and partial densities of states within the valence band and the conduction band of Cs2HgBr4, we have made band-structure calculations based on density functional theory (DFT) employing the augmented plane wave+local orbitals (APW+lo) method as incorporated in the WIEN2k package. The APW+lo calculations allow for concluding that the Br 4p states make the major contributions in the upper portion of the valence band, while its lower portion is dominated by contributors of the Hg 5d and Cs 5p states. Further, the main contributors to the bottom of the conduction band of Cs2HgBr4 are the unoccupied Br p and Hg s states. In addition, main optical characteristics of Cs2HgBr4 such as dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity have been explored from the first-principles band-structure calculations.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-30

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

Luminescent characteristic of the CsBr phosphor activated with Eu{sup 2+} and Mn{sup 2+} ions

Energy Technology Data Exchange (ETDEWEB)

Téllez-Flores, E., E-mail: bluedays8i@hotmail.com [Programa de Posgrado en Ciencias (Física), Departamento de Investigación en Física, Universidad de Sonora, Rosales y Blvd. Transversal S/N, 83000 Hermosillo, Son., México (Mexico); Aceves, R., E-mail: raceves@cifus.uson.mx [Centro de Investigación en Física, Universidad de Sonora, Apartado Postal 5-88, 83190 Hermosillo, Son., México (Mexico); Pérez-Salas, R., E-mail: rperez@cifus.uson.mx [Centro de Investigación en Física, Universidad de Sonora, Apartado Postal 5-88, 83190 Hermosillo, Son., México (Mexico); Camarillo, I., E-mail: as99@xanum.uam.mx [Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, Delegación Iztapalapa, C.P. 09340 México D.F. (Mexico); Caldiño, U., E-mail: cald@xanum.uam.mx [Departamento de Física, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, Delegación Iztapalapa, C.P. 09340 México D.F. (Mexico)

2013-12-15

Spectra of excitation and emission were measured at RT and 15 K in crystals quenched (Q) of CsBr:Eu{sup 2+}, CsBr:Mn{sup 2+} and CsBr:Eu{sup 2+},Mn{sup 2+}. Emission bands at 444, 480, 520 and 570 nm with different relative intensities are generated in the samples after UV excitation. The blue band at 444 nm was ascribed with unknown clusters or aggregated centers (AC) of dipoles type Eu{sup 2+}–V{sub C}{sup −} and insulated dipole centers (IDC) like Eu{sup 2+}–O{sup 2−}. The bands at 480, 520 and 570 nm were assigned to Cs{sub 4}EuBr{sub 6} nanocrystals; AC containing MnBr{sub 4}{sup 2−} units in tetrahedral symmetry and another yet unidentified AC defect, respectively. In crystals of CsBr:Eu{sup 2+},Mn{sup 2+} the excitation and emission spectra taken at 15 K show no clear evidence of an energy transfer mechanism. Instead, the results suggest that the emission is produced by direct excitation of the ions of Eu{sup 2+} and Mn{sup 2+}. Accordingly, single- or double-doped CsBr crystals may contain the same type of defects, either AC and/or IDC. -- Highlights: • The PL consists of several overlapping bands in the entire visible region. • The emission bands were ascribed to dipoles, aggregated and nanocrystals of different nature. • No clear evidence of energy transfer, meaning Eu and Mn pairs are not formed. • The material shows potential characteristics for its use as LED to white emission.

Single-crystal X-ray diffraction study of Cs2Er[Si6O14]F and Cs2Er[Si4O10]F

International Nuclear Information System (INIS)

Dabic, Predrag; Kremenovic, Aleksandar; Vulic, Predag; Kahlenberg, Volker; Schmidmair, Daniela

2016-01-01

Single-crystal growth experiments in the system CsF-Er 2 O 3 -SiO 2 resulted in the simultaneous crystallization of two chemically related compounds within the same run: Cs 2 Er[Si 6 O 14 ]F (phase I) and Cs 2 Er[Si 4 O 10 ]F (phase II). They represent the first examples for cesium erbium silicates containing fluorine. Basic crystallographic data are - phase I: space group Cmca, a=17.2556(6) Aa, b=24.6565(7) Aa, c=14.4735(5) Aa, V=6157.9(3) Aa 3 , Z=16; phase II: space group Pnma, a=22.3748(7) Aa, b=8.8390(2) Aa, c=11.9710(4) Aa, V=2367.5(1) Aa 3 , Z=8. The structures were determined by direct methods and refined to residuals of R(vertical stroke F vertical stroke)=0.0229 for 2920 (phase I) and 0.0231 for 2314 (phase II) independent observed reflections with I>2σ(I). The structure of phase I represents a previously unknown structure type with a three dimensional tetrahedral framework consisting of Q 3 and Q 4 groups in the ratio 2:1. Basic building units of the network are unbranched sechser single-chains running parallel to [001]. The network can be conveniently built up from the condensation of tetrahedral layers parallel to (010) or (100), respectively. The crystal structure of phase II can be classified as a tubular or columnar chain silicate indicating that the backbones of the structure are multiple chains of silicate tetrahedra. This structure is isotypic to a Cs 2 Y[Si 4 O 10 ]F, a compound that has been characterized previously. Alternatively, both compounds can be described as mixed octahedral-tetrahedral frameworks, which can be classified according to their polyhedral microensembles. A topological analysis of both nets is presented.

Thiol/disulfide redox states in signaling and sensing

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2015-01-01

Rapid advances in redox systems biology are creating new opportunities to understand complexities of human disease and contributions of environmental exposures. New understanding of thiol-disulfide systems have occurred during the past decade as a consequence of the discoveries that thiol and disulfide systems are maintained in kinetically controlled steady-states displaced from thermodynamic equilibrium, that a widely distributed family of NADPH oxidases produces oxidants that function in cell signaling, and that a family of peroxiredoxins utilize thioredoxin as a reductant to complement the well-studied glutathione antioxidant system for peroxide elimination and redox regulation. This review focuses on thiol/disulfide redox state in biologic systems and the knowledge base available to support development of integrated redox systems biology models to better understand the function and dysfunction of thiol-disulfide redox systems. In particular, central principles have emerged concerning redox compartmentalization and utility of thiol/disulfide redox measures as indicators of physiologic function. Advances in redox proteomics show that, in addition to functioning in protein active sites and cell signaling, cysteine residues also serve as redox sensors to integrate biologic functions. These advances provide a framework for translation of redox systems biology concepts to practical use in understanding and treating human disease. Biological responses to cadmium, a widespread environmental agent, are used to illustrate the utility of these advances to the understanding of complex pleiotropic toxicities. PMID:23356510

Forms and rates of release of Cs-137 in 2 peat soils

International Nuclear Information System (INIS)

Livens, F.R.; Howe, M.T.; Hemingway, J.D.; Goulding, K.W.T.; Howard, B.J.; IACR Rothamsted, Harpenden; Liverpool Univ.; Institute of Terrestrial Ecology, Grange-on-Sands

1996-01-01

Cation exchange resin saturated with H+ and Ca2+ was used to extract Cs-137 from peat soil at two sites in Britain affected by Cs-137 deposition following the Chernobyl accident. The technique identified three classes of Cs-137, similar to those observed for K+ in soils: ''Fast'', ''Intermediate'' and ''Slow''. These classes are probably related to the selectivity for Cs-137 of the cation exchange sites on the organic matter and the clay minerals, and to the structure of the soil. With one exception, most Cs-137 was in the ''Slow'' form and was only very slowly released to the resins, if at all. However, there was enough Cs-137 in the ''Fast'' and ''Intermediate'' forms to contaminate pasture and thus grazing animals for some years. Based on the resin technique, it is estimated that contamination will persist for several decades in uplands contaminated at these activity concentrations. (Author)

Thermodynamic study of gaseous CsBO2 by Knudsen effusion mass spectrometry

Science.gov (United States)

Nakajima, K.; Takai, T.; Furukawa, T.; Osaka, M.

2017-08-01

One of the main chemical forms of cesium in the gas phase during severe light-water reactor accidents is expected to be cesium metaborate, CsBO2, according to thermodynamic equilibrium calculations considering its reaction with boron. However, the accuracy of the thermodynamic data of the gaseous metaborate, CsBO2(g), has been judged as poor. Thus, Knudsen effusion mass spectrometric measurements of CsBO2 were carried out to obtain reliable thermodynamic data. The evaluated values of the standard enthalpy of formation of CsBO2(g), obtained by the 2nd and 3rd-law treatments, are -700.7 ± 10.7 kJ/mol and -697.0 ± 10.6 kJ/mol, respectively, and agree with each other within the experimental errors, which indicates that our data are reliable. Furthermore, it was found that the existing data of the Gibbs energy function and the standard enthalpy of formation agreed well with the values evaluated in this study, which indicates that the existing thermodynamic data are also reliable.

Bacillus sp. Acting as Dual Role for Corrosion Induction and Corrosion Inhibition with Carbon Steel (CS

Directory of Open Access Journals (Sweden)

Santosh K. Karn

2017-10-01

Full Text Available Present work investigated the role of five different bacteria species as a corrosion inducer as well as corrosion inhibitor with carbon steel (CS. We observed the ability of different bacteria species on the metal surface attachment, biofilm formation, and determined Peroxidase, Catalase enzyme activity in the detached biofilm from the CS surface. We found that each strain has diverse conduct for surface attachment like DS1 3.3, DS2 2.5, DS3 4.3, DS4 4.0, and DS5 4.71 log cfu/cm2 and for biofilm 8.3 log cfu/cm2. The enzyme Peroxidase, Catalase was found in huge concentration inside the biofilm Peroxidase was maximum for DS4 36.0 U/ml and least for DS3 19.54 U/ml. Whereas, Catalase was highest for DS4, DS5 70.14 U/ml and least 57.2 U/ml for DS2. Scanning electron microscopy (SEM was conducted to examine the biofilm and electrochemical impedance spectroscopy (EIS were utilized to observe corrosion in the presence of bacteria. The electrochemical results confirmed that DS1, DS3, DS4, and DS5 strains have statistically significant MIC-factors (Microbially Influenced Corrosion of 5.46, 8.51, 2.36, and 1.04, while DS2 protective effect factor of 0.89. Weight reduction results with carbon steel likewise supports that corrosion was initiated by DS1 and DS3, while DS2 and DS5 have no any impact though with DS4 we watched less weight reduction however assumed no role in the corrosion. We established the relation of Peroxidase enzyme activity of the isolates. DS1, DS3 and having Peroxidase in the range 22.18, 19.54 U/ml which induce the corrosion whereas DS2 and DS5 having 28.57 and 27.0 U/ml has no any effect and DS4 36 U/ml has inhibitory effect, increasing concentration inhibiting the corrosion. For Catalase DS1, DS3 have 67.28, 61.57 U/ml which induce corrosion while DS2 and DS5 57.71 and 59.14 U/ml also has no effect whereas DS4 70.14 U/ml can inhibit corrosion. Results clearly express that in a specific range both enzymes can induce the corrosion

Cu-modified carbon spheres/reduced graphene oxide as a high sensitivity of gas sensor for NO2 detection at room temperature

Science.gov (United States)

Su, Zhibin; Tan, Li; Yang, Ruiqiang; Zhang, Yu; Tao, Jin; Zhang, Nan; Wen, Fusheng

2018-03-01

Nitrogen dioxide (NO2) as one of the most serious air pollution is harmful to people's health, therefore high-performance gas sensors is critically needed. Here, Cu-modified carbon spheres/reduced graphene oxide (Cu@CS/RGO) composite have been prepared as NO2 gas sensor material. Carbon sphere in the interlayer of RGO can increase the specific surface area of RGO. Copper nanoparticles decorated on the surface of CS can effectively enhance the adsorption activity of RGO as supplier of free electrons. The experimental results showed that its particular structure improved the gas sensitivity of RGO at different NO2 concentrations at room temperature.

Levels of 137Cs and 40K in wood ash-amended soils

International Nuclear Information System (INIS)

Ohno, Tsutomu; Hess, C.T.

1994-01-01

Wood ash is a residual material produced at an annual rate of 1.5-3.0 million tons by wood burning power plants in the USA. Up to 80% of the wood ash generated in northeastern USA is landspread on agricultural soils. Recently, concern has arisen regarding the 137 Cs content of wood ash and levels of 137 Cs of wood ash-amended soils. The 137 Cs originated primarily from above ground nuclear weapons testing in the 1950s and 1960s. This study examined the total and pH 3, NH 4 OAc extractable levels of 137 Cs and 40 K in three soils incubated in the laboratory with 0, 3 and 9 g of wood ash on a calcium carbonate equivalence basis kg -1 soil. The wood ash contained 137 Cs and 40 K at 3920 and 21'700 pCi kg -1 , respectively. At the regulated wood ash application rate limit, 3 g wood ash (calcium carbonate equivalent basis) kg -1 of soil, there was no statistical difference from the control treatment in both total and soluble 137 Cs and 40 K levels. For one soil, there was an increase in the 137 Cs level when wood ash was amended at 9 g wood ash (calcium carbonate equivalent basis) kg -1 soil. The 137 Cs was strongly bound to the cation exchange sites of the soils with the average fraction soluble in pH 3, NH 4 OAc solution at 4.8% in the mineral soils and 0.9% in the organic soil. Considering the current limits on permitted wood ash application rates to soils, there was no statistically significant effect on the levels of 137 Cs or 40 K found in wood ash-amended soils

Separation of CsCl and SrCl_2 from a ternary CsCl-SrCl_2-LiCl via a zone refining process for waste salt minimization of pyroprocessing

International Nuclear Information System (INIS)

Shim, Moonsoo; Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon; Lee, Jong Hyeon

2016-01-01

The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl_2 salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The k_e_f_f of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively. - Highlights: • The LiCl-CsCl-SrCl_2 salt ingot was purified by zone refining technique to minimize waste salt. • The concentration distribution of Cs and Sr were analyzed by mass transfer equation. • The decontamination factors of Cs and Sr were 1600 and 450 respectively in case of 60% of recovery yield.

Structural study of caesium-based britholites Sr7La2Cs(PO4)5(SiO4)F2

International Nuclear Information System (INIS)

Boughzala, K.; Gmati, N.; Bouzouita, K.; Ben Cherifa, A.; Gravereau, P.

2010-01-01

Several studies demonstrated the ability of britholites to retain radionuclides such as the caesium and actinides. Therefore, three compounds with formulas Sr 8 LaCs(PO 4 ) 6 F 2 , Sr 7 La 2 Cs(PO 4 ) 5 (SiO 4 )F 2 and Sr 2 La 7 Cs(SiO 4 ) 6 F 2 , were prepared by solid state reaction. However, it seems that only the mono-silicated composition was obtained in a pure state. In this present work, the X-ray diffraction and magnetic nuclear resonance have been used to investigate the structure for this composition. The results showed that in fact this phase was not pure, but it was mixed with a secondary phase, SrLaCs(PO 4 ) 2 . The refinement by the Rietveld method allowed also to precise the distribution of La 3+ and Cs + ions between the two cationic sites of the apatite. (authors)

New thiol-responsive mono-cleavable block copolymer micelles labeled with single disulfides.

Science.gov (United States)

Sourkohi, Behnoush Khorsand; Schmidt, Rolf; Oh, Jung Kwon

2011-10-18

Thiol-responsive symmetric triblock copolymers having single disulfide linkages in the middle blocks (called mono-cleavable block copolymers, ss-ABP(2)) were synthesized by atom transfer radical polymerization in the presence of a disulfide-labeled difunctional Br-initiator. These brush-like triblock copolymers consist of a hydrophobic polyacrylate block having pendent oligo(propylene oxide) and a hydrophilic polymethacrylate block having pendent oligo(ethylene oxide). Gel permeation chromatography and (1)H NMR results confirmed the synthesis of well-defined mono-cleavable block copolymers and revealed that polymerizations were well controlled. Because of amphiphilic nature, these copolymers self-assembled to form colloidally stable micelles above critical micellar concentration of 0.032 mg · mL(-1). In response to reductive reactions, disulfides in thiol-responsive micelles were cleaved. Atomic force microscopy and dynamic light scattering analysis suggested that the cleavage of disulfides caused dissociation of micelles to smaller-sized assembled structures in water. Moreover, in a biomedical perspective, the mono-cleavable block copolymer micelles are not cytotoxic and thus biocompatible. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NARCIS (Netherlands)

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

2002-01-01

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

Quantifying the global cellular thiol-disulfide status

DEFF Research Database (Denmark)

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

2009-01-01

It is widely accepted that the redox status of protein thiols is of central importance to protein structure and folding and that glutathione is an important low-molecular-mass redox regulator. However, the total cellular pools of thiols and disulfides and their relative abundance have never been...... determined. In this study, we have assembled a global picture of the cellular thiol-disulfide status in cultured mammalian cells. We have quantified the absolute levels of protein thiols, protein disulfides, and glutathionylated protein (PSSG) in all cellular protein, including membrane proteins. These data...... cell types. However, when cells are exposed to a sublethal dose of the thiol-specific oxidant diamide, PSSG levels increase to >15% of all protein cysteine. Glutathione is typically characterized as the "cellular redox buffer"; nevertheless, our data show that protein thiols represent a larger active...

Radiation-induced cleavage of disulfide bonds in proteins. Clivage radiolytique des ponts disulfure des proteines

Energy Technology Data Exchange (ETDEWEB)

Favaudon, V; Tourbez, H; Lhoste, J M [Paris-11 Univ., 91 - Orsay (FR); Houee-Levin, C [Paris-5 Univ., 75 (FR)

1991-06-01

The reduction of the disulfide bonds in apo-Riboflavin-Binding Protein (apoRBP) by the CO{sub 2}{sup -}{center dot} radical occurred under {gamma}-ray irradiation as a chain reaction whose efficiency increased upon acidification of the medium. Pulse-radiolysis analysis showed a rapid one-electron oxidation of the disulfide bonds yielding the anionic or protonated form of the disulfide radical. The main decay path of this radical under acidic conditions consisted of the rapid formation of a thiyl radical intermediate in equilibrium with the closed, cyclic form. At pH 8 the disulfide radical anion decayed via intramolecular and/or intermolecular routes including disproportionation, protein-protein crosslinking, non-dismutative recombination processes, and reaction with sulfhydryl groups in pre-reduced systems.

Conformational analysis and design of cross-strand disulfides in antiparallel β-sheets.

Science.gov (United States)

Indu, S; Kochat, V; Thakurela, S; Ramakrishnan, C; Varadarajan, Raghavan

2011-01-01

Cross-strand disulfides bridge two cysteines in a registered pair of antiparallel β-strands. A nonredundant data set comprising 5025 polypeptides containing 2311 disulfides was used to study cross-strand disulfides. Seventy-six cross-strand disulfides were found of which 75 and 1 occurred at non-hydrogen-bonded (NHB) and hydrogen-bonded (HB) registered pairs, respectively. Conformational analysis and modeling studies demonstrated that disulfide formation at HB pairs necessarily requires an extremely rare and positive χ¹ value for at least one of the cysteine residues. Disulfides at HB positions also have more unfavorable steric repulsion with the main chain. Thirteen pairs of disulfides were introduced in NHB and HB pairs in four model proteins: leucine binding protein (LBP), leucine, isoleucine, valine binding protein (LIVBP), maltose binding protein (MBP), and Top7. All mutants LIVBP T247C V331C showed disulfide formation either on purification, or on treatment with oxidants. Protein stability in both oxidized and reduced states of all mutants was measured. Relative to wild type, LBP and MBP mutants were destabilized with respect to chemical denaturation, although the sole exposed NHB LBP mutant showed an increase of 3.1°C in T(m). All Top7 mutants were characterized for stability through guanidinium thiocyanate chemical denaturation. Both exposed and two of the three buried NHB mutants were appreciably stabilized. All four HB Top7 mutants were destabilized (ΔΔG⁰ = -3.3 to -6.7 kcal/mol). The data demonstrate that introduction of cross-strand disulfides at exposed NHB pairs is a robust method of improving protein stability. All four exposed Top7 disulfide mutants showed mild redox activity. © 2010 Wiley-Liss, Inc.

Magnetic MoS2 on multiwalled carbon nanotubes for sulfide sensing.

Science.gov (United States)

Li, Chunxiang; Zhang, Dan; Wang, Jiankang; Hu, Pingan; Jiang, Zhaohua

2017-07-04

A novel hybrid metallic cobalt insided in multiwalled carbon nanotubles/molybdenum disulfide (Co@CNT/MoS 2 ) modified glass carbon electrode (GCE) was fabricated with a adhesive of Nafion suspension and used as chemical sensors for sulfide detection. Single-layered MoS 2 was coated on CNTs through magnetic traction force between paramagnetic monolayer MoS 2 and Co particles in CNTs. Co particles faciliated the collection of paramagnetic monolayer MoS 2 exfoliated from bulk MoS 2 in solution. Amperometric analysis, cycle voltammetry, cathodic stripping analysis and linear sweep voltammetry results showed the Co@CNT/MoS 2 modified GCE exhibited excellent electrochemical activity to sulfide in buffer solutions, but amperometric analysis was found to be more sensitive than the other methods. The amperometric response result indicated the Co@CNT/MoS 2 -modified GCE electrode was an excellent electrochemical sensor for detecting S 2- with a detection limit of 7.6 nM and sensitivity of 0.23 mA/μM. The proposed electrode was used for the determination of sulfide levels in hydrogen sulfide-pretreated fruits, and the method was also verified with recovery studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Time-resolved luminescence of Eu2+-aggregate centers in CsBr crystals

International Nuclear Information System (INIS)

Zorenko, Yu.V.; Turchak, R.M.; Voznjak, T.I.; Stryganjuk, G.B.

2005-01-01

The luminescence of Eu 2+ -V Cs dipole centers and CsEuBr 3 aggregate centers, as well as the features of the energy transfer to these centers by excitons have been studied in CsBr:Eu crystals by means of investigation of the time-resolved emission spectra and luminescence decay kinetics under excitation by synchrotron radiation at RT. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

The Disulfide Bond Cys255-Cys279 in the Immunoglobulin-Like Domain of Anthrax Toxin Receptor 2 Is Required for Membrane Insertion of Anthrax Protective Antigen Pore.

Directory of Open Access Journals (Sweden)

Pedro Jacquez

Full Text Available Anthrax toxin receptors act as molecular clamps or switches that control anthrax toxin entry, pH-dependent pore formation, and translocation of enzymatic moieties across the endosomal membranes. We previously reported that reduction of the disulfide bonds in the immunoglobulin-like (Ig domain of the anthrax toxin receptor 2 (ANTXR2 inhibited the function of the protective antigen (PA pore. In the present study, the disulfide linkage in the Ig domain was identified as Cys255-Cys279 and Cys230-Cys315. Specific disulfide bond deletion mutants were achieved by replacing Cys residues with Ala residues. Deletion of the disulfide bond C255-C279, but not C230-C315, inhibited the PA pore-induced release of the fluorescence dyes from the liposomes, suggesting that C255-C279 is essential for PA pore function. Furthermore, we found that deletion of C255-C279 did not affect PA prepore-to-pore conversion, but inhibited PA pore membrane insertion by trapping the PA membrane-inserting loops in proteinaceous hydrophobic pockets. Fluorescence spectra of Trp59, a residue adjacent to the PA-binding motif in von Willebrand factor A (VWA domain of ANTXR2, showed that deletion of C255-C279 resulted in a significant conformational change on the receptor ectodomain. The disulfide deletion-induced conformational change on the VWA domain was further confirmed by single-particle 3D reconstruction of the negatively stained PA-receptor heptameric complexes. Together, the biochemical and structural data obtained in this study provides a mechanistic insight into the role of the receptor disulfide bond C255-C279 in anthrax toxin action. Manipulation of the redox states of the receptor, specifically targeting to C255-C279, may become a novel strategy to treat anthrax.

Selective disulfide reduction for labeling and enhancement of Fab antibody fragments.

Science.gov (United States)

Kirley, Terence L; Greis, Kenneth D; Norman, Andrew B

2016-11-25

Many methods have been developed for chemical labeling and enhancement of the properties of antibodies and their common fragments, including the Fab and F(ab') 2 fragments. Somewhat selective reduction of some antibody disulfide bonds has been previously achieved, yielding antibodies and antibody fragments that can be labeled at defined sites, enhancing their utility and properties. Selective reduction of the two hinge disulfide bonds present in F(ab') 2 fragments using mild reduction has been useful. However, such reduction is often not quantitative and results in the reduction of multiple disulfide bonds, and therefore subsequent multiple labeling or conjugation sites are neither homogenous nor stoichiometric. Here, a simple and efficient selective reduction of the single disulfide bond linking the partial heavy chain and the intact light chain which compose the Fab fragment is accomplished utilizing tris(2-carboxyethyl)phosphine (TCEP) immobilized on agarose beads. The resultant reduced cysteine residues were labeled with several cysteine-selective fluorescent reagents, as well as by cysteine-directed PEGylation. These two cysteine residues can also be re-ligated by means of a bifunctional cysteine cross-linking agent, dibromobimane, thereby both restoring a covalent linkage between the heavy and light chains at this site, far removed from the antigen binding site, and also introducing a fluorescent probe. There are many other research and clinical uses for these selectively partially reduced Fab fragments, including biotinylation, toxin and drug conjugation, and incorporation of radioisotopes, and this technique enables simple generation of very useful Fab fragment derivatives with many potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Variable dimensionality and framework found in a series of quaternary zinc selenites, A2Zn3(SeO3)4·xH2O (A = Na, Rb, and Cs; 0≤x≤1) and Cs2Zn2(SeO3)3·2H2O

Science.gov (United States)

Lü, Minfeng; Jo, Hongil; Oh, Seung-Jin; Ok, Kang Min

2017-01-01

Five new alkali metal zinc selenites, A2Zn3(SeO3)4·xH2O (A = Na, Rb, and Cs; 0≤x≤1) and Cs2Zn2(SeO3)3·2H2O have been synthesized by heating a mixture of ZnO, SeO2 and A2CO3 (A = Na, Rb, and Cs), and characterized by X-ray diffraction (XRD) and spectroscopic analyses techniques. All of the reported materials revealed a rich structural chemistry with different frameworks and connection modes of Zn2+. While Rb2Zn3(SeO3)4 and Cs2Zn3(SeO3)4·H2O revealed three-dimensional frameworks consisting of isolated ZnO4 tetrahedra and SeO3 polyhedra, Na2Zn3(SeO3)4, Cs2Zn3(SeO3)4, and Cs2Zn2(SeO3)3·2H2O contained two-dimensional [Zn3(SeO3)4]2- layers. Specifically, whereas isolated ZnO4 tetrahedra and SeO3 polyhedra are arranged into two-dimensional [Zn3(SeO3)4]2- layers in two cesium compounds, circular [Zn3O10]14- chains and SeO3 linkers are formed in two-dimensional [Zn3(SeO3)4]2- layers in Na2Zn3(SeO3)4. Close structural examinations suggest that the size of alkali metal is significant in determining the framework geometry as well as connection modes of transition metal cations.

Properties of CsI and CsI-TMAE photocathodes

International Nuclear Information System (INIS)

Anderson, D.F.; Kwan, S.; Peskov, V.; Hoeneisen, B.

1992-06-01

The importance of heating the CsI or CsI-TMAE photocathodes during preparation, as well as the importance of the gas environment on the quantum efficiency is presented. The dependence of the aging characteristics of these photocathodes on the operating temperature, on the presence of gas, and on the charge amplification of the chamber is also discussed. For CsI photocathodes charges in excess of 2x10 14 e - /mm 2 can be collected with little degradation of performance. A timing resolution of 0.55 ns is also achieved for single photoelectrons suggesting a possible time-of-flight detector

Synthesis and crystal structure of hydrogen selenates K(HSeO4)(H2SeO4) and Cs(HSeO4)(H2SeO4)

International Nuclear Information System (INIS)

Troyanov, S.I.; Morozov, I.V.; Zakharov, M.A.; Kemnitz, E.

1999-01-01

Hydrogen selenates of the compositions K(HSeO 4 )(H 2 SeO 4 ) and Cs(HSeO 4 )(H 2 SeO 4 ) are synthesized by the reaction of alkali metal carbonates with an excess of the concentrated selenic acid. The X-ray diffraction study showed that both compounds are isostructural to the corresponding hydrogen sulfates. The difference in the systems of hydrogen bonding are caused by various combinations of the acceptor functions of the oxygen atoms in the HSeO 4 and H 2 SeO 4 groups

Positronium formation in CS2 and C6F6 mixtures with triethylamine or tetrahydrofuran

International Nuclear Information System (INIS)

Zhicheng Zhang; Ito, Yasuo; Tabata, Yoneho

1990-01-01

Positronium (Ps) yields were measured for CS 2 /THF, CS 2 /TEA, C 6 F 6 THF and C 6 F 6 /TEA mixtures. Addition of C 6 F 6 or CS 2 into TEA or THF showed a similar influence which induces a decrease of Ps yield. This is ascribed to the non-dissociative electron scavenging by both CS 2 and C 6 F 6 . On the other hand, the effect of addition of TEA and THF has been found to be different for C 6 F 6 and CS 2 , i.e. both TEA and THF did not change Ps yield in CS 2 substantially, while they caused a sharp decrease of Ps yield in C 6 F 6 . The latter sharp decreases was ascribed to quenching of excited state of C 6 F 6 . This interpretation is supported by pulse radiolysis emission measurements for the same system, in which it was found that TEA quenches the excited state of C 6 F 6 efficiently. (author)

Trace gas measurements from tethered balloon platforms

Science.gov (United States)

Bandy, Alan R.; Bandy, Terese L.; Youngbluth, Otto; Owens, Thomas L.

1987-01-01

Instrumentation and chemical sampling and analysis procedures are described for making measurements of atmospheric carbon disulfide in the concentration range 1-1000 pptv from tethered balloon platforms. Results of a study on the CS2 composition of air downward of a saltwater marsh are reported. A method for obtaining the necessary data for solving the budget equations for surface fluxes, chemical formation rates and chemical destruction rates using data acquired from tethered balloon platforms is presented.

Effects of Propylene Carbonate Content in CsPF ₆ -Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo; Xiang, Hongfa [School of; Engelhard, Mark H.; Polzin, Bryant J. [Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States; Wang, Chongmin; Zhang, Ji-Guang; Xu, Wu

2016-02-15

The effects Of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite parallel to LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly-affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs+ additive. The synergistic effects of Cs+ additive and appropriate amount of PC enable the formation of a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li+ ions and allows fast Li+ ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite parallel to NCA full cells under a wide temperature range. The fundamental findings also shed light On the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.

Radiation damage in undoped CsI and CsI(Tl)

International Nuclear Information System (INIS)

Woody, C.L.; Kierstead, J.A.; Levy, P.W.; Stoll, S.

1992-01-01

Radiation damage has been studied in undoped CsI and CsI(TI) crystals using 60 Co gamma radiation for doses up to ∼ 4.2 x 10 6 . Samples from various manufacturers were measured ranging in size from 2.54 cm long cylinders to a 30 cm long block. Measurements were made on the change in optical transmission and scintillation light output as a function of dose. Although some samples showed a small change in transmission, a significant change in light output was observed for all samples. Recovery from damage was also studied as a function of time and exposure to UV light. A short lived phosphorescence was observed in undoped CsI, similar to the phosphorescence seen in CsI(TI)

[Energy pooling collisions for K(4P) + Cs(5D) in a K-Cs mixture].

Science.gov (United States)

Aihemaiti, Pulati; Dai, Kang; Lu, Xin-hong; Shen, Yi-fan

2005-04-01

The rate coefficients for energy-pooling collisions K(4P) + Cs(5D) --> Cs(6S) + K(4D, 6S) in the K-Cs vapor mixture were measured relative to a known energy-pooling rate coefficient of a homonuclear reaction [i. e., Cs(6P) + Cs(5D) --> Cs(6S) + Cs (7D(J))]. Populations of the Cs(6P, 5D) and K(4P) states were produced by photodissociation of K2 and Cs2 molecules through the use of a dye laser radiation. The resulting fluorescence included the direct components emitted in the decay of the excited states produced by photodissociation and the induced components arising from the collisionally populated states. By combining relative intensities of the components with the effective lifetimes of Cs(6P) and K(4P) states, the rate coefficients (in units of 10(-9) cm3 x s(-1)) for the heteronuclear energy-pooling were found to be 2.6 and 3.6, respectively. The contribution to the rate coefficients from other processes are discussed.

Thermodynamic properties and behaviour of A2[(UO2)(MoO4)2] compounds with A = Li, Na, K, Rb, and Cs

International Nuclear Information System (INIS)

Lelet, Maxim I.; Suleimanov, Evgeny V.; Golubev, Aleksey V.; Geiger, Charles A.; Depmeier, Wulf; Bosbach, Dirk; Alekseev, Evgeny V.

2014-01-01

Highlights: • Low temperature heat capacity of A 2 [(UO 2 )(MoO 4 ) 2 ] (A = Li, Na, K, Rb, and Cs) series was determined. • Enthalpy of formation of Li 2 [(UO 2 )(MoO 4 ) 2 ] was determined by HF solution calorimetry. • Δ f G° (T = 298 K) of all phases from studied series were calculated. - Abstract: A thermodynamic investigation of five alkali-metal uranyl molybdates of the general formula A 2 [(UO 2 )(MoO 4 ) 2 ], where A = Li, Na, K, Rb, and Cs, was undertaken. The various phases were synthesized by solid-state reaction of ANO 3, with A = Li, Na, K, Rb, or Cs, MoO 3 and γ-UO 3 . The synthetic products were characterized by X-ray powder diffraction and X-ray fluorescence methods. The low-temperature heat capacity, S r °, was measured using adiabatic calorimetry from T = (6 to 335) K. Based on these data, the third law entropy at T = 298.15 K, S°, is (345 ± 1) J · K −1 · mol −1 for Li 2 [(UO 2 )(MoO 4 ) 2 ], (373 ± 1) J · K −1 · mol −1 for Na 2 [(UO 2 )(MoO 4 ) 2 ], (390 ± 1) J · K −1 · mol −1 for K 2 [(UO 2 )(MoO 4 ) 2 ], (377 ± 1) J · K −1 · mol −1 for Rb 2 [(UO 2 )(MoO 4 ) 2 ] and (394 ± 1) J · K −1 · mol −1 for Cs 2 [(UO 2 )(MoO 4 ) 2 ]. The enthalpy of formation of Li 2 [(UO 2 )(MoO 4 ) 2 ] was determined using HF solution calorimetry giving Δ f H°(T = 298 K, Li 2 [(UO 2 )(MoO 4 ) 2 ], cr) = −(3456 ± 9) kJ · mol −1 . Using these new experimental results, together with literature data, the Gibbs free energy of formation of each compound was calculated, giving: Δ f G°(T = 298 K, Li 2 [(UO 2 )(MoO 4 ) 2 ], cr) = −(3204 ± 9) kJ · mol −1 , Δ f G°(T = 298 K, Na 2 [(UO 2 )(MoO 4 ) 2 ], cr) = −(3243 ± 2) kJ · mol −1 , Δ f G°(T = 298 K, K 2 [(UO 2 )(MoO 4 ) 2 ], cr) = −(3269 ± 3) kJ · mol −1 , Δ f G°(T = 298 K, Rb 2 [(UO 2 )(MoO 4 ) 2 ], cr) = −(3262 ± 3) kJ · mol −1 , and Δ f G°(T = 298 K, Cs 2 [(UO 2 )(MoO 4 ) 2 ], cr) = −(3259 ± 3) kJ · mol −1 . Smoothed S r °(T) values

Variable dimensionality and framework found in a series of quaternary zinc selenites, A2Zn3(SeO3)4·xH2O (A = Na, Rb, and Cs; 0≤x≤1) and Cs2Zn2(SeO3)3·2H2O

International Nuclear Information System (INIS)

Lü, Minfeng; Jo, Hongil; Oh, Seung-Jin; Ok, Kang Min

2017-01-01

Five new alkali metal zinc selenites, A 2 Zn 3 (SeO 3 ) 4 ·xH 2 O (A = Na, Rb, and Cs; 0≤x≤1) and Cs 2 Zn 2 (SeO 3 ) 3 ·2H 2 O have been synthesized by heating a mixture of ZnO, SeO 2 and A 2 CO 3 (A = Na, Rb, and Cs), and characterized by X-ray diffraction (XRD) and spectroscopic analyses techniques. All of the reported materials revealed a rich structural chemistry with different frameworks and connection modes of Zn 2+ . While Rb 2 Zn 3 (SeO 3 ) 4 and Cs 2 Zn 3 (SeO 3 ) 4 ·H 2 O revealed three-dimensional frameworks consisting of isolated ZnO 4 tetrahedra and SeO 3 polyhedra, Na 2 Zn 3 (SeO 3 ) 4 , Cs 2 Zn 3 (SeO 3 ) 4 , and Cs 2 Zn 2 (SeO 3 ) 3 ·2H 2 O contained two-dimensional [Zn 3 (SeO 3 ) 4 ] 2- layers. Specifically, whereas isolated ZnO 4 tetrahedra and SeO 3 polyhedra are arranged into two-dimensional [Zn 3 (SeO 3 ) 4 ] 2- layers in two cesium compounds, circular [Zn 3 O 10 ] 14- chains and SeO 3 linkers are formed in two-dimensional [Zn 3 (SeO 3 ) 4 ] 2- layers in Na 2 Zn 3 (SeO 3 ) 4 . Close structural examinations suggest that the size of alkali metal is significant in determining the framework geometry as well as connection modes of transition metal cations. - Graphical abstract: Variable dimensions and frameworks were found in a series of quaternary zinc selenites, A 2 Zn 3 (SeO 3 ) 4 (A = Na, Rb and Cs). - Highlights: • Five novel quaternary zinc selenites are synthesized. • All the selenites with different structures contain polarizable d 10 and lone pair cations. • The size of alkali metal cations is significant in determining the framework geometry.

Identification of intra- and intermolecular disulfide bridges in the multidrug resistance transporter ABCG2

DEFF Research Database (Denmark)

Henriksen, Ulla Birk; Fog, Jacob U; Litman, Thomas

2005-01-01

cysteines predicted to be on the extracellular face of ABCG2. Upon mutation of Cys-592 or Cys-608 to alanine (C592A and C608A), ABCG2 migrated as a dimer in SDS-PAGE under non-reducing conditions; however, mutation of Cys-603 to Ala (C603A) caused the transporter to migrate as a single monomeric band....... Despite this change, C603A displayed efficient membrane targeting and preserved transport function. Because the transporter migrated as a dimer in SDS-PAGE, when only Cys-603 was present (C592A-C608A), the data suggest that Cys-603 forms a symmetrical intermolecular disulfide bridge in the ABCG2 homodimer...

Photodegradable, Photoadaptable Hydrogels via Radical-Mediated Disulfide Fragmentation Reaction.

Science.gov (United States)

Fairbanks, Benjamin D; Singh, Samir P; Bowman, Christopher N; Anseth, Kristi S

2011-04-26

Various techniques have been adopted to impart a biological responsiveness to synthetic hydrogels for the delivery of therapeutic agents as well as the study and manipulation of biological processes and tissue development. Such techniques and materials include polyelectrolyte gels that swell and deswell with changes in pH, thermosensitive gels that contract at physiological temperatures, and peptide cross-linked hydrogels that degrade upon peptidolysis by cell-secreted enzymes. Herein we report a unique approach to photochemically deform and degrade disulfide cross-linked hydrogels, mitigating the challenges of light attenuation and low quantum yield, permitting the degradation of hydrogels up to 2 mm thick within 120 s at low light intensities (10 mW/cm(2) at 365 nm). Hydrogels were formed by the oxidation of thiol-functionalized 4-armed poly(ethylene glycol) macromolecules. These disulfide cross-linked hydrogels were then swollen in a lithium acylphosphinate photoinitiator solution. Upon exposure to light, photogenerated radicals initiate multiple fragmentation and disulfide exchange reactions, permitting and promoting photodeformation, photowelding, and photodegradation. This novel, but simple, approach to generate photoadaptable hydrogels portends the study of cellular response to mechanically and topographically dynamic substrates as well as novel encapsulations by the welding of solid substrates. The principles and techniques described herein hold implications for more than hydrogel materials but also for photoadaptable polymers more generally.

134Cs uptake by four plant species and Cs-K relations in the soil-plant system as affected by Ca(OH)2 application to an acid soil

International Nuclear Information System (INIS)

Massas, I.; Skarlou, V.; Haidouti, C.; Giannakopoulou, F.

2010-01-01

Three rates of Ca(OH) 2 were applied to an acid soil and the 134 Cs uptake by radish, cucumber, soybean and sunflower plants was studied. The 134 Cs concentration in all plant species was reduced from 1.6-fold in the sunflower seeds to 6-fold in the soybean vegetative parts at the higher Ca(OH) 2 rate. Potassium (K) concentration in plants was also reduced, but less effectively. The significantly decreased 134 Cs-K soil to plant distribution factors (D.F.) clearly suggest a stronger effect of soil liming on 134 Cs than on K plant uptake. This observation was discussed in terms of ionic interactions in the soil matrix and within the plants. The results also indicated that the increased Ca 2+ concentration in the exchange phase and in the soil solution along with the improved root activity, due to the soil liming, enhanced the immobilization of 134 Cs in the soil matrix and consequently lowered the 134 Cs availability for plant uptake.

Acid-base chemistry and proton conductivity of CsHSO₄, CsH₂PO₄ and their mixtures with N-heterocycles  

DEFF Research Database (Denmark)

Aili, David; Gao, Ying; Han, Junyoung

2017-01-01

temperature range of CsH2PO4 as well. Binary mixtures of CsH2PO4 with 1,2,4-triazole, benzimidazole or imidazole were prepared by means of mechanochemical synthesis. Mixtures based on CsHSO4 were prepared as a basis for a comparative discussion. It was found that CsHSO4 formed organic-inorganic salts, while...

Crystal Growth and Scintillation Properties of Eu2+ doped Cs4CaI6 and Cs4SrI6

Science.gov (United States)

Stand, L.; Zhuravleva, M.; Chakoumakos, B.; Johnson, J.; Loyd, M.; Wu, Y.; Koschan, M.; Melcher, C. L.

2018-03-01

In this work we present the crystal growth and scintillation properties of two new ternarymetal halide scintillators activated with divalent europium, Cs4CaI6 and Cs4SrI6. Single crystals of each compound were grown in evacuated quartz ampoules via the vertical Bridgman technique using a two-zone transparent furnace. Single crystal X-ray diffraction experiments showed that both crystals have a trigonal (R-3c) structure, with a density of 3.99 g/cm3 and 4.03 g/cm3. The radioluminescence and photoluminescence measurements showed typical luminescence properties due to the 5d-4f radiative transitions in Eu2+. At this early stage of development Cs4SrI6:Eu and Cs4CaI6:Eu have shown very promising scintillation properties, with light yields and energy resolutions of 62,300 ph/MeV and 3.3%, and 51,800 photons/MeV and 3.6% at 662 keV, respectively.

Simulated UO{sub 2} fuel containing CsI by spark plasma sintering

Energy Technology Data Exchange (ETDEWEB)

Wangle, T. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, 76125 Karlsruhe (Germany); Czech Technical University in Prague, Faculty of Nuclear Sciences and Physical Engineering, Břehová 7, Praha 1, 115 19 (Czech Republic); Tyrpekl, V. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, 76125 Karlsruhe (Germany); Cologna, M., E-mail: marco.cologna@ec.europa.eu [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, 76125 Karlsruhe (Germany); Somers, J. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, 76125 Karlsruhe (Germany)

2015-11-15

Herein, an innovative preparation procedure has been deployed enabling, for the first time, the incorporation of volatile fission product simulant into highly dense nuclear fuel pellets. Highly volatile fission products were embedded in a dense UO{sub 2} matrix in the form of CsI by simply mixing starting materials and consolidation in a Spark Plasma Sintering step at 1000 °C with a 5 min dwell time. CsI particles were evenly distributed throughout the pellet and were located at the grain boundaries. The sintering rate is dependent on the O/U ratio of the powder. Addition of CsI also acts as a sintering aid, reducing the temperature of maximum densification. - Highlights: • A new method was developed to incorporation of volatile fission products simulants into dense nuclear fuel pellets. • CsI doped UO{sub 2} pellets were synthetized for the first time, by Spark Plasma Sintering. • The sintering rate in Spark Plasma Sintering is dependent on the O/U ratio of UO{sub 2+x}.

Alkali/TX{sub 2} catalysts for CO/H{sub 2} conversion to C{sub 1}-C{sub 4} alcohols. Technical progress report, March 1989--August 1989

Energy Technology Data Exchange (ETDEWEB)

Klier, K.; Herman, R.G.; Bastian, R.D.; Flanagan, K.L.

1989-12-31

Ruthenium disulfide catalysts have been synthesized, tested, and characterized during this period of research. It was observed that both the undoped and Cs-doped RuS{sub 2} catalysts produced alcohols and lower amounts of hydrocarbons from H{sub 2}/CO = 1.0 synthesis gas at temperatures above 300{degree}C. Calcination and catalytic testing resulted in partial reduction of the RuS{sub 2} to Ru{sup o}. Calcination under H{sub 2}S prevented the partial reduction of the RuS{sub 2} catalyst, but subsequent catalytic testing again resulted in the formation of a quantity of Ru{sup o}. A Cs-doped RuS{sub 2} catalyst was prepared, but it might have had too high of a loading of Cs. Upon testing, a lower activity was observed for the doped catalyst compared with the undoped catalyst, but the alcohol selectivity was the same for the two catalysts.

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

Science.gov (United States)

Niyitanga, Theophile; Jeong, Hae Kyung

2018-05-01

Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

Evaluation of the 137Cs technique for estimating wind erosion losses for some sandy Western Australian soils

International Nuclear Information System (INIS)

Harper, R.J.; Gilkes, R.J.

1994-01-01

The utility of the caesium-137 technique, for estimating the effects of wind erosion, was evaluated on the soils of a semi-arid agricultural area near Jerramungup, Western Australia. The past incidence of wind erosion was estimated from field observations of soil profile morphology and an existing remote sensing study. Erosion was limited to sandy surfaced soils (0-4% clay), with a highly significant difference (P 137 Cs values between eroded and non-eroded sandy soils, with mean values of 243±17 and 386±13 Bq m -2 respectively. Non-eroded soils, with larger clay contents, had a mean 137 Cs content of 421±26 Bq m -2 , however, due to considerable variation between replicate samples, this value was not significantly different from that of the non-eroded sands. Hence, although the technique discriminates between eroded and non-eroded areas, the large variation in 137 Cs values means that from 27 to 96 replicate samples are required to provide statistically valid estimates of 137 Cs loss. The occurrence of around 18% of the total 137 Cs between 10 and 20 cm depth in these soils, despite cultivation being confined to the surface 9 cm, suggests that leaching of 137 Cs occurs in the sandy soils, although there was no relationship between clay content and 137 Cs value for either eroded or non-eroded soils. In a multiple linear regression, organic carbon content and the mean grain size of the eroded soils explained 35% of the variation in 137 Cs content. This relationship suggests that both organic carbon and 137 Cs are removed by erosion, with erosion being more prevalent on soils with a finer sand fraction. Clay and silt contents do not vary with depth in the near-surface horizons of the eroded sandy soils, hence it is likely that wind erosion strips the entire surface horizon with its 137 Cs content, rather than selectively winnowing fine material. 71 refs., 6 tabs., 2 fig

Identification of Thioredoxin Target Disulfides Using Isotope-Coded Affinity Tags

DEFF Research Database (Denmark)

Hägglund, Per; Bunkenborg, Jakob; Maeda, Kenji

2014-01-01

Thioredoxins (Trx) are small redox proteins that reduce disulfide bonds in various target proteins and maintain cellular thiol redox control. Here, a thiol-specific labeling and affinity enrichment approach for identification and relative quantification of Trx target disulfides in complex protein...... reduction is determined by LC-MS/MS-based quantification of tryptic peptides labeled with "light" (12C) and "heavy" (13C) ICAT reagents. The methodology can be adapted to monitor the effect of different reductants or oxidants on the redox status of thiol/disulfide proteomes in biological systems....... extracts is described. The procedure utilizes the isotope-coded affinity tag (ICAT) reagents containing a thiol reactive iodoacetamide group and a biotin affinity tag to target peptides containing reduced cysteine residues. The identification of substrates for Trx and the extent of target disulfide...

Thermodynamic and mechanical effects of disulfide bonds in CXCLl7 chemokine

Science.gov (United States)

Singer, Christopher

Chemokines are a family of signaling proteins mainly responsible for the chemotaxis of leukocytes, where their biological activity is modulated by their oligomerization state. Here, the dynamics and thermodynamic stability are characterized in monomer and homodimer structures of CXCL7, one of the most abundant platelet chemokines. The effects of dimerization and disulfide bond formation are investigated using computational methods that include molecular dynamics (MD) simulations and the Distance Constraint Model (DCM). A consistent picture emerges for the effect of dimerization and role of the Cys5-Cys31 and Cys7- Cys47 disulfide bonds. Surprisingly, neither disulfide bond is critical for maintaining structural stability in the monomer or dimer, although the monomer is destabilized more than the dimer upon removal of disulfide bonds. Instead, it is found that disulfide bonds influence the native state dynamics as well as modulates the relative stability between monomer and dimer. The combined analysis elucidates how CXCL7 is mechanically stable as a monomer, and how upon dimerization flexibly correlated motions are induced between the 30s and 50s loop within each monomer and across the dimer interface. Interestingly, the greatest gain in flexibility upon dimerization occurs when both disulfide bonds are present in each domain, and the homodimer is least stable relative to its two monomers. These results suggest the highly conserved disulfide bonds in chemokines facilitate a structural mechanism for distinguishing functional characteristics between monomer and dimer.

Electronic Spectra of Cs2NaYb(NO2)6: Is There Quantum Cutting?

Science.gov (United States)

Luo, Yuxia; Liu, Zhenyu; Hau, Sam Chun-Kit; Yeung, Yau Yuen; Wong, Ka-Leung; Shiu, Kwok Keung; Chen, Xueyuan; Zhu, Haomiao; Bao, Guochen; Tanner, Peter A

2018-05-03

The crystal structure and electronic spectra of the T h symmetry hexanitritoytterbate(III) anion have been studied in Cs 2 NaY 0.96 Yb 0.04 (NO 2 ) 6 , which crystallizes in the cubic space group Fm3̅. The emission from Yb 3+ can be excited via the NO 2 - antenna. The latter electronic transition is situated at more than twice the energy of the former, but at room temperature, one photon absorbed at 470 nm in the triplet state produces no more than one photon emitted. Some degree of quantum cutting is observed at 298 K under 420 nm excitation into the singlet state and at 25 K using excitation into either state. The quantum efficiency is ∼10% at 25 K. The energy level scheme of Yb 3+ has been deduced from excitation and emission spectra and calculated by crystal field theory. New improved energy level calculations are also reported for the Cs 2 NaLn(NO 2 ) 6 (Ln = Pr, Eu, Tb) series using the f- Spectra package. The neat crystal Cs 2 NaYb(NO 2 ) 6 has also been studied, but results were unsatisfactory due to sample decomposition, and this chemical instability makes it unsuitable for applications.

Electrospinning in Situ Synthesis of Graphene-Doped Porous Copper Indium Disulfide/Carbon Composite Nanofibers for Highly Efficient Counter Electrode in Dye-Sensitized Solar Cells

International Nuclear Information System (INIS)

He, Jianxin; Zhou, Mengjuan; Wang, Lidan; Zhao, Shuyuan; Wang, Qian; Ding, Bin; Cui, Shizhong

2016-01-01

Highlights: • P-GN@CuInS 2(*) /C nanofibers were fabricated via electrospinning, in situ synthesis. • CuInS 2 nanocrystals were uniformly anchored in wrapped RGO to form nanofiber structure. • P-GN@CuInS 2 /C nanofibers exhibited porous and 3D superfine fiber morphology. • Graphene nanosheets led well-dispersed growth of CuInS 2 nanocrystals in nanofibers. • DSSC assembled using p-GN@CuInS 2 /C CE delivered a conversion efficiency of 7.23%. - Abstract: Porous graphene-doped copper indium disulfide/carbon (p-GN@CuInS 2 /C) composite nanofibers were fabricated via electrospinning, in situ synthesis, and carbonization. A polyacrylonitrile (PAN) solution containing graphene oxide nanosheets, copper dichloride (CuCl 2 ), indium trichloride (InCl 3 ), and thiourea (Tu.) in a mixed solvent of N,N-dimethylformamide/trichloromethane (DMF/CF) was used as the precursor solution for electrospinning. The resulting porous GN@CuInS 2 /C nanofibers were 107 ± 24 nm in diameter, and graphene nanosheets anchored with chalcopyrite CuInS 2 nanocrystals 7–12 nm in diameter were overlapped and embedded in the carbon matrix, aligning along the fiber axial direction. The Brunauer–Emmett–Teller (BET) surface area of the p-GN@CuInS 2 /C composite nanofibers was 795 m 2 /g, with a total pore volume of 0.71 cm 3 /g. These values were significantly larger than those of the sample without graphene and CuInS 2 /C nanofibers. A dye-sensitized solar cell (DSSC) assembled using the p-GN@CuInS 2 /C nanofibers as the counter electrode (CE) delivered a photoelectric conversion efficiency of 7.23%, which was higher than the efficiencies of DSSCs assembled using the samples without graphene (6.48%) and with the CuInS 2 /C nanofibers (5.45%). It was also much higher than that of the DSSC with a Pt CE (6.34%). The excellent photoelectric performance of the p-GN@CuInS 2 /C CE was attributed to its special hierarchical porous structure, which facilitated permeation of the liquid

Sedimentation rates measurements in former channels of the upper Rhône river using Chernobyl 137Cs and 134Cs as tracers.

Science.gov (United States)

Rostan, J C; Juget, J; Brun, A M

1997-01-30

Former river channels are aquatic ecosystems with a different geomorphology generated by fluvial dynamics more or less linked to the main channel. They present different ecological successions to become terrestrial ecosystems and are thus supposed to have different sedimentation rates. The aim of this paper is to assess this sedimentation rate using radioactive tracer methodology commonly used in lake studies. Chernobyl impacts, expressed in 137Cs concentration and 137Cs/134Cs ratio, were determined in sediment cores. Sites (21) were sampled in the alluvial plain of the Upper Rhône River from 1989 to 1994. The contamination presented a high spatial heterogeneity. The maximum values encountered by site ranged between 34 and 541 Bq/kg of dry matter. The method generally gave good core profiles. Sedimentation rate ranged between 0.14 and 0.70 cm/year for the former meanders and between 0.14 and 2.86 cm/year for the braided channels. The sediment accumulation rates ranged from 0.03 to 0.25 g/cm2 per year and 0.03 to 2.26 g/cm2 per year, respectively. These values are similar to those found for Lake Geneva. The importance of the former channels in relation to the main channel is enhanced by the higher contamination and radionuclides retention. The sediment accumulation rate is related to the organic carbon content in the sediment. A comparison between two former channels with different productivity showed that the the allogenous driven system presents a high organic sediment accumulation rate with a low organic content in the sediment and inversely, a low organic sediment accumulation rate with a high organic carbon content was found for the autogenous drive system.

Elegant Face-Down Liquid-Space-Restricted Deposition of CsPbBr3 Films for Efficient Carbon-Based All-Inorganic Planar Perovskite Solar Cells.

Science.gov (United States)

Teng, Pengpeng; Han, Xiaopeng; Li, Jiawei; Xu, Ya; Kang, Lei; Wang, Yangrunqian; Yang, Ying; Yu, Tao

2018-03-21

It is a great challenge to obtain the uniform films of bromide-rich perovskites such as CsPbBr 3 in the two-step sequential solution process (two-step method), which was mainly due to the decomposition of the precursor films in solution. Herein, we demonstrated a novel and elegant face-down liquid-space-restricted deposition to inhibit the decomposition and fabricate high-quality CsPbBr 3 perovskite films. This method is highly reproducible, and the surface of the films was smooth and uniform with an average grain size of 860 nm. As a consequence, the planar perovskite solar cells (PSCs) without the hole-transport layer based on CsPbBr 3 and carbon electrodes exhibit enhanced power conversion efficiency (PCE) along with high open circuit voltage ( V OC ). The champion device has achieved a PCE of 5.86% with a V OC of 1.34 V, which to our knowledge is the highest performing CsPbBr 3 PSC in planar structure. Our results suggest an efficient and low-cost route to fabricate the high-quality planar all-inorganic PSCs.

Calcite Phase Conversion Prediction Model for CaO-Al2O3-SiO2 Slag: An Aqueous Carbonation Process at Ambient Pressure

Science.gov (United States)

Zhang, Huining; Dong, Jianhong; Li, Hui; Xiong, Huihui; Xu, Anjun

2018-06-01

To evaluate the effect of the mineralogical phase on carbonation efficiency for CaO-Al2O3-SiO2 slag, a calcite phase conversion prediction model is proposed. This model combines carbon dioxide solubility with carbonation reaction kinetic analysis to improve the prediction capability. The effect of temperature and carbonation time on the carbonation degree is studied in detail. Results show that the reaction rate constant ranges from 0.0135 h-1 to 0.0458 h-1 and that the mineralogical phase contribution sequence for the carbonation degree is C2S, CaO, C3A and CS. The model accurately predicts the effect of temperature and carbonation time on the simulated calcite conversion, and the results agree with the experimental data. The optimal carbonation temperature and reaction time are 333 K and 90 min, respectively. The maximum carbonation efficiency is about 184.3 g/kg slag, and the simulation result of the calcite phase content in carbonated slag is about 20%.

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

DEFF Research Database (Denmark)

Björnberg, Olof; Maeda, Kenji; Svensson, Birte

2012-01-01

Thioredoxin reduces disulfide bonds, thus regulating activities of target proteins in various biological systems, e.g., inactivation of inhibitors of starch hydrolases and proteases in germinating plant seeds. In the three-dimensional structure of a complex with barley α-amylase/subtilisin inhibi......Thioredoxin reduces disulfide bonds, thus regulating activities of target proteins in various biological systems, e.g., inactivation of inhibitors of starch hydrolases and proteases in germinating plant seeds. In the three-dimensional structure of a complex with barley α...... thioredoxin reductase. HvTrxh2 M88G and M88A adjacent to the invariant cis-proline lost efficiency in both BASI disulfide reduction and recycling by thioredoxin reductase. These effects were further pronounced in M88P lacking a backbone NH group. Remarkably, HvTrxh2 E86R in the same loop displayed overall...... retained catalytic properties, with the exception of a 3-fold increased activity toward BASI. From the 104VGA106 loop, a backbone hydrogen bond donated by A106 appears to be important for target disulfide recognition as A106P lost 90% activity toward BASI but was efficiently recycled by thioredoxin...

Protein disulfide bond generation in Escherichia coli DsbB–DsbA

International Nuclear Information System (INIS)

Inaba, Kenji

2008-01-01

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

Separation of CsCl and SrCl{sub 2} from a ternary CsCl-SrCl{sub 2}-LiCl via a zone refining process for waste salt minimization of pyroprocessing

Energy Technology Data Exchange (ETDEWEB)

Shim, Moonsoo [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Choi, Ho Gil; Yi, Kyung Woo; Hwang, Il Soon [Graduate School of Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Graduate School of Energy Science and Technology, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Graduate School of Department of Advanced Materials Engineering, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of); Rapid Solidified Materials Research Center, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 34134 (Korea, Republic of)

2016-11-15

The purification of LiCl salt mixture has traditionally been carried out by a melt crystallization process. To improve the throughput of zone refining, three heaters were installed in the zone refiner. The zone refining method was used to grow pure LiCl salt ingots from LiCl-CsCl-SrCl{sub 2} salt mixture. The main investigated parameters were the heater speed and the number of passes. A change in the LiCl crystal grain size was observed according to the horizontal direction. From each zone refined salt ingot, samples were collected horizontally. To analyze the concentrations of Sr and Cs, an inductively coupled plasma optical emission spectrometer and inductively coupled plasma mass spectrometer were used, respectively. The experimental results show that Sr and Cs concentrations at the initial region of the ingot were low and reached their peak at the final freezing region of the salt ingot. Concentration results of zone refined salt were compared with theoretical results yielded by the proposed model to validate its predictions. The k{sub eff} of Sr and Cs were 0.13 and 0.11, respectively. The decontamination factors of Sr and Cs were 450 and 1650, respectively. - Highlights: • The LiCl-CsCl-SrCl{sub 2} salt ingot was purified by zone refining technique to minimize waste salt. • The concentration distribution of Cs and Sr were analyzed by mass transfer equation. • The decontamination factors of Cs and Sr were 1600 and 450 respectively in case of 60% of recovery yield.

Moessbauer Spectroscopy of Martian and Sverrefjell Carbonates

Science.gov (United States)

Agresti, David G.; Morris, Richard V.

2011-01-01

Mars, in its putative "warmer, wetter: early history, could have had a CO2 atmosphere much denser than its current value of Chocolate Pots in Yellowstone National Park (YNP) are shown; they are the same within error. For Comanche carbonate summed over 210-270 K, (CS, QS) = (1.23, 1.95) mm/s. The value of QS for Sverrefjell carbonate at 295 K, (CS, QS) = (1.25, 1.87) mm/s, is also plotted, and the plot shows that the QS for the Sverrefjell carbonate agrees within error with the Comanche data extrapolated to 295 K. This agreement is additional evidence that the Sverrefjell carbonates are Mossbauer analogues for the Comanche carbonates, and that both carbonates might have precipitated from solutions that became carbonate rich by passing through buried carbonate deposits.

An evidence for the strong association of N-methyl-2-pyrrolidinone with some organic species in three Chinese bituminous coals

Energy Technology Data Exchange (ETDEWEB)

Liu, C.M.; Zong, Z.M.; Jia, J.X.; Liu, G.F.; Wei, X.Y. [China University of Mining and Technology, Xuzhou (China). School for Chemical Engineering

2008-04-15

Three Chinese bituminous coals collected from Shenfu, Heidaigou and Feicheng coal fields were respectively extracted with carbon-disulfide/N-methyl-2-pyrrolidinone (CS{sub 2}/NMP) mixed solvent (volume ratio 1:1) at room temperature followed by distillation of CS{sub 2} under ambient pressure and subsequent removal of most of NMP by distillation at 110{sup o}C under reduced pressure to afford mixed solvent-extractable fractions (MSEFs) with small amount of NMP. Acetone-extractable fraction 1 (AEF1) was obtained by extracting each MSEF under ultrasonic irradiation at room temperature and subsequently using a Soxhlet extractor. Direct extraction of each bituminous coal affords acetone-soluble fraction 2 (AEF2). GC/MS analysis shows that mlz of base or secondary peak in mass spectra of a series of components from each AEF1 is 98, whereas such components were not detected in AEF2. Since m/z of base peak in mass spectrum of NMP itself is 99, the base or secondary peak at m/z 98 should result from loss of a-H from NMP, i.e., NMP is strongly associated with some organic species (OSs) and thereby the components detected with base or secodary peak at m/z 98 in their mass spectra should be associated NMP-OS.

Disulfide bonds in the ectodomain of anthrax toxin receptor 2 are required for the receptor-bound protective-antigen pore to function.

Directory of Open Access Journals (Sweden)

Jianjun Sun

Full Text Available BACKGROUND: Cell-surface receptors play essential roles in anthrax toxin action by providing the toxin with a high-affinity anchor and self-assembly site on the plasma membrane, mediating the toxin entry into cells through endocytosis, and shifting the pH threshold for prepore-to-pore conversion of anthrax toxin protective antigen (PA to a more acidic pH, thereby inhibiting premature pore formation. Each of the two known anthrax toxin receptors, ANTXR1 and ANTXR2, has an ectodomain comprised of an N-terminal von Willebrand factor A domain (VWA, which binds PA, and an uncharacterized immunoglobulin-like domain (Ig that connects VWA to the membrane-spanning domain. Potential roles of the receptor Ig domain in anthrax toxin action have not been investigated heretofore. METHODOLOGY/PRINCIPAL FINDINGS: We expressed and purified the ANTXR2 ectodomain (R2-VWA-Ig in E. coli and showed that it contains three disulfide bonds: one in R2-VWA and two in R2-Ig. Reduction of the ectodomain inhibited functioning of the pore, as measured by K(+ release from liposomes or Chinese hamster ovary cells or by PA-mediated translocation of a model substrate across the plasma membrane. However, reduction did not affect binding of the ectodomain to PA or the transition of ectodomain-bound PA prepore to the pore conformation. The inhibitory effect depended specifically on reduction of the disulfides within R2-Ig. CONCLUSIONS/SIGNIFICANCE: We conclude that disulfide integrity within R2-Ig is essential for proper functioning of receptor-bound PA pore. This finding provides a novel venue to investigate the mechanism of anthrax toxin action and suggests new strategies for inhibiting toxin action.

A study of calcium carbonate/multiwalled-carbon nanotubes/chitosan composite coatings on Ti–6Al–4V alloy for orthopedic implants

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Rasha A., E-mail: rashaauf@yahoo.com [Chemistry Department, Faculty of Science, Taif University (Saudi Arabia); Forensic Chemistry Laboratories, Medico Legal Department, Ministry of Justice, Cairo (Egypt); Fekry, Amany M. [Chemistry Department, Faculty of Science, Cairo University, Giza 12613 (Egypt); Farghali, R.A. [Chemistry Department, Faculty of Science, Taif University (Saudi Arabia); Chemistry Department, Faculty of Science, Cairo University, Giza 12613 (Egypt)

2013-11-15

In an attempt to increase the stability, bioactivity and corrosion resistance of Ti–6Al–4V alloy, chitosan (CS) biocomposite coatings reinforced with multiwalled-carbon nanotubes (MWCNTs), and calcium carbonate (CaCO{sub 3}) for surface modification were utilized by electroless deposition. Scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) reveals the formation of a compact and highly crosslinked coatings. Electrochemical techniques were used to investigate the coats stability and resistivity for orthopedic implants in simulated body fluid (SBF). The results show that E{sub st} value is more positive in the following order: CaCO{sub 3}/MWCNTs/CS > CS/MWCNTs > CS > MWCNTs. The calculated i{sub corr} was 0.02 nA cm{sup −2} for CaCO{sub 3}/MWCNTs/CS which suggested a high corrosion resistance.

Cs+ and Sr2+ adsorption selectivity of zeolites in relation to radioactive decontamination

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M.W. Munthali

2015-09-01

Full Text Available Zeolites are used as adsorbents of cationic elements in the radioactive decontamination process of water, soil and others. We determined Cs+ and Sr2+ adsorption selectivity of some zeolites to know effective zeolite species for the decontamination of radioactive Cs and Sr. A 30 mL mixed solution containing up to 15 mg L−1 of non-radioactive Cs+ or Sr+ and up to 0.50 M of Na+ or K+ was mixed with 0.5 g of Linde-type A, Na-P1, faujasite X, faujasite Y and mordenite. Among the zeolites, mordenite had the highest Cs+ adsorption selectivity, and the selectivity had no correlation to the cation exchange capacity (CEC of the zeolites. In contrast, Sr2+ adsorption selectivity of the zeolites positively correlated with the CEC of the zeolites; Linde-type A with the highest CEC showed the highest adsorption selectivity, and its adsorption rate was more than 99.9% even in the presence of 0.5 M K+. A simulated soil decontamination experiment of Cs from a Cs-retaining vermiculite by using mordenite and that of Sr from a Sr-retaining vermiculite by using Linde-type A showed decontamination rates of more than 90%.

Preventing disulfide bond formation weakens non-covalent forces among lysozyme aggregates.

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Vijay Kumar Ravi

Full Text Available Nonnative disulfide bonds have been observed among protein aggregates in several diseases like amyotrophic lateral sclerosis, cataract and so on. The molecular mechanism by which formation of such bonds promotes protein aggregation is poorly understood. Here in this work we employ previously well characterized aggregation of hen eggwhite lysozyme (HEWL at alkaline pH to dissect the molecular role of nonnative disulfide bonds on growth of HEWL aggregates. We employed time-resolved fluorescence anisotropy, atomic force microscopy and single-molecule force spectroscopy to quantify the size, morphology and non-covalent interaction forces among the aggregates, respectively. These measurements were performed under conditions when disulfide bond formation was allowed (control and alternatively when it was prevented by alkylation of free thiols using iodoacetamide. Blocking disulfide bond formation affected growth but not growth kinetics of aggregates which were ∼50% reduced in volume, flatter in vertical dimension and non-fibrillar in comparison to control. Interestingly, single-molecule force spectroscopy data revealed that preventing disulfide bond formation weakened the non-covalent interaction forces among monomers in the aggregate by at least ten fold, thereby stalling their growth and yielding smaller aggregates in comparison to control. We conclude that while constrained protein chain dynamics in correctly disulfide bonded amyloidogenic proteins may protect them from venturing into partial folded conformations that can trigger entry into aggregation pathways, aberrant disulfide bonds in non-amyloidogenic proteins (like HEWL on the other hand, may strengthen non-covalent intermolecular forces among monomers and promote their aggregation.

The effects of O-MWNTs on the performances of PVA-CS-O-MWNTs/PAN pervaporation membrane

Directory of Open Access Journals (Sweden)

Yan Xi

2017-08-01

Full Text Available Oxidized multi-wall carbon nanotubes(O-MWNTs were used as inorganic nanofillers and added in the coating solution of polyvinyl alcohol (PVA-chitosan (CS mixtures,and the PVA-CS-O-MWNTs/PAN hollow fiber membranes were prepared by the dip-coating method for the pervaporation separation of methanol (MeOH/dimethyl carbonate (DMC mixture.The process conditions including the O-MWNTs amount,heat treatment temperature,and feed temperature were investigated in detail.The results indicate that the addition of O-MWNTs can enhance the permeation flux,hydrophilicity and mechanical properties of PVA-CS-O-MWNTs/PAN membranes.The preferable conditions are that O-MWNTs amount,heat treatment temperature,feed temperature,and the concentration of MeOH are 0.1%,80℃,40℃ and 70%,respectively.Thus,the permeation fluxand MeOHselectivity can attain 210 g·m-2·h-1and 7.82,respectively.

The quinternary thiophosphate Cs0.5Ag0.5Nb2PS10

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Sojeong Park

2010-07-01

Full Text Available The quinternary thiophosphate Cs0.5Ag0.5Nb2PS10, cesium silver tris(disulfido[tetrathiophosphato(V]diniobate(IV, has been prepared from the elements using a CsCl flux. The crystal structure is made up of ∞1[Nb2PS10] chains expanding along [010]. These chains are built up from bicapped trigonal-prismatic [Nb2S12] units and tetrahedral [PS4] groups and are linked through a linear S—Ag—S bridge, forming a two-dimensional layer. These layers then stack on top of each other, completing the three-dimensional structure with an undulating van der Waals gap. The disordered Cs+ ions reside on sites with half-occupation in the voids of this arrangement. Short [2.8843 (5 Å] and long [3.7316 (4 Å] Nb—Nb distances alternate along the chains, and anionic S22− and S2− species are observed. The charge balance of the compound can be represented by the formula [Cs+]0.5[Ag+]0.5[Nb4+]2[PS43−][S22−]3.

Cs2CO3-promoted polycondensation of CO2with diols and dihalides for the synthesis of miscellaneous polycarbonates

KAUST Repository

Chen, Zuliang

2016-07-12

A one-pot protocol for the direct synthesis of polycarbonates through polycondensation of diols, dihalides and CO2 in the presence of Cs2CO3 is described. The conditions were optimized by studying the polycondensation of CO2 with 1,4-phenylenedimethanol and 1,4-dibromobutane as model monomers. Then, diols and dihalides with different spacers between the reactive groups including aliphatic, aromatic and poly(ethylene glycol) were tested under optimal conditions. Miscellaneous polycarbonates exhibiting molar masses in the range of 43 000 g mol-1 (GPC) and conversion higher than 96% could be obtained. The proposed mechanism rules out the possibility of ether linkage formation during polycondensation and accounts for the creation of carbonate linkages in two different ways. The thermal properties of the synthesized polycarbonates were unveiled by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). © 2016 The Royal Society of Chemistry.

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

Science.gov (United States)

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

2018-02-16

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

Synthesis and Performance of Tungsten Disulfide/Carbon (WS2/C) Composite as Anode Material

Science.gov (United States)

Yuan, Zhengyong; Jiang, Qiang; Feng, Chuanqi; Chen, Xiao; Guo, Zaiping

2018-01-01

The precursors of an amorphous WS2/C composite were synthesized by a simple hydrothermal method using Na2WO4·2H2O and CH3CSNH2 as raw materials, polyethylene glycol as dispersant, and glucose as the carbon source. The as-synthesized precursors were further annealed at a low temperature in flowing argon to obtain the final materials (WS2/C composite). The structure and morphology of the WS2/C composite were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical properties were tested by galvanostatic charge/discharge testing and alternating current (AC) impedance measurements. The results show that the as-prepared amorphous WS2/C composite features both high specific capacity and good cycling performance at room temperature within the potential window from 3.0 V to 0.01 V (versus Li+/Li) at current density of 100 mAg-1. The achieved initial discharge capacity was 1080 mAhg-1, and 786 mAhg-1 was retained after 170 cycles. Furthermore, the amorphous WS2/C composite exhibited a lower charge/discharge plateau than bare WS2, which is more beneficial for use as an anode. The cyclic voltammetry and AC impedance testing further confirmed the change in the plateau and the decrease in the charge transfer resistance in the WS2/C composite. The chemical formation process and the electrochemical mechanism of the WS2/C composite are also presented. The amorphous WS2/C composite can be used as a new anode material for future applications.

ReaxFF Reactive Force-Field Study of Molybdenum Disulfide (MoS2).

Science.gov (United States)

Ostadhossein, Alireza; Rahnamoun, Ali; Wang, Yuanxi; Zhao, Peng; Zhang, Sulin; Crespi, Vincent H; van Duin, Adri C T

2017-02-02

Two-dimensional layers of molybdenum disulfide, MoS 2 , have been recognized as promising materials for nanoelectronics due to their exceptional electronic and optical properties. Here we develop a new ReaxFF reactive potential that can accurately describe the thermodynamic and structural properties of MoS 2 sheets, guided by extensive density functional theory simulations. This potential is then applied to the formation energies of five different types of vacancies, various vacancy migration barriers, and the transition barrier between the semiconducting 2H and metallic 1T phases. The energetics of ripplocations, a recently observed defect in van der Waals layers, is examined, and the interplay between these defects and sulfur vacancies is studied. As strain engineering of MoS 2 sheets is an effective way to manipulate the sheets' electronic and optical properties, the new ReaxFF description can provide valuable insights into morphological changes that occur under various loading conditions and defect distributions, thus allowing one to tailor the electronic properties of these 2D crystals.

Chest pain in rubber chemical workers exposed to carbon disulphide and methaemoglobin formers

Energy Technology Data Exchange (ETDEWEB)

Oliver, L.C.; Weber, R.P.

1984-08-01

A cross sectional prevalence study of chest pain in 94 rubber chemical workers exposed to carbon disulfide (CS2) and methemoglobin forming aromatic amines was carried out. The purpose of the study was to determine whether the prevalence of chest pain or coronary heart disease (CHD), or both, in exposed individuals exceeded that of a group of non-exposed individuals from the same plant. Cardiovascular, smoking, and occupational histories were obtained. Blood pressure, height, weight, serum cholesterol, and fasting blood glucose were measured. Resting electrocardiograms (ECGs) were obtained on all study participants, as were exercise stress tests on selected exposed individuals. Matching eliminated important known risk factors for coronary artery disease. Both chest pain and angina were significantly related to exposure, controlling for age and cigarette smoking. This association was not dependent on duration of exposure as defined by 10 or more years of employment in the department of interest. CHD as defined by angina, a history of myocardial infarction, or a coronary ECG or a combination of these occurred more frequently among exposed workers. The number of abnormal ECGs in the exposed group was twice that in the control group, but the difference was not statistically significant. Age rather than exposure appeared to be the important variable associated with raised blood pressure. Neither biological measures of exposure nor ECGs showed an acute effect of workplace exposures on the myocardium. Possible additive or multiplicative effects of individual chemical agents could not be evaluated. Appropriate modification of medical surveillance of rubber chemical workers with exposure to CS2 and aromatic amines is warranted.

UV absorption cross-sections of selected sulfur-containing compounds at temperatures up to 500°C

DEFF Research Database (Denmark)

Grosch, Helge; Fateev, Alexander; Clausen, Sønnik

2015-01-01

The temperature dependence of the ultraviolet absorption cross-sections of three different sulfur containing compounds, hydrogen sulfide (H2S), carbon disulfide (CS2) and carbonyl sulfide (OCS), are presented between 200nm and 360nm at a resolution of 0.018nm. The absorption cross-sections for each...... compound are initially compared with those available in the literature, followed by the discussion of the measurements and their spectral features at three temperatures up to 500°C/773K. Uncertainties in the measured absorption cross-sections are also addressed....

Energy transfer between the Eu2+ dipole and aggregate centers in CsBr:Eu crystals

International Nuclear Information System (INIS)

Zorenko, Yu.; Turchak, R.; Voznjak, T.

2007-01-01

The energy transfer between the Eu 2+ -V Cs dipole centers and presumable CsEuBr 3 aggregate centers has been studied in CsBr:Eu crystals by means of investigation of their time-resolved emission spectra and luminescence decay kinetics at 300 K

One-dimensional zinc selenophosphates: A_2ZnP_2Se_6 (A = K, Rb, Cs)

International Nuclear Information System (INIS)

Haynes, Alyssa S.; Lee, Katherine; Kanatzidis, Mercouri G.

2016-01-01

The new compounds A_2ZnP_2Se_6 (A = K, Rb, Cs) were synthesized via molten salt flux syntheses. The crystals feature one-dimensional "1/_∞[ZnP_2Se_6]"2"- chains charge balanced by alkali metal ions between the chains. K_2ZnP_2Se_6 crystallizes in the monoclinic space group P2_1/c; cell parameters a = 12.537(3) Aa, b = 7.2742(14) Aa, c = 14.164(3) Aa, β = 109.63(3) , Z = 4, and V = 1216.7(4) Aa"3. Rb_2ZnP_2Se_6 and Cs_2ZnP_2Se_6 are isotypic, crystallizing in the triclinic space group P anti 1. Rb_2ZnP_2Se_6 has cell parameters of a = 7.4944(15) Aa, b = 7.6013(15) Aa, c = 12.729(3) Aa, α = 96.57(3) , β = 105.52(3) , γ = 110.54(3) , Z = 2, and V = 636.6(2) Aa"3. Cs_2ZnP_2Se_6 has cell parameters of a = 7.6543(6) Aa, b = 7.7006(6) Aa, c = 12.7373(11) Aa, α = 97.007(7) , β = 104.335(7) , γ = 109.241(6) , Z = 2, and V = 669.54(10) Aa"3. (Copyright copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Science.gov (United States)

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

2016-01-01

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

Influence of air exposure on CsI photocathodes

Energy Technology Data Exchange (ETDEWEB)

Xie, Yuguang, E-mail: ygxie@mail.ihep.ac.cn [State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, CAS and University of Science and Technology of China, Beijing 100049 (China); Zhang, Aiwu; Liu, Yingbiao [State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, CAS and University of Science and Technology of China, Beijing 100049 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Liu, Hongbang [Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Guangxi University, Naning 530004 (China); Hu, Tao; Zhou, Li; Cai, Xiao; Fang, Jian; Yu, Boxiang [State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, CAS and University of Science and Technology of China, Beijing 100049 (China); Ge, Yongshuai [State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, CAS and University of Science and Technology of China, Beijing 100049 (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Lue, Qiwen [Shanxi University, Taiyuan 030006 (China); Sun, Xilei; Sun, Lijun; Xue, Zheng [State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, CAS and University of Science and Technology of China, Beijing 100049 (China); Xie, Yigang; Zheng, Yangheng [Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Lue, Junguang [State Key Laboratory of Particle Detection and Electronics, Institute of High Energy Physics, CAS and University of Science and Technology of China, Beijing 100049 (China)

2012-10-11

We investigate the influence of air exposure on the quantum efficiency (QE) and surface morphology of CsI photocathodes (PCs), at relative humidities (RH) higher than 80% down to nearly 3% (both at room temperature) and a 60 Degree-Sign C baking condition. By atomic force microscopy (AFM) surface analysis, it is clearly seen that RH >60% speeds up water film formation and CsI dissolution on the surface of the photocathode at the minute scale, while both grain size and QE change slowly at RH <30% at the hour scale. In the baking environment, the peak QE decreases less than 1.5% (absolute) within one week, and a stainless steel substrate and electron beam evaporation technique tend to effectively weaken the influence of air. With an Au-coated FR-4 substrate, the QE degradation is found to strongly depend on wavelength in the range of 120-210 nm. According to spectra of X-ray photoelectron spectroscopy (XPS), an excess of cesium was observed and the chemical reaction between water and CsI when exposed to humid air is proved. It is found that carbon, and not H{sub 2}O or O{sub 2}, is the main pollutant in the baking condition.

Free tropospheric measurements of CS2 over a 45 deg N to 45 deg S latitude range

Science.gov (United States)

Tucker, B. J.; Maroulis, P. J.; Bandy, A. R.

1985-01-01

The mean value obtained from 52 free tropospheric measurements of CS2 over the 45 deg N-45 deg S latitude range was 5.7 pptv, with standard deviation and standard error of 1.9 and 0.3 pptv, respectively. Large fluctuations in the CS2 concentration are observed which reflect the apparent short atmospheric residence time and inhomogeneities in the surface sources of CS2. The amounts of CS2 in the Northern and Southern Hemispheres are statistically equal.

Reactive transport at the pore-scale: Geological Labs on Chip studies (GLoCs) for CO2 storage in saline aquifers

Science.gov (United States)

Azaroual, M. M.; Lassin, A., Sr.; André, L., Sr.; Devau, N., Sr.; Leroy, P., Sr.

2017-12-01

The near well bore of CO2 injection in saline aquifer is the main sensitive part of the targeted carbone storage reservoirs. The recent development of microfluidics tools mimicking porous media of geological reservoirs allowed studying physical, physico-chemical and thermodynamic mechanisms. We used the GLoCs "Geological Labs on Chip" to study dynamic and reactive transport processes at the pore scale induced by the CO2 geological storage. The present work is a first attempt to reproduce, by reactive transport modeling, an experiment of calcium carbonate precipitation during the co-injection of two aqueous solutions in a GLoC device. For that purpose, a new kinetics model, based on the transition-state-theory and on surface complexation modeling, was developed to describe the co-precipitation of amorphous calcium carbonate (ACC) and calcite. ACC precipitates and creates surface complexation sites from which calcite can nucleate and create new surface complexation sites. When the kinetics of calcite precipitation are fast enough, the consumption of matter leads to the dissolution of ACC. The modeling results were first compared to batch experiments (from the literature) and then applied with success to dynamic experiment observations carried out on a GLoC device (from the literature). On the other hand, we evaluated the solubility of CO2 in capillary waters that increases between 5 to 10 folds for reservoir conditions (200 bar and 100°C) compared to the bulk water. The GLoCs tools started to address an excellent and much finer degree of processes control (reactive transport processes, mixing effects, minerals precipitation and dissolution kinetics, etc.) thanks to in situ analysis and characterization techniques, allowing access in real time to relevant properties. Current investigations focus on key parameters influencing the flowing dynamics and trapping mechanisms (relative permeability, capillary conditions, kinetics of dissolution and precipitation of minerals).

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

DEFF Research Database (Denmark)

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

2001-01-01

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

Regeneration of Used Frying Palm Oil with Coffee Silverskin (CS), CS Ash (CSA) and Nanoparticles of CS (NCS).

Science.gov (United States)

Ismail, Samir Abd-Elmonem A; El-Anany, Ayman Mohammed; Ali, Rehab Farouk M

2017-01-01

The present investigation aimed to evaluate the efficiency of coffee silverskin (CS), CS ash (CSA) and nanoparticles of CS (NCS) in regeneration the quality of used frying palm oil. The adsorbents were mixed individually with used frying palm oil at level 4% (w/v) for 60 min. The properties of CS, CSA and NCS adsorbents were studied using (SEM) scanning electron microscopy technique. Some of physico-chemical characteristics of used frying palm oil (UFPO) and UFPO treated with adsorbents were determined. The results showed that the CS ash particles composed of irregular spherical and semispherical grains with deep cavities. The size of particles of CS ash ranged in diameter from 1.1 to 1.7 µm. The morphology of NCS consisted of cluster-type spherical nanoparticles and flakes. The particle size of NCS varies from 0.9 to 1.7 µm. Purification treatments caused marked (poil compared to untreated oil. The treatment of UFPO with 4% of adsorbents caused significant reductions in the content of free fatty acids ranged from 51.2 to 65.0%. The lowest level of peroxide (2.1 meq/kg) was recorded for UFPO treated with 4% of NCS. The highest reductions (72.8; 70.0%) in p-anisidine value were observed in UFPO treated with 4% of CSA and NCS, respectively. Treatment of UFPO with 4% of CS, CSA and NCS significantly lowered the polar content from 13.9% to 6.3, 4.8 and 3.9%, respectively. The results also indicate that CSA and NCS have nearly the same adsorption efficiency in lowering polymer content of UFPO. Filtration treatment of UFPO with 4% of CS, CSA and NCS markedly lowered the viscosity and colour values of treated UFPO.

Study of organic sulphur compounds (DMS, DMSP and CS2) in lagoon ecosystems: the case of the Venice lagoon.

Science.gov (United States)

Gambaro, Andrea; Moret, Ivo; Piazza, Rossano; Andreoli, Carlo; Corami, Fabiana; Turetta, Clara; Cescon, Paolo

2003-03-01

This study of the origin and fate of dimethyl sulphide (DMS) in a particular and complex lagoon ecosystem such as that of the Venice lagoon focuses on the temporal evolutions of DMS concentrations in surface water together with those of dimethylsulphoniopropionate (DMSP), carbon disulphide (CS2), nutrients (nitrate, nitrite, ammonium, phosphate, silicate), sulphate, chlorophyll a, chlorinity, water temperature and phytoplankton (composition and density). Measurements were made from 3 March 1997 to 23 July 1998 at three stations in the central part of the Venice lagoon. The temporal trends of DMS concentration showed an absolute maximum concentration in winter (65 nmol S/l, 19/2/1998, Stn. 1; 119 nmol S/l, 19/2/1998, Stn. 2; 29 nmol S/l, 17/2/1998, Stn. 3) and two relative maxima in the spring-summer period. The spring-summer secondary maxima of DMS concentration were related to the maxima of DMSP and chlorophyll a concentrations and consequently to phytoplanktonic abundance while the winter DMS maximum showed no relation to DMSP or to chlorophyll a suggesting that the production and the fate of DMS could be different for the two periods. According to previous studies the CS2 concentration increased in the spring, achieved its maximum in summer, decreased in autumn and fell to its minimum in winter.

Geochronology of Lake Baikal from 210Pb and 137Cs radioisotopes

International Nuclear Information System (INIS)

Carroll, J.; Williamson, M.; Lerche, I.; Karabanov, E.; Williams, D.F.

1999-01-01

Two box cores of near surface sediments were obtained from Lake Baikal in Southeastern Siberia, Russia. The cores were taken from the northern and southern basins of the lake during a joint American-Russian research expedition in the summer of 1994. The cores were analyzed for 210 Pb, 137 Cs and total organic carbon (TOC). Organic carbon is an indicator of photosynthetic production by phytoplankton, taking place primarily in the euphotic zone of the water column. Accumulation rates of TOC may be used as indicators of paleo-productivity when sedimentation rates are determined using the 210 Pb dating method and combined with both the density of sediment and organic carbon content. Accordingly, the lake is characterized by changes in accumulations of TOC, which may be linked to rates of sedimentation. Accumulations of TOC and sedimentation rates were higher in the southern basin site than in the northern basin site. The southern station core was taken from an area in close proximity to the Selenga River delta, which carries 50% of the water input to Lake Baikal. Productivity should thus be higher in this region due to the high nutrient input and sediment accumulation higher due to influx of riverine sediment input. Traces of 137 Cs (an anthropogenic product) were found in both cores. However, activities of 137 Cs were significantly higher in the southern basin, likely due to the input of the Selenga River in the southern region, which extends to a region in Mongolia in close proximity to the area of the Chinese atomic-bomb atmospheric testing of the 1970s. Application of a quantitative inverse model to the 210 Pb profiles yielded the following results: (i) station 12, near the Selenga Delta, had an accumulation rate of about 0.38 cm/y in 1957 but this rate was halved by 1980 to about 0.22 cm/y and has been roughly steady since that time; 137 Cs values are consistent with the age-to-depth determination from 210 Pb for station 12; (ii) since about 1960, station 5A in

Fluorescence Blinking and Photoactivation of All-Inorganic Perovskite Nanocrystals CsPbBr3 and CsPbBr2I.

Science.gov (United States)

Seth, Sudipta; Mondal, Navendu; Patra, Satyajit; Samanta, Anunay

2016-01-21

Study of the emission behavior of all-inorganic perovskite nanocrystals CsPbBr3 and CsPbBr2I as a function of the excitation power employing fluorescence correlation spectroscopy and conventional techniques reveals fluorescence blinking in the microsecond time scale and photoinduced emission enhancement. The observation provides insight into the radiative and nonradiative deactivation pathways of these promising substances. Because both blinking and photoactivation processes are intimately linked to the charge separation efficiency and dynamics of the nanocrystals, these key findings are likely to be helpful in realizing the true potential of these substances in photovoltaic and optoelectronic applications.

Production of recombinant disulfide-rich venom peptides for structural and functional analysis via expression in the periplasm of E. coli.

Directory of Open Access Journals (Sweden)

Julie K Klint

Full Text Available Disulfide-rich peptides are the dominant component of most animal venoms. These peptides have received much attention as leads for the development of novel therapeutic agents and bioinsecticides because they target a wide range of neuronal receptors and ion channels with a high degree of potency and selectivity. In addition, their rigid disulfide framework makes them particularly well suited for addressing the crucial issue of in vivo stability. Structural and functional characterization of these peptides necessitates the development of a robust, reliable expression system that maintains their native disulfide framework. The bacterium Escherichia coli has long been used for economical production of recombinant proteins. However, the expression of functional disulfide-rich proteins in the reducing environment of the E. coli cytoplasm presents a significant challenge. Thus, we present here an optimised protocol for the expression of disulfide-rich venom peptides in the periplasm of E. coli, which is where the endogenous machinery for production of disulfide-bonds is located. The parameters that have been investigated include choice of media, induction conditions, lysis methods, methods of fusion protein and peptide purification, and sample preparation for NMR studies. After each section a recommendation is made for conditions to use. We demonstrate the use of this method for the production of venom peptides ranging in size from 2 to 8 kDa and containing 2-6 disulfide bonds.

Solid-state e.m.f. and calorimetric measurements on Cs2Cr2O7(I)

International Nuclear Information System (INIS)

Venugopal, V.; Iyer, V.S.; Agarwal, R.; Roy, K.N.; Prasad, R.; Sood, D.D.

1987-01-01

The standard molar Gibbs free energy of formation of Cs 2 Cr 2 O 7 (1) has been determined in the temperature range 797 to 874 K, using a solid-oxide-electrolyte galvanic cell. The melting and transition temperatures, molar enthalpies of fusion and of transition of the same caesium compound were determined in the temperature range 662 to 826 K, using a high temperature Calvet microcalorimeter. Results on the standard molar enthalpy of formation of Cs 2 Cr 2 O 7 at 298.15 K are in good agreement with those reported by other workers. (U.K.)

Efficient soluble expression of disulfide bonded proteins in the cytoplasm of Escherichia coli in fed-batch fermentations on chemically defined minimal media.

Science.gov (United States)

Gąciarz, Anna; Khatri, Narendar Kumar; Velez-Suberbie, M Lourdes; Saaranen, Mirva J; Uchida, Yuko; Keshavarz-Moore, Eli; Ruddock, Lloyd W

2017-06-15

The production of recombinant proteins containing disulfide bonds in Escherichia coli is challenging. In most cases the protein of interest needs to be either targeted to the oxidizing periplasm or expressed in the cytoplasm in the form of inclusion bodies, then solubilized and re-folded in vitro. Both of these approaches have limitations. Previously we showed that soluble expression of disulfide bonded proteins in the cytoplasm of E. coli is possible at shake flask scale with a system, known as CyDisCo, which is based on co-expression of a protein of interest along with a sulfhydryl oxidase and a disulfide bond isomerase. With CyDisCo it is possible to produce disulfide bonded proteins in the presence of intact reducing pathways in the cytoplasm. Here we scaled up production of four disulfide bonded proteins to stirred tank bioreactors and achieved high cell densities and protein yields in glucose fed-batch fermentations, using an E. coli strain (BW25113) with the cytoplasmic reducing pathways intact. Even without process optimization production of purified human single chain IgA 1 antibody fragment reached 139 mg/L and hen avidin 71 mg/L, while purified yields of human growth hormone 1 and interleukin 6 were around 1 g/L. Preliminary results show that human growth hormone 1 was also efficiently produced in fermentations of W3110 strain and when glucose was replaced with glycerol as the carbon source. Our results show for the first time that efficient production of high yields of soluble disulfide bonded proteins in the cytoplasm of E. coli with the reducing pathways intact is feasible to scale-up to bioreactor cultivations on chemically defined minimal media.

Iodide-photocatalyzed reduction of carbon dioxide to formic acid with thiols and hydrogen sulfide

OpenAIRE

Berton, Mateo Otao; Mello, Rossella C. C.; González Núñez, María Elena

2016-01-01

The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO2 capture coupled with H2S removal may have been relevant as a prebiotic carbon dioxide fixation.

Analysis of Disulfide Bond Formation

NARCIS (Netherlands)

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

2017-01-01

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

Laser ionization of molecular clusters

International Nuclear Information System (INIS)

Desai, S.; Feigerle, C.S.

1995-01-01

Multiphoton ionization coupled with mass spectrometry was used to investigate molecular cluster distributions. Three examples will be discussed in this presentation. First, in studies of neat nitric oxide clusters, (NO) m , an interesting odd-even intensity alternation was observed and will be discussed in terms of electron-pairing considerations. In a separate study, the binary clusters comprising nitric oxide and methane preferentially form a stoichiometric cluster made up of repeating units of (NO) 2 CH 4 . These presumably represent a particularly strongly bound open-quotes van der Waalsclose quotes subunit. Finally, in similar studies of neat carbon disulfide clusters, (CS 2 ) m , additional photon absorption after the two-photon ionization step stimulates a series of intracluster ion-molecular reactions leading to formation of S m + and (CS) m + polymers, as well as intermediate species such as S m + (CS 2 ). This molecular cluster analogue of open-quotes laser snowclose quotes will be described in detail

TF insert experiment log book. 2nd Experiment of CS model coil

International Nuclear Information System (INIS)

Sugimoto, Makoto; Isono, Takaaki; Matsui, Kunihiro

2001-12-01

The cool down of CS model coil and TF insert was started on August 20, 2001. It took almost one month and immediately started coil charge since September 17, 2001. The charge test of TF insert and CS model coil was completed on October 19, 2001. In this campaign, total shot numbers were 88 and the size of the data file in the DAS (Data Acquisition System) was about 4 GB. This report is a database that consists of the log list and the log sheets of every shot. This is an experiment logbook for 2nd experiment of CS model coil and TF insert for charge test. (author)

Chemical Vapor Transport Deposition of Molybdenum Disulfide Layers Using H2O Vapor as the Transport Agent

Directory of Open Access Journals (Sweden)

Shichao Zhao

2018-02-01

Full Text Available Molybdenum disulfide (MoS2 layers show excellent optical and electrical properties and have many potential applications. However, the growth of high-quality MoS2 layers is a major bottleneck in the development of MoS2-based devices. In this paper, we report a chemical vapor transport deposition method to investigate the growth behavior of monolayer/multi-layer MoS2 using water (H2O as the transport agent. It was shown that the introduction of H2O vapor promoted the growth of MoS2 by increasing the nucleation density and continuous monolayer growth. Moreover, the growth mechanism is discussed.

[Neurologic diagnosis and certification in persons chronically exposed to certain organic solvents in light of personal cases].

Science.gov (United States)

Sińczuk-Walczak, H

1995-01-01

A clinical picture of selected cases diagnosed or suspected of chronic poisoning by organic solvents such as: Trichlorethylene (TRI), Tetrachlorethylene (PER), Carbon Disulfide (CS2) is presented. Based on examples of diagnosed neurological syndromes, some diagnostic and certification issues concerning occupational diseases of the neurological system, are analysed. An objective assessment of patients' complaints, differentiation between occupational diseases, so called idiopathic diseases of the nervous system, selection of appropropriate diagnostic methods in order to confirm or exclude these diseases belong to essential problems among those discussed.

Novel bioadhesive polymers as intra-articular agents: Chondroitin sulfate-cysteine conjugates.

Science.gov (United States)

Suchaoin, Wongsakorn; Bonengel, Sonja; Griessinger, Julia Anita; Pereira de Sousa, Irene; Hussain, Shah; Huck, Christian W; Bernkop-Schnürch, Andreas

2016-04-01

The aim of this study was to generate and characterize a chondroitin sulfate-cysteine conjugate (CS-cys) as a novel bioadhesive agent for intra-articular use. Mucoadhesive properties of synthesized CS-cys were investigated by rheological measurement of polymer-mucus mixture and rotating cylinder method, while bioadhesive features of CS-cys on porcine articular cartilage were evaluated via tensile studies. Thiolation was achieved by attachment of l-cysteine to CS via amide bond formation mediated by carbodiimide as a coupling reagent. The conjugate exhibited 421.17±35.14 μmol free thiol groups per gram polymer. The reduced CS-cys displayed 675.09±39.67 μmol free thiol groups per gram polymer after disulfide bonds reduction using tris(2-carboxyethyl)phosphine hydrochloride. The increase in dynamic viscosity of thiolated CS due to oxidative disulfide bond formation was demonstrated using capillary viscometer. The combination of CS-cys and mucus led to 4.57-fold increase in dynamic viscosity in comparison with mucus control. Furthermore, adhesion time to porcine mucosa of CS-cys-based test disk was enhanced by 2.48-fold compared to unmodified CS as measured by rotating cylinder method suggesting the interaction between thiomers and mucus gel layer via disulfide bonds formation. Tensile studies of thiolated CS on porcine articular cartilage showed 5.37- and 1.76-fold increase in the total work of adhesion and the maximum detachment force, respectively, in comparison with unmodified CS indicating bioadhesive features of CS-cys. Cytotoxicity of CS-cys was assessed in Caco-2 cells and rat primary articular chondrocytes using MTT and LDH release assay, thereby showing the safety of CS-cys at a concentration of 0.25% (w/v) in Caco-2 cells. Furthermore, 0.1% of CS-cys was found non-toxic to rat primary articular chondrocytes. According to these results, CS-cys provides improved bioadhesive properties that might be useful as an intra-articular agent for treatment of

Relaxation phenomena in CsCoCl3·2 H2O

NARCIS (Netherlands)

Flokstra, Jakob; Gerritsma, G.J.; Vermeulen, A.J.W.A; Botterman, A.C.

1973-01-01

Dynamic susceptibility measurements have been performed on a single crystal of CsCoCl3·2H2O at liquid temperatures by means of a Hartshorn mutual inductance bridge. At the magnetic phase transition a maximum in τabs(H) has been observed. A jump in τabs(T) has been found at the λ-point of liquid

X-ray enhancement of CsI:Eu{sup 2+} radioluminescence

Energy Technology Data Exchange (ETDEWEB)

Leblans, P., E-mail: paul.leblans@agfa.com [Agfa-HealthCare NV, Septestraat 27, B-2640 Mortsel (Belgium); Struye, L.; Elen, S.; Mans, I. [Agfa-HealthCare NV, Septestraat 27, B-2640 Mortsel (Belgium); Vrielinck, H.; Callens, F. [Electron Magnetic Resonance Research Group, Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Gent (Belgium)

2015-09-15

CsI:Eu{sup 2+} needle crystal layers were produced by Physical Vapour Deposition (PVD). The luminescence properties were studied before and after thermal anneal. It was shown by Electron Paramagnetic Resonance (EPR) that annealing produces Eu{sup 2+} monomer centres, probably starting from Eu clusters in the needle crystalline layers. These centres seem structurally very similar to the Eu{sup 2+} monomer centres in annealed CsBr:Eu{sup 2+} needle layers. They give rise to a narrow luminescence band peaking at about 450 nm (2.76 eV) at room temperature, both under X-ray and UV excitation. The luminescence intensity of as-deposited layers is low. Annealing enhances photo- and radioluminescence on average by a factor of 1.5–3. Surprisingly, further sensitization of radioluminescence with a factor of up to 7 is possible by exposing the annealed needle layers to X-rays or UV, while in contrast, UV excited luminescence is slightly reduced. X-ray enhancement thus leads to a structured scintillator with a conversion efficiency of about 42,000 photons/MeV upon X-ray excitation. A similar radioluminescence enhancement is observed for annealed CsI:Eu{sup 2+} fine powder, but not for large single crystals or conglomerated polycrystals. The measurements and observations are consistent with Eu{sup 2+} monomer centres stabilized by water molecules. These molecules are incorporated via annealing, and that this happens when the morphology is such that water can diffuse throughout the volume of the crystals. The presence of stabilized Eu{sup 2+} monomers is necessary to enhance radioluminescence by X-ray exposure. A mechanism is proposed for the phenomenon.

New alkali metal diphosphates how materials to preserve the security of the environment: CsNaCu(P2O7), Rb2Cu(P2O7) and CsNaCo(P2O7) synthesis and crystal structure determination

Science.gov (United States)

Chernyatieva, Anastasiya; Filatova, Alyona; Spiridonova, Dariya; Krivovichev, Sergey

2013-04-01

In this work we describe preliminary results of the synthesis and of a crystal-chemical study of synthetic phosphates with transition metals. Due to the increasing requirements for environmental safety specialists from various industries, we are searching for sustainable forms of immobilization of hazardous waste during storage. We are also developing a component-based waste for new materials. In our continued exploratory synthesis of compounds containing transition-metals, we were able to produce the new diphosphate phases CsNaCu(P2O7), Rb2Cu(P2O7) and CsNaCo(P2O7). A crystal chemical study has allowed us to identify new phosphates. Crystals of CsNaCu(P2O7) (Phase 1) is orthorhombic, crystallizes in space group Pmn21, with a = 5.147(8), b = 15.126(2), c = 9.717(2) Å, V = 756.20 Å3, R1 = 0.066 and Rb2Cu(P2O7) (Phase 2) is orthorhombic as well, crystallizes in space group Pmcn, with a = 5.183(8), b = 10.096(1), c = 15.146(3) Å, V = 793.55 Å3, R1 = 0.063, they have been obtained by high-temperature reaction of RbNO3, CsNO3, Cu(NO3)2, NaOH and (NH4)4P2O7. Synthetic crystals of the phosphate of copper and rubidium were studied in detail by us on the structures of Rb2Cu(P2O7) and Rb2Cu3(P2O7)2 - new alkali metal copper diphosphates (CHERNYATIEVA et al., 2008). Here we report the synthesis, the structure and the properties of the title compounds and we compare these phases with the previously discovered K2CuP2O7 (ELMAADI et al., 1995) and CsNaMnP2O7 (HUANG et al., 1998). These structures crystallize in other space groups, although their structures are also based on 2-D layers, formed by P2O7 groups combined with polyhedra of the transition metals (CHERNYATIEVA et al., 2012). A crystal chemical study has allowed us to identify even new diphosphates CsNaCu(P2O7) (Phase 3). Crystals of CsNaCoP2O7 is monoclinic, space group P 21/n, with a = 7,424(2), b = 7,648(1), c = 12,931(3)Å, β = 90,71(2)° , V = 734.2(3) Å3 and R1 = 0.060. The structure is based framework of Co

Reactive barriers for 137Cs retention

International Nuclear Information System (INIS)

Krumhansl, James L.; Brady, Patrick V.; Anderson, Howard L.

2000-01-01

137 Cs was dispersed globally by cold war activities and, more recently, by the Chernobyl accident. Engineered extraction of 137 Cs from soils and groundwaters is exceedingly difficult. Because the half life of 137 Cs is only 30.2 years, remediation might be more effective (and less costly) if 137 Cs bioavailability could be demonstrably limited for even a few decades by use of a reactive barrier. Essentially permanent isolation must be demonstrated in those few settings where high nuclear level wastes contaminated the environment with 135 Cs (half life 2.3x10 6 years) in addition to 137 Cs. Clays are potentially a low-cost barrier to Cs movement, though their long-term effectiveness remains untested. To identify optimal clays for Cs retention Cs resorption was measured for five common clays: Wyoming Montmorillonite (SWy-1), Georgia Kaolinites (KGa-1 and KGa-2), Fithian Illite (F-Ill), and K-Metabentonite (K-Mbt). Exchange sites were pre-saturated with 0.16 M CsCl for 14 days and readily exchangeable Cs was removed by a series of LiNO 3 and LiCl washes. Washed clay were then placed into dialysis bags and the Cs release to the deionized water outside the bags measured. Release rates from 75 to 139 days for SWy-1, K-Mbt and F- 111 were similar; 0.017 to 0.021% sorbed Cs released per day. Both kaolinites released Cs more rapidly (0.12 to 0.05% of the sorbed Cs per day). In a second set of experiments, clays were doped for 110 days and subjected to an extreme and prolonged rinsing process. All the clays exhibited some capacity for irreversible Cs uptake so most soils have some limited ability to act as a natural barrier to Cs migration. However, the residual loading was greatest on K-Mbt (∼ 0.33 wt% Cs). Thus, this clay would be the optimal material for constructing artificial reactive barriers

Electron Dynamics in the Core-Excited CS_{2} Molecule Revealed through Resonant Inelastic X-Ray Scattering Spectroscopy

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T. Marchenko

2015-08-01

Full Text Available We present an experimental and theoretical study of resonant inelastic x-ray scattering (RIXS in the carbon disulphide CS_{2} molecule near the sulfur K-absorption edge. We observe a strong evolution of the RIXS spectral profile with the excitation energy tuned below the lowest unoccupied molecular orbital (LUMO absorption resonance. The reason for this is twofold. Reducing the photon energy in the vicinity of the LUMO absorption resonance leads to a relative suppression of the LUMO contribution with respect to the emission signal from the higher unoccupied molecular orbitals, which results in the modulation of the total RIXS profile. At even larger negative photon-energy detuning from the resonance, the excitation-energy dependence of the RIXS profile is dominated by the onset of electron dynamics triggered by a coherent excitation of multiple electronic states. Furthermore, our study demonstrates that in the hard x-ray regime, localization of the S 1s core hole occurs in CS_{2} during the RIXS process because of the orientational dephasing of interference between the waves scattering on the two sulfur atoms. Core-hole localization leads to violation of the symmetry selection rules for the electron transitions observed in the spectra.

{sup 134}Cs uptake by four plant species and Cs-K relations in the soil-plant system as affected by Ca(OH){sub 2} application to an acid soil

Energy Technology Data Exchange (ETDEWEB)

Massas, I., E-mail: massas@aua.g [Soil Science Laboratory, Department of Natural Resources Management and Agricultural Engineering, Agricultural University of Athens, Iera Odos 75, 11855 Athens (Greece); Skarlou, V.; Haidouti, C.; Giannakopoulou, F. [Soil Science Laboratory, Department of Natural Resources Management and Agricultural Engineering, Agricultural University of Athens, Iera Odos 75, 11855 Athens (Greece)

2010-03-15

Three rates of Ca(OH){sub 2} were applied to an acid soil and the {sup 134}Cs uptake by radish, cucumber, soybean and sunflower plants was studied. The {sup 134}Cs concentration in all plant species was reduced from 1.6-fold in the sunflower seeds to 6-fold in the soybean vegetative parts at the higher Ca(OH){sub 2} rate. Potassium (K) concentration in plants was also reduced, but less effectively. The significantly decreased {sup 134}Cs-K soil to plant distribution factors (D.F.) clearly suggest a stronger effect of soil liming on {sup 134}Cs than on K plant uptake. This observation was discussed in terms of ionic interactions in the soil matrix and within the plants. The results also indicated that the increased Ca{sup 2+} concentration in the exchange phase and in the soil solution along with the improved root activity, due to the soil liming, enhanced the immobilization of {sup 134}Cs in the soil matrix and consequently lowered the {sup 134}Cs availability for plant uptake.

Cs2Te normal conducting photocathodes in the superconducting rf gun

CERN Document Server

Xiang, R; Buettig, H; Janssen, D; Justus, M; Lehnert, U; Michel, P; Murcek, P; Schamlott, A; Schneider, Ch; Schurig, R; Staufenbiel, F; Teichert, J

2010-01-01

The superconducting radio frequency photoinjector (SRF gun) is one of the latest applications of superconducting rf technology in the accelerator field. Since superconducting photocathodes with high quantum efficiency are yet unavailable, normal conducting cathode material is the main choice for SRF photoinjectors. However, the compatibility between the photocathode and the cavity is one of the challenges for this concept. Recently, a SRF gun with Cs2Te cathode has been successfully operated in Forschungszentrum Dresden-Rossendorf. In this paper, we will present the physical properties of Cs2Te photocathodes in the SC cavity, such as the quantum efficiency, the lifetime, the rejuvenation, the charge saturation, and the dark current.

Study on the mechanisms of solidification for Cs+ and Sr2+ in alkali-activated slag cement waste forms

International Nuclear Information System (INIS)

Yan Sheng; Shen Xiaodong; Lu Linchao; Wu Xuequan; Wen Yinghui

1994-09-01

The mechanisms of adsorption and chemical immobilization in Alkali-Activated Slag Cement (AASC) waste forms were quantitatively studied for Cs + and Sr 2+ . Experimental results show that, hardened AASC paste with zeolite and silica fume possesses strong adsorption ability and anti-desorption ability for Cs + and Sr 2+ . The results and analyzed by XRD show that CS + and SR 2+ could be incorporated into the lattice of C-S-H by replacing Ca 2+ in C-S-H. The d 111 values of C-S-H increase with increasing CsNO 3 and Sr(NO 3 ) 2 dosages in a limited and regular step. After washed out by deionized water in a ultrasonic washer, samples were analyzed by SEM-EDS and a lot of Cs + and Sr 2+ were detected. This means that the hydration products of AASC have a high retaining ability for Cs + and Sr 2+ . (3 tabs., 8 figs.)

Intradomain Confinement of Disulfides in the Folding of Two Consecutive Modules of the LDL Receptor.

Directory of Open Access Journals (Sweden)

Juan Martínez-Oliván

Full Text Available The LDL receptor internalizes circulating LDL and VLDL particles for degradation. Its extracellular binding domain contains ten (seven LA and three EGF cysteine-rich modules, each bearing three disulfide bonds. Despite the enormous number of disulfide combinations possible, LDLR oxidative folding leads to a single native species with 30 unique intradomain disulfides. Previous folding studies of the LDLR have shown that non native disulfides are initially formed that lead to compact species. Accordingly, the folding of the LDLR has been described as a "coordinated nonvectorial" reaction, and it has been proposed that early compaction funnels the reaction toward the native structure. Here we analyze the oxidative folding of LA4 and LA5, the modules critical for ApoE binding, isolated and in the LA45 tandem. Compared to LA5, LA4 folding is slow and inefficient, resembling that of LA5 disease-linked mutants. Without Ca++, it leads to a mixture of many two-disulfide scrambled species and, with Ca++, to the native form plus two three-disulfide intermediates. The folding of the LA45 tandem seems to recapitulate that of the individual repeats. Importantly, although the folding of the LA45 tandem takes place through formation of scrambled isomers, no interdomain disulfides are detected, i.e. the two adjacent modules fold independently without the assistance of interdomain covalent interactions. Reduction of incredibly large disulfide combinatorial spaces, such as that in the LDLR, by intradomain confinement of disulfide bond formation might be also essential for the efficient folding of other homologous disulfide-rich receptors.

The concentration of "1"3"7Cs and organic carbon on sediment at Rat island in Indian ocean

International Nuclear Information System (INIS)

Muslim; Reza Agung Arjana; Wahyu Retno Prihatiningsih

2016-01-01

Rat Island is one of the islands in Indonesia, located in the Indian Ocean, about 10 kilometers west of Bengkulu, which has a beautiful scenery both on its land and on the seabed, making it a favorite tourist in Bengkulu. The purpose of this study was to determine the condition of "1"3"7Cs in sediments and its relation to the total carbon and sediment texture. Sediment sampling carried out on 17 September 2014 at six stations where three stations are still relatively close to The Rat island with water depth of ≤ 1 m and 3 others are far from Rat Island waters with a depth of 14-18 meters. Sediment texture and TOC content at waters depth of ≤ 1 m is sand and its TOC contents were <5.5%. On other hand at water depth of 14-18 meters sediment texture are silt sand mixture and the TOC content were ≥6%. The concentration of "1"3"7Cs in sediment were influenced by texture characteristic and TOC content. (author)

Mutational analysis of Kex2 recognition sites and a disulfide bond in tannase from Aspergillus oryzae.

Science.gov (United States)

Koseki, Takuya; Otsuka, Motohiro; Mizuno, Toshiyuki; Shiono, Yoshihito

2017-01-22

Aspergillus oryzae tannase (AoTanA), which contains two Kex2 recognition sites at positions Arg311 and Arg316, consists of two subunits that are generated by the cleavage of tannase gene product by the Kex2 protease. Based on the crystal structure of feruloyl esterase from Aspergillus oryzae (AoFaeB), which has been classified as a member of the fungal tannase family, the catalytic triad residues of AoTanA are predicted to be Ser195, Asp455, and His501, with the serine and histidine residues brought together by a disulfide bond of the neighboring cysteines, Cys194 and Cys502. In this study, we investigated the functional role of the Kex2 recognition sites and disulfide bond between the neighboring cysteines in AoTanA. We constructed a double variant (R311A/R316A), a seven amino-acid deletion variant of region Lys310-Arg316 (ΔKR), and two single variants (C194A and C502A). While the R311A/R316A variant exhibited the two bands similar to wild type by SDS-PAGE after treatment with endoglycosidase H, the ΔKR variant exhibited only one band. R311A/R316A variation had no effect on tannase activity and stability. Meanwhile, the ΔKR variant exhibited higher activity compared to the wild-type. The activities of the C194A and C502A variants decreased considerably (<0.24% of the wild-type) toward methyl gallate. Copyright © 2016 Elsevier Inc. All rights reserved.

Determination of thermal properties of Cs2Cr2O7(s,l) by high temperature Calvet calorimetry

International Nuclear Information System (INIS)

Prasad, R.; Agarwal, R.; Roy, K.N.; Iyer, V.S.; Venugopal, V.; Sood, D.D.

1989-01-01

Enthalpy increments have been determined for caesium dichromate in the temperature range 335 to 826 K using a high temperature Calvet micro calorimeter. A solid-solid transition has been observed at (620.5±1.5 K) and the melting temperature was found to be (657.0±1.0) K. The corresponding enthalpy values are 15.6±0.2) kJ/mol and 17.0±0.22) kJ/mol. The results thus obtained are utilised for the evaluation of molar heat capacities, standard entropies and free energy functions for Cs 2 Cr 2 O 7 (s,l). The enthalpy increment values were fitted to a polynomial and can be presented by eqs. (1) to (3), respectivley: (1) (H T 0 -H 0 298.15 )(Cs 2 Cr 2 O 7 ,s) (J/mol)=-6.410x10 4 +1.939x10 2 T(K)+7.441x10 -2 T(K) 2 (335 to 620.5 K), (2) (H T 0 -H 0 298.15 )(Cs 2 Cr 2 O 7 ,s) (J/mol)=1.313x10 6 -4.137x10 3 T(K)+3.517T(K) 2 (620.5 to 656 K), (3) (H T 0 -H 0 298.15 )(Cs 2 Cr 2 O 7 ,l) (J/mol)=-1.218x10 5 +3.890x10 2 T(K) (657 to 826 K). (orig.)

Cs2.5H0.5PWO40/SiO2 as addition self-humidifying composite membrane for proton exchange membrane fuel cells

International Nuclear Information System (INIS)

Wang, L.; Yi, B.L.; Zhang, H.M.; Xing, D.M.

2007-01-01

In this paper, we first reported a novel self-humidifying composite membrane for the proton exchange membrane fuel cell (PEMFC). Cs 2.5 H 0.5 PWO 40 /SiO 2 catalyst particles were dispersed uniformly into the Nafion (registered) resin, and then Cs 2.5 H 0.5 PWO 40 -SiO 2 /Nafion composite membrane was prepared using solution-cast method. Compared with the H 3 PWO 40 (PTA) , the Cs 2.5 H 0.5 PWO 40 /SiO 2 was steady due to the substitute of H + with Cs + and the interaction between the Cs 2.5 H 0.5 PWO 40 and SiO 2 . And compared with the performance of the fuel cell with commercial Nafion (registered) NRE-212 membrane, the cell performance with the self-humidifying composite membrane was obviously improved under both humidified and dry conditions at 60 and 80 o C. The best performance under dry condition was obtained at 60 o C. The self-humidifying composite membrane could minimize membrane conductivity loss under dry conditions due to the presence of catalyst and hydrophilic Cs 2.5 H 0.5 PWO 40 /SiO 2 particles