Self-Driven Photoelectrochemical Splitting of H2S for S and H2 Recovery and Simultaneous Electricity Generation.

PubMed

Luo, Tao; Bai, Jing; Li, Jinhua; Zeng, Qingyi; Ji, Youzhi; Qiao, Li; Li, Xiaoyan; Zhou, Baoxue

2017-11-07

A novel, facile self-driven photoelectrocatalytic (PEC) system was established for highly selective and efficient recovery of H 2 S and simultaneous electricity production. The key ideas were the self-bias function between a WO 3 photoanode and a Si/PVC photocathode due to their mismatched Fermi levels and the special cyclic redox reaction mechanism of I - /I 3 - . Under solar light, the system facilitated the separation of holes in the photoanode and electrons in the photocathode, which then generated electricity. Cyclic redox reactions were produced in the photoanode region as follows: I - was transformed into I 3 - by photoholes or hydroxyl radicals, H 2 S was oxidized to S by I 3 - , and I 3 - was then reduced to I - . Meanwhile, H + was efficiently converted to H 2 in the photocathode region. In the system, H 2 S was uniquely oxidized to sulfur but not to polysulfide (S x n- ) because of the mild oxidation capacity of I 3 - . High recovery rates for S and H 2 were obtained up to ∼1.04 mg h -1 cm -1 and ∼0.75 mL h -1 cm -1 , respectively, suggesting that H 2 S was completely converted into H 2 and S. In addition, the output power density of the system reached ∼0.11 mW cm -2 . The proposed PEC-H 2 S system provides a self-sustaining, energy-saving method for simultaneous H 2 S treatment and energy recovery.

1-(2-Cyano­ethyl)-2-(2-pyrid­yl)-1H,3H-benzimidazol-3-ium perchlorate

PubMed Central

Li, Yan; Tang, Xiaoliang; Chen, Jiayu; Wu, Daxiang; Liu, Weisheng

2010-01-01

The title compound, C15H13N4 +·ClO4 −, comprises a nonplanar 1-(2-cyano­ethyl)-2-(2-pyrid­yl)-1H,3H-benzimidazol-3-ium cation [dihedral angle between the imidazole and pyridine rings = 22.5 (8)°] and a perchlorate anion. The cation is formed by protonation of the N atom of the benzimidazole ring. A charged N—H⋯O hydrogen bond connects the anion and cation, and inter­molecular C—H⋯O and C—H⋯N inter­actions contribute to the crystal packing. PMID:21579831

A neural network potential energy surface for the NaH2 system and dynamics studies on the H(2S) + NaH(X1Σ+) → Na(2S) + H2(X1Σg+) reaction.

PubMed

Wang, Shufen; Yuan, Jiuchuang; Li, Huixing; Chen, Maodu

2017-08-02

In order to study the dynamics of the reaction H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), a new potential energy surface (PES) for the ground state of the NaH 2 system is constructed based on 35 730 ab initio energy points. Using basis sets of quadruple zeta quality, multireference configuration interaction calculations with Davidson correction were carried out to obtain the ab initio energy points. The neural network method is used to fit the PES, and the root mean square error is very small (0.00639 eV). The bond lengths, dissociation energies, zero-point energies and spectroscopic constants of H 2 (X 1 Σ g + ) and NaH(X 1 Σ + ) obtained on the new NaH 2 PES are in good agreement with the experiment data. On the new PES, the reactant coordinate-based time-dependent wave packet method is applied to study the reaction dynamics of H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ), and the reaction probabilities, integral cross-sections (ICSs) and differential cross-sections (DCSs) are obtained. There is no threshold in the reaction due to the absence of an energy barrier on the minimum energy path. When the collision energy increases, the ICSs decrease from a high value at low collision energy. The DCS results show that the angular distribution of the product molecules tends to the forward direction. Compared with the LiH 2 system, the NaH 2 system has a larger mass and the PES has a larger well at the H-NaH configuration, which leads to a higher ICS value in the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction. Because the H( 2 S) + NaH(X 1 Σ + ) → Na( 2 S) + H 2 (X 1 Σ g + ) reaction releases more energy, the product molecules can be excited to a higher vibrational state.

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14-

NASA Astrophysics Data System (ADS)

Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

2003-08-01

Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

Chanabayaite, Cu2(N3C2H2)Cl(NH3,Cl,H2O,□)4, a new mineral containing triazolate anion

NASA Astrophysics Data System (ADS)

Chukanov, N. V.; Zubkova, N. V.; Möhn, G.; Pekov, I. V.; Pushcharovsky, D. Yu.; Zadov, A. E.

2015-12-01

A new mineral, chanabayaite, has been discovered at a guano deposit located at Mt. Pabellón de Pica near the village of Chanabaya, Iquique Province, Tarapacá region, Chile. It is associated with salammoniac, halite, joanneumite, nitratine and earlier chalcopyrite. Chanabayaite occurs as blue translucent imperfect prismatic crystals, up to 0.05 × 0.1 × 0.5 mm in size, and their radial aggregates. Chanabayaite is brittle, with a Mohs' hardness of 2. The cleavage is perfect on (001) and imperfect on (100) and (010). D meas = 1.48(2) g/cm3, D calc = 1.464 g/cm3. The mineral is optically biaxial (-), α = 1.561(2), β = 1.615(3), γ = 1.620(2), 2 V meas = 25(10)°, 2 V calc = 33°. Pleochroism is strong, Z ≈ Y (deep blue) ≫ X (pale blue with gray tint). IR spectrum is given. The chemical composition (electron microprobe data for Cu, Fe and Cl; gas chromatography data for H, N, C and O) is as follows (wt %): 32.23 Cu, 1.14 Fe, 16.13 Cl, 3.1 H, 29.9 N, 12.2 C, 3.4 O, total is 98.1. The empirical formula is ( Z = 4): Cu1.92Fe0.08Cl1.72N8.09C3.85H11.66O0.81. The structural model was based on the single-crystal X-ray diffraction data ( R = 0.1627). Chanabayaite is orthorhombic, space group Imma, a = 19.484(3), b = 7.2136(10), c = 11.999(4) Å, V = 1686.5(7) Å3, Z = 2. In chanabayaite, chains of the corner-sharing Cu(l)-centered octahedra and single Cu(2)-centered octahedra are linked via 1,2,4-triazolate anions C2N3H2 -. NH3 and Cl- are additional ligands coordinating Cu2+. Chanabayaite is a transformational mineral species formed by leaching of Na and one third of Cl and partial dehydration of the protophase Na2Cu2Cl3(N3C2H2)2(NH3)2 • 4H2O. The strongest reflections in the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are detected: 10.19 (100) (101), 6.189 (40) (011), 5.729 (23) (301), 5.216 (75) (211, 202), 4.964 (20) (400), 2.830 (20) (602, 413, 503), 2.611 (24) (123, 422, 404).

Photochemical Generation of H_{2}NCNX, H_{2}NNCX, H_{2}NC(NX) (x = O, s) in Low-Temperature Matrices

NASA Astrophysics Data System (ADS)

Voros, Tamas; Lajgut, Gyozo Gyorgy; Magyarfalvi, Gabor; Tarczay, Gyorgy

2017-06-01

The [NH_{2}, C, N, O] and the [NH_{2}, C, N, S] systems were investigated by quantum-chemical computations and matrix-isolation spectroscopic methods. The equilibrium structures of the isomers and their relative energies were determined by CCSD(T) method. This was followed by the computation of the harmonic and anharmonic vibrational wavenumbers, infrared intensities, relative Raman activities and UV excitation energies. These computed data were used to assist the identification of products obtained by UV laser photolysis of 3,4-diaminofurazan, 3,4-diaminothiadiazole and 1,2,4-thiadiazole-3,5-diamine in low-temperature Ar and Kr matrices. Experimentally, first the precursors were studied by matrix-isolation IR and UV spectroscopic methods. Based on these UV spectra, different wavelengths were selected for photolysis. The irradiations, carried out by a tunable UV laser-light source, resulted in the decomposition of the precursors, and in the appearance of new bands in the IR spectra. Some of these bands were assigned to cyanamide (H_{2}NCN) and its isomer, the carbodiimide molecule (HNCNH), generated from H_{2}NCN. By the analysis of the relative absorbance vs. photolysis time curves, the other bands were grouped to three different species both for the O- and the S-containing systems. In the case of the O-containing isomers, these bands were assigned to the H_{2}NNCO:H_{2}NCN, and H_{2}NCNO:H_{2}NCN complexes, and to the ring-structure H_{2}NC(NO) isomer. In a similar way, the complexes of H_{2}NNCS and H_{2}NCNS with the H_{2}NCN, and H_{2}NC(NS) were also identified. 1,2,4-thiadiazole-3,5-diamine was also investigated in similar way like the above mentioned precursors. The results of this study also support the identification of the new S-containing isomers. Except for H_{2}NNCO and H_{2}NCNS, these molecules were not identified previously. It is expected that at least some of these species, like the methyl isocyanate (CH_{3}CNO) isomer, are present and could be

Trapping {BW12}2 tungstoborate: synthesis and crystal structure of hybrid [{(H2BW12O42)2O}{Mo6O6S6(OH)4(H2O)2}]14- anion.

PubMed

Korenev, V S; Abramov, P A; Vicent, C; Mainichev, D A; Floquet, S; Cadot, E; Sokolov, M N; Fedin, V P

2012-12-28

Reaction between monolacunary {BW(11)} tungstoborate and oxothiocationic building block, {Mo(2)O(2)S(2)}, results in the formation of a new polyoxothiometalate with a unique architecture in which two [H(2)BW(12)O(43)](9-) tungstoborate subunits are linked together with a hexamolybdate [Mo(V)(6)O(6)S(6)(OH)(4)(H(2)O)(2)](2+) bridge.

Nitric oxide reactivity of [2Fe-2S] clusters leading to H2S generation.

PubMed

Tran, Camly T; Williard, Paul G; Kim, Eunsuk

2014-08-27

The crosstalk between two biologically important signaling molecules, nitric oxide (NO) and hydrogen sulfide (H2S), proceeds via elusive mechanism(s). Herein we report the formation of H2S by the action of NO on synthetic [2Fe-2S] clusters when the reaction environment is capable of providing a formal H(•) (e(-)/H(+)). Nitrosylation of (NEt4)2[Fe2S2(SPh)4] (1) in the presence of PhSH or (t)Bu3PhOH results in the formation of (NEt4)[Fe(NO)2(SPh)2] (2) and H2S with the concomitant generation of PhSSPh or (t)Bu3PhO(•). The amount of H2S generated is dependent on the electronic environment of the [2Fe-2S] cluster as well as the type of H(•) donor. Employment of clusters with electron-donating groups or H(•) donors from thiols leads to a larger amount of H2S evolution. The 1/NO reaction in the presence of PhSH exhibits biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution. However, the rates of decay increase significantly with the use of 4-MeO-PhSH or 4-Me-PhSH in place of PhSH. These results provide the first chemical evidence to suggest that [Fe-S] clusters are likely to be a site for the crosstalk between NO and H2S in biology.

AOI [3] High-Temperature Nano-Derived Micro-H 2 and - H 2S Sensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sabolsky, Edward M.

2014-08-01

The emissions from coal-fired power plants remain a significant concern for air quality. This environmental challenge must be overcome by controlling the emission of sulfur dioxide (SO 2) and hydrogen sulfide (H 2S) throughout the entire coal combustion process. One of the processes which could specifically benefit from robust, low cost, and high temperature compatible gas sensors is the coal gasification process which converts coal and/or biomass into syngas. Hydrogen (H 2), carbon monoxide (CO) and sulfur compounds make up 33%, 43% and 2% of syngas, respectively. Therefore, development of a high temperature (>500°C) chemical sensor for in-situ monitoring ofmore » H 2, H 2S and SO2 2 levels during coal gasification is strongly desired. The selective detection of SO 2/H 2S in the presence of H 2, is a formidable task for a sensor designer. In order to ensure effective operation of these chemical sensors, the sensor system must inexpensively function within harsh temperature and chemical environment. Currently available sensing approaches, which are based on gas chromatography, electrochemistry, and IR-spectroscopy, do not satisfy the required cost and performance targets. This work focused on the development microsensors that can be applied to this application. In order to develop the high- temperature compatible microsensor, this work addressed various issues related to sensor stability, selectivity, and miniaturization. In the research project entitled “High-Temperature Nano-Derived Micro-H 2 and -H 2S Sensors”, the team worked to develop micro-scale, chemical sensors and sensor arrays composed of nano-derived, metal-oxide composite materials to detect gases like H 2, SO 2, and H 2S within high-temperature environments (>500°C). The research was completed in collaboration with NexTech Materials, Ltd. (Lewis Center, Ohio). NexTech assisted in the testing of the sensors in syngas with contaminate levels of H 2S. The idea of including nanomaterials as the

Anionic pH-Sensitive Lipoplexes.

PubMed

Mignet, Nathalie; Scherman, Daniel

2017-01-01

To provide long circulating nanoparticles able to carry a gene to tumors, we have designed anionic pegylated lipoplexes which are pH sensitive. Anionic pegylated lipoplexes have been prepared from the combined formulation of cationic lipoplexes and pegylated anionic liposomes. The neutralization of the particle surface charge as a function of the pH was monitored by light scattering in order to determine the ratio between anionic and cationic lipids that would give pH sensitive complexes. This ratio has been optimized to form particles sensitive to pH change in the range 5.5-6.5. Compaction of DNA into these newly formed anionic complexes is checked by DNA accessibility to picogreen. The transfection efficiency and pH sensitive property of these formulations has been shown in vitro using bafilomycin, a vacuolar H + -ATPase inhibitor.

Inelastic rate coefficients for collisions of C6H- with H2 and He

NASA Astrophysics Data System (ADS)

Walker, Kyle M.; Lique, François; Dumouchel, Fabien; Dawes, Richard

2017-04-01

The recent detection of anions in the interstellar medium has shown that they exist in a variety of astrophysical environments - circumstellar envelopes, cold dense molecular clouds and star-forming regions. Both radiative and collisional processes contribute to molecular excitation and de-excitation in these regions so that the 'local thermodynamic equilibrium' approximation, where collisions cause the gas to behave thermally, is not generally valid. Therefore, along with radiative coefficients, collisional excitation rate coefficients are needed to accurately model the anionic emission from these environments. We focus on the calculation of state-to-state rate coefficients of the C6H- molecule in its ground vibrational state in collisions with para-H2, ortho-H2 and He using new potential energy surfaces. Dynamical calculations for the pure rotational excitation of C6H- were performed for the first 11 rotational levels (up to j1 = 10) using the close-coupling method, while the coupled-states approximation was used to extend the H2 rate coefficients to j1 = 30, where j1 is the angular momentum quantum number of C6H-. State-to-state rate coefficients were obtained for temperatures ranging from 2 to 100 K. The rate coefficients for H2 collisions for Δj1 = -1 transitions are of the order of 10-10 cm3 s-1, a factor of 2 to 3 greater than those of He. Propensity rules are discussed. The collisional excitation rate coefficients produced here impact astrophysical modelling since they are required for obtaining accurate C6H- level populations and line emission for regions that contain anions.

Inhibitory effect of selective cyclooxygenase-2 inhibitor lumiracoxib on human organic anion transporters hOAT1 and hOAT3.

PubMed

Uwai, Yuichi; Honjo, Hiroaki; Iwamoto, Kikuo

2010-01-01

Nonsteroidal anti-inflammatory drugs (NSAIDs) delay renal excretion of antifolate methotrexate by inhibiting human organic anion transporters hOAT1 (SLC22A6) and hOAT3 (SLC22A8). In this study, we performed uptake experiments using Xenopus laevis oocytes to assess the inhibitory effect of selective cyclooxygenase-2 inhibitors on hOAT1 and hOAT3. The uptake of methotrexate into oocytes was increased by the injection of hOAT1 and hOAT3 cRNA, and transport was strongly inhibited by lumiracoxib. The apparent 50% inhibitory concentrations of lumiracoxib were estimated to be 3.3 µM and 1.9 µM for uptake of p-aminohippurate by hOAT1 and of estrone sulfate by hOAT3, respectively. Eadie-Hofstee plot analysis showed that lumiracoxib inhibited hOAT1 and hOAT3 in a competitive manner. For other cyclooxygenase-2 inhibitors celecoxib, etoricoxib, rofecoxib and valdecoxib, slight to moderate inhibition of hOAT3 only was observed. These findings show that lumiracoxib has inhibitory potential toward hOAT1 and hOAT3, comparable to that of nonselective NSAIDs.

Anionic ordering and thermal properties of FeF3·3H2O.

PubMed

Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; Wattiaux, Alain; Demourgues, Alain; Salanne, Mathieu; Groult, Henri; Dambournet, Damien

2015-10-05

Iron fluoride trihydrate can be used to prepare iron hydroxyfluoride with the hexagonal-tungsten-bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F(-) and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.

A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

PubMed

Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

2013-03-01

The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

A comparative study of the Au + H{sub 2}, Au{sup +} + H{sub 2}, and Au{sup −} + H{sub 2} systems: Potential energy surfaces and dynamics of reactive collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dorta-Urra, Anaís; Zanchet, Alexandre; Roncero, Octavio

2015-04-21

In order to study the Au{sup −} + H{sub 2} collision, a new global potential energy surface (PES) describing the ground electronic state of AuH{sub 2}{sup −} system is developed and compared with the PESs of the neutral [Zanchet et al., J. Chem. Phys. 132, 034301 (2010)] and cationic systems [Anaís et al., J. Chem. Phys. 135, 091102 (2011)]. We found that Au{sup −} − H{sub 2} presents a H-Au-H insertion minimum attributed to the stabilization of the LUMO 3b{sub 2} orbital, which can be considered as the preamble of the chemisorption well appearing in larger gold clusters. While themore » LUMO orbital is stabilized, the HOMO 6a{sub 1} is destabilized, creating a barrier at the geometry where the energy orbitals’ curves are crossing. In the anion, this HOMO is doubly occupied, while in the neutral system is half-filled and completely empty in the cation, explaining the gradual disappearance of the well and the barrier as the number of electrons decreases. The cation presents a well in the entrance channel partially explained by electrostatic interactions. The three systems’ reactions are highly endothermic, by 1.66, 2.79, and 3.23 eV for AuH, AuH{sup +}, and AuH{sup −} products, respectively. The reaction dynamics is studied using quasi-classical trajectory method for the three systems. The one corresponding to the anionic system is new in this work. Collision energies between 1.00 and 8.00 eV, measured for the cation, are in good agreement with the simulated cross section for the AuH{sup +}. It was also found that the total fragmentation, in three atoms, competes becoming dominant at sufficiently high energy. Here, we study the competition between the two different reaction pathways for the anionic, cationic, and neutral species, explaining the differences using a simple model based on the topology of the potential energy surfaces.« less

Mineralization of Basalts in the CO 2-H 2O-H 2S System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

2013-05-10

Basalt samples representing five different formations were immersed in water equilibrated with supercritical carbon dioxide containing 1% hydrogen sulfide (H2S) at reservoir conditions (100 bar, 90°C) for up to 3.5 years. Surface coatings in the form of pyrite and metal cation substituted carbonates were identified as reaction products associated with all five basalts. In some cases, high pressure tests contained excess H2S, which produced the most corroded basalts and largest amount of secondary products. In comparison, tests containing limited amounts of H2S appeared least reacted with significantly less concentrations of reaction products. In all cases, pyrite appeared to precede carbonation,more » and in some instances, was observed in the absence of carbonation such as in cracks, fractures, and within the porous glassy mesostasis. Armoring reactions from pyrite surface coatings observed in earlier shorter duration tests were found to be temporary with carbonate mineralization observed with all the basalts tested in these long duration experiments. Geochemical simulations conducted with the geochemical code EQ3/6 accurately predicted early pyrite precipitation followed by formation of carbonates. Reactivity with H2S was correlated with measured Fe(II)/Fe(III) ratios in the basalts with more facile pyrite formation occurring with basalts containing more Fe(III) phases. These experimental and modeling results confirm potential for long term sequestration of acid gas mixtures in continental flood basalt formations.« less

Solvent-Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge-Separated Layered Compound: [NH4 ][Ag3 (C9 H5 NO4 S)2 (C13 H14 N2 )2 ]⋅8 H2 O.

PubMed

Sushrutha, Sringeri Ramesh; Mohana, Shivanna; Pal, Somnath; Natarajan, Srinivasan

2017-01-03

A new anionic coordination polymer, [NH 4 ][Ag 3 (C 9 H 5 NO 4 S) 2 (C 13 H 14 N 2 ) 2 ]⋅8 H 2 O, with a two-dimensional structure, has been synthesized by a reaction between silver nitrate, 8-hydroxyquinoline-5-sulfonic acid (HQS), and 4,4'-trimethylene dipyridine (TMDP). The compound stabilizes in a noncentrosymmetric space group, and the lattice water molecules and the charge-compensating [NH 4 ] + group occupy the inter-lamellar spaces. The lattice water molecules can be fully removed and reinserted, which is accompanied by a crystalline-amorphous-crystalline transformation. This transformation resembles the collapse/delamination and restacking of the layers. To the best of our knowledge, this is the first observation of delamination and restacking in an inorganic coordination polymer that contains silver. The presence of a natural dipole (the anionic framework and cationic ammonium ions) along with the noncentrosymmetric space group gives rise to the room-temperature ferroelectric behavior of the compound. The ferroelectric behavior is also water-dependent and exhibits a ferroelectric-paraelectric transformation. The temperature-dependent dielectric measurements indicate that the ferroelectric/ paraelectric transformation occurs at 320 K. This transformation has also been investigated by using in-situ IR spectroscopy and PXRD studies. The second-harmonic generation (SHG) study indicated values that are comparable to some of the known SHG solids, such as potassium dihydrogen phosphate (KDP) and urea. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

2013-03-01

''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

Anionic ordering and thermal properties of FeF 3·3H 2O

DOE PAGES

Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; ...

2015-09-17

In this study, iron fluoride tri-hydrate can be used to prepare iron hydroxyfluoride with the Hexagonal-Tungsten-Bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF 3·3H 2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF 6]n and [FeF 2(H2O) 4] n. The decomposition of FeF 3·3H 2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF 3-x(OH) x with the HTB structure. The releasemore » of H 2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF 3·3H 2O. An average distribution of FeF 4(OH) 2 distorted octahedra in HTB-FeF 3-x(OH) x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F- and H 2O. This study provides a clear understanding of the structure and thermal properties of FeF 3·3H 2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.« less

Pentacoordinate silicon(IV): cationic, anionic and neutral complexes derived from the reaction of NHC→SiCl4 with highly Lewis acidic (C2F5)2SiH2.

PubMed

Böttcher, T; Steinhauer, S; Neumann, B; Stammler, H-G; Röschenthaler, G-V; Hoge, B

2014-06-14

Addition of NHC→SiCl4 to the highly Lewis acidic bis(pentafluoroethyl)silane ((C2F5)2SiH2) afforded the salt [(NHC)2SiCl2H][(C2F5)2SiCl3] with pentacoordinate silicon in the cation and the anion. The anion represents the first example of a chlorosilicate structurally characterized in the solid state. In this reaction, the long sought pentacoordinate NHC-adduct of silicochloroform was identified as an intermediate and its crystal structure is presented.

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1989-01-01

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

Precipitation synthesis of lanthanide hydroxynitrate anion exchange materials, Ln{sub 2}(OH){sub 5}NO{sub 3}.H{sub 2}O (Ln=Y, Eu-Er)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hindocha, Sheena A.; McIntyre, Laura J.; Fogg, Andrew M., E-mail: afogg@liverpool.ac.u

2009-05-15

Layered lanthanide hydroxynitrate anion exchange host lattices have been prepared via a room temperature precipitation synthesis. These materials have the composition Ln{sub 2}(OH){sub 5}NO{sub 3}.H{sub 2}O and are formed for Y and the lanthanides from Eu to Er and as such include the first Eu containing nitrate anion exchange host lattice. The interlayer separation of these materials, approximately 8.5 A, is lower than in the related phases Ln{sub 2}(OH){sub 5}NO{sub 3}.1.5H{sub 2}O which have a corresponding value of 9.1 A and is consistent with the reduction in the co-intercalated water content of these materials. These new intercalation hosts have beenmore » shown to undergo facile anion exchange reactions with a wide range of organic carboxylate and sulfonate anions. These reactions produce phases with up to three times the interlayer separation of the host lattice demonstrating the flexibility of these materials. - Graphical abstract: New anion exchangeable layered hydroxynitrates, Ln{sub 2}(OH){sub 5}NO{sub 3}.H{sub 2}O (Ln=Y, Eu - Er) have been synthesized via a precipitation route. These materials have been shown to be very flexible intercalation hosts undergoing facile exchange reactions with organic carboxylate and sulfonate anions.« less

Relative Importance of H2 and H2S as Energy Sources for Primary Production in Geothermal Springs▿ †

PubMed Central

D'Imperio, Seth; Lehr, Corinne R.; Oduro, Harry; Druschel, Greg; Kühl, Michael; McDermott, Timothy R.

2008-01-01

Geothermal waters contain numerous potential electron donors capable of supporting chemolithotrophy-based primary production. Thermodynamic predictions of energy yields for specific electron donor and acceptor pairs in such systems are available, although direct assessments of these predictions are rare. This study assessed the relative importance of dissolved H2 and H2S as energy sources for the support of chemolithotrophic metabolism in an acidic geothermal spring in Yellowstone National Park. H2S and H2 concentration gradients were observed in the outflow channel, and vertical H2S and O2 gradients were evident within the microbial mat. H2S levels and microbial consumption rates were approximately three orders of magnitude greater than those of H2. Hydrogenobaculum-like organisms dominated the bacterial component of the microbial community, and isolates representing three distinct 16S rRNA gene phylotypes (phylotype = 100% identity) were isolated and characterized. Within a phylotype, O2 requirements varied, as did energy source utilization: some isolates could grow only with H2S, some only with H2, while others could utilize either as an energy source. These metabolic phenotypes were consistent with in situ geochemical conditions measured using aqueous chemical analysis and in-field measurements made by using gas chromatography and microelectrodes. Pure-culture experiments with an isolate that could utilize H2S and H2 and that represented the dominant phylotype (70% of the PCR clones) showed that H2S and H2 were used simultaneously, without evidence of induction or catabolite repression, and at relative rate differences comparable to those measured in ex situ field assays. Under in situ-relevant concentrations, growth of this isolate with H2S was better than that with H2. The major conclusions drawn from this study are that phylogeny may not necessarily be reliable for predicting physiology and that H2S can dominate over H2 as an energy source in terms of

Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-kappa3S,S',P} 2] and [W{P(2-SC6H4)3-kappa4S,S',S",P}2]: synthesis, structures and redox chemistry.

PubMed

Hildebrand, Alexandra; Lönnecke, Peter; Silaghi-Dumitrescu, Luminita; Hey-Hawkins, Evamarie

2008-09-14

PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

Molecular structure studies of (1S,2S)-2-benzyl-2,3-dihydro-2-(1H-inden-2-yl)-1H-inden-1-ol

PubMed Central

Zhang, Tao; Paluch, Krzysztof; Scalabrino, Gaia; Frankish, Neil; Healy, Anne-Marie; Sheridan, Helen

2015-01-01

The single enantiomer (1S,2S)-2-benzyl-2,3-dihydro-2-(1H-inden-2-yl)-1H-inden-1-ol (2), has recently been synthesized and isolated from its corresponding diastereoisomer (1). The molecular and crystal structures of this novel compound have been fully analyzed. The relative and absolute configurations have been determined by using a combination of analytical tools including X-ray crystallography, X-ray Powder Diffraction (XRPD) analysis and Nuclear Magnetic Resonance (NMR) spectroscopy. PMID:25750458

The solubility of gold in H 2 O-H 2 S vapour at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zezin, Denis Yu.; Migdisov, Artashes A.; Williams-Jones, Anthony E.

2011-09-01

This experimental study sheds light on the complexation of gold in reduced sulphur-bearing vapour, specifically, in H 2O-H 2S gas mixtures. The solubility of gold was determined in experiments at temperatures of 300, 350 and 365 °C and reached 2.2, 6.6 and 6.3 μg/kg, respectively. The density of the vapour varied from 0.02 to 0.22 g/cm 3, the mole fraction of H 2S varied from 0.03 to 0.96, and the pressure in the cell reached 263 bar. Statistically significant correlations of the amount of gold dissolved in the fluid with the fugacity of H 2O and H 2S permit the experimental data to be fitted to a solvation/hydration model. According to this model, the solubility of gold in H 2O-H 2S gas mixtures is controlled by the formation of sulphide or bisulphide species solvated by H 2S or H 2O molecules. Formation of gold sulphide species is favoured statistically over gold bisulphide species and thus the gold is interpreted to dissolve according to reactions of the form: Au(s)+(n+1)HS(g)=AuS·(HS)n(g)+H(g) Au(s)+HS(g)+mHO(g)=AuS·(HO)m(g)+H(g) Equilibrium constants for Reaction (A1) and the corresponding solvation numbers ( K A1 and n) were evaluated from the study of Zezin et al. (2007). The equilibrium constants as well as the hydration numbers for Reaction (A2) ( K A2 and m) were adjusted simultaneously by a custom-designed optimization algorithm and were tested statistically. The resulting values of log K A2 and m are -15.3 and 2.3 at 300 and 350 °C and -15.1 and 2.2 at 365 °C, respectively. Using the calculated stoichiometry and stability of Reactions (A1) and (A2), it is now possible to quantitatively evaluate the contribution of reduced sulphur species to the transport of gold in aqueous vapour at temperatures up to 365 °C. This information will find application in modelling gold ore-forming processes in vapour-bearing magmatic hydrothermal systems, notably those of epithermal environments.

Unimolecular reactivity of organotrifluoroborate anions, RBF3- , and their alkali metal cluster ions, M(RBF3 )2- (M = Na, K; R = CH3 , CH3 CH2 , CH3 (CH2 )3 , CH3 (CH2 )5 , c-C3 H5 , C6 H5 , C6 H5 CH2 , CH2 CHCH2 , CH2 CH, C6 H5 CO).

PubMed

Bathie, Fiona L B; Bowen, Chris J; Hutton, Craig A; O'Hair, Richard A J

2018-07-15

Potassium organotrifluoroborates (RBF 3 K) are important reagents used in organic synthesis. Although mass spectrometry is commonly used to confirm their molecular formulae, the gas-phase fragmentation reactions of organotrifluoroborates and their alkali metal cluster ions have not been previously reported. Negative-ion mode electrospray ionization (ESI) together with collision-induced dissociation (CID) using a triple quadrupole mass spectrometer were used to examine the fragmentation pathways for RBF 3 - (where R = CH 3 , CH 3 CH 2 , CH 3 (CH 2 ) 3 , CH 3 (CH 2 ) 5 , c-C 3 H 5 , C 6 H 5 , C 6 H 5 CH 2 , CH 2 CHCH 2 , CH 2 CH, C 6 H 5 CO) and M(RBF 3 ) 2 - (M = Na, K), while density functional theory (DFT) calculations at the M06/def2-TZVP level were used to examine the structures and energies associated with fragmentation reactions for R = Me and Ph. Upon CID, preferentially elimination of HF occurs for RBF 3 - ions for systems where R = an alkyl anion, whereas R - formation is favoured when R = a stabilized anion. At higher collision energies loss of F - and additional HF losses are sometimes observed. Upon CID of M(RBF 3 ) 2 - , formation of RBF 3 - is the preferred pathway with some fluoride transfer observed only when M = Na. The DFT-calculated relative thermochemistry for competing fragmentation pathways is consistent with the experiments. The main fragmentation pathways of RBF 3 - are HF elimination and/or R - loss. This contrasts with the fragmentation reactions of other organometallate anions, where reductive elimination, beta hydride transfer and bond homolysis are often observed. The presence of fluoride transfer upon CID of Na(RBF 3 ) 2 - but not K(RBF 3 ) 2 - is in agreement with the known fluoride affinities of Na + and K + and can be rationalized by Pearson's HSAB theory. Copyright © 2018 John Wiley & Sons, Ltd.

Yb3O(OH)6Cl·2H2O: an anion-exchangeable hydroxide with a cationic inorganic framework structure.

PubMed

Goulding, Helen V; Hulse, Sarah E; Clegg, William; Harrington, Ross W; Playford, Helen Y; Walton, Richard I; Fogg, Andrew M

2010-10-06

The first anion-exchangeable framework hydroxide, Yb(3)O(OH)(6)Cl·2H(2)O, has been synthesized hydrothermally. This material has a three-dimensional cationic ytterbium oxyhydroxide framework with one-dimensional channels running through the structure in which the chloride anions and water molecules are located. The framework is thermally stable below 200 °C and can be reversibly dehydrated and rehydrated with no loss of crystallinity. Additionally, it is able to undergo anion-exchange reactions with small ions such as carbonate, oxalate, and succinate with retention of the framework structure.

Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid D2-H2 and HD -H2 mixtures: An electron-spin-resonance study

NASA Astrophysics Data System (ADS)

Kumada, Takayuki

2006-03-01

Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid HD -H2 and D2-H2 mixtures were studied in the temperature range between 4 and 8K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within ˜300s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H2 molecules, D(H2)n(HD)12-n→H(H2)n-1(HD)13-n or D(H2)n(D2)12-n→H(HD )(H2)n-1(D2)12-n for 12⩾n⩾1. Rate constant for the D +H2 reaction between neighboring D atom-H2 molecule pair is determined to be (7.5±0.7)×10-3s-1 in solid HD -H2 and (1.3±0.3)×10-2s-1 in D2-H2 at 4.1K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7K within experimental error of ±30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D2 molecules, D(HD)12 or D(D2)12. This D atom undergoes the D +DH reaction with one of its nearest-neighboring HD molecules in solid HD -H2 or diffuses to the neighbor of H2 molecules to allow the D +H2 reaction in solid HD -H2 and D2-H2. The former is the main channel in solid HD -H2 below 6K where D atoms diffuse very slowly, whereas the latter dominates over the former above 6K. Rate for the reactions in the slow process is independent of temperature below 6K but increases with the increase in temperature above 6K. We found that the increase is due to the increase in hopping rate of D atoms to the neighbor of H2 molecules. Rate

Working with "H2S": facts and apparent artifacts.

PubMed

Wedmann, Rudolf; Bertlein, Sarah; Macinkovic, Igor; Böltz, Sebastian; Miljkovic, Jan Lj; Muñoz, Luis E; Herrmann, Martin; Filipovic, Milos R

2014-09-15

Hydrogen sulfide (H2S) is an important signaling molecule with physiological endpoints similar to those of nitric oxide (NO). Growing interest in its physiological roles and pharmacological potential has led to large sets of contradictory data. The principle cause of these discrepancies can be the common neglect of some of the basic H2S chemistry. This study investigates how the experimental outcome when working with H2S depends on its source and dose and the methodology employed. We show that commercially available NaHS should be avoided and that traces of metal ions should be removed because these can reduce intramolecular disulfides and change protein structure. Furthermore, high H2S concentrations may lead to a complete inhibition of cell respiration, mitochondrial membrane potential depolarization and superoxide generation, which should be considered when discussing the biological effects observed upon treatment with high concentrations of H2S. In addition, we provide chemical evidence that H2S can directly react with superoxide. H2S is also capable of reducing cytochrome c(3+) with the concomitant formation of superoxide. H2S does not directly react with nitrite but with NO electrodes that detect H2S. In addition, H2S interferes with the Griess reaction and should therefore be removed from the solution by Cd(2+) or Zn(2+) precipitation prior to nitrite quantification. 2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO) is reduced by H2S, and its use should be avoided in combination with H2S. All these constraints must be taken into account when working with H2S to ensure valid data. Copyright © 2014 Elsevier Inc. All rights reserved.

Structural evolution of the [(CO2)n(H2O)]- cluster anions: quantifying the effect of hydration on the excess charge accommodation motif.

PubMed

Muraoka, Azusa; Inokuchi, Yoshiya; Hammer, Nathan I; Shin, Joong-Won; Johnson, Mark A; Nagata, Takashi

2009-08-06

The [(CO2)n(H2O)]- cluster anions are studied using infrared photodissociation (IPD) spectroscopy in the 2800-3800 cm(-1) range. The observed IPD spectra display a drastic change in the vibrational band features at n = 4, indicating a sharp discontinuity in the structural evolution of the monohydrated cluster anions. The n = 2 and 3 spectra are composed of a series of sharp bands around 3600 cm(-1), which are assignable to the stretching vibrations of H2O bound to C2O4- in a double ionic hydrogen-bonding (DIHB) configuration, as was previously discussed (J. Chem. Phys. 2005, 122, 094303). In the n > or = 4 spectrum, a pair of intense bands additionally appears at approximately 3300 cm(-1). With the aid of ab initio calculations at the MP2/6-31+G* level, the 3300 cm(-1) bands are assigned to the bending overtone and the hydrogen-bonded OH vibration of H2O bound to CO2- via a single O-H...O linkage. Thus, the structures of [(CO2)n(H2O)]- evolve with cluster size such that DIHB to C2O4- is favored in the smaller clusters with n = 2 and 3 whereas CO2- is preferentially stabilized via the formation of a single ionic hydrogen-bonding (SIHB) configuration in the larger clusters with n > or = 4.

A new global analytical potential energy surface of NaH2+ system and dynamical calculation for H(2S) + NaH+(X2Σ+) → Na+(1S) + H2(X1Σg+) reaction

NASA Astrophysics Data System (ADS)

Yuan, Meiling; Li, Wentao; Yuan, Jiuchuang

2018-05-01

A new global potential energy surface (PES) of the NaH2+ system is constructed by fitting 27,621 ab initio energy points with the neural network method. The root mean square error of the new PES is only 4.1609 × 10-4 eV. Based on the new PES, dynamical calculations have been performed using the time-dependent quantum wave packet method. These results are then compared with the H(2S) + LiH+(X2Σ+) → Li+(1S) + H2(X1Σg+) reaction. The direct abstract mechanism is found to play an important role in the reaction because only forward scattering signals on the differential cross section results for all calculated collision energies.

Xenobiotic metal-induced autoimmunity: mercury and silver differentially induce antinucleolar autoantibody production in susceptible H-2s, H-2q and H-2f mice

PubMed Central

Hansson, M; Abedi-Valugerdi, M

2003-01-01

Xenobiotic-metals such as mercury (Hg) and silver (Ag) induce an H-2 linked antinucleolar autoantibody (ANolA) production in susceptible mice. The mechanism for induction of ANolA synthesis is not well understood. However, it has been suggested that both metals interact with nucleolar proteins and reveal cryptic self-peptides to nontolerant autoreactive T cells, which in turn stimulate specific autoreactive B cells. In this study, we considered this suggestion and asked if mercury and silver display, if not identical, similar cryptic self-peptides, they would induce comparable ANolA responses in H-2 susceptible mice. We analysed the development of ANolA production in mercury- and/or silver-treated mice of H-2s, H-2q and H-2f genotypes. We found that while mercury stimulated ANolA synthesis in all strains tested, silver induced ANolA responses of lower magnitudes in only H-2s and H-2q mice, but not in H-2f mice. Resistance to silver in H-2f mice was independent of the dosage/time-period of silver-treatment and non-H-2 genes. Further studies showed that F1 hybrid crosses between silver-susceptible A.SW (H-2s) and -resistant A.CA (H-2f) mice were resistant to silver, but not mercury with regard to ANolA production. Additionally, the magnitudes of mercury-induced ANolA responses in the F1 hybrids were lower than those of their parental strains. The above differential ANolA responses to mercury and silver can be explained by various factors, including the different display of nucleolar cryptic peptides by these xenobiotics, determinant capture and coexistence of different MHC molecules. Our findings also suggest that the ability of a xenobiotic metal merely to create cryptic self-peptides may not be sufficient for the induction of an ANolA response. PMID:12605692

Investigation of H2S separation from H2S/CH4 mixtures using functionalized and non-functionalized vertically aligned carbon nanotube membranes

NASA Astrophysics Data System (ADS)

Gilani, Neda; Towfighi, Jafar; Rashidi, Alimorad; Mohammadi, Toraj; Omidkhah, Mohammad Reza; Sadeghian, Ahmad

2013-04-01

Separation of H2S from binary mixtures of H2S/CH4 using vertically aligned carbon nanotube membranes fabricated in anodic aluminum oxide (AAO) template was studied experimentally. Carbon nanotubes (CNTs) were grown in five AAO templates with different pore diameters using chemical vapor deposition, and CNT/AAO membranes with tubular carbon nanotube structure and open caps were selected for separation of H2S. For this, two tubular CNT/AAO membranes were fabricated with the CNT inner diameters of 23 and 8 nm. It was found that permeability and selectivity of the membrane with inner diameter of 23 nm for CNT were independent of upstream feed pressure and H2S feed concentration unlike that of CNT having an inner diameter of 8 nm. Selectivity of these membranes for separation of H2S was obtained in the ranges of 1.36-1.58 and 2.11-2.86, for CNTs with internal diameters of 23 and 8 nm, respectively. In order to enhance the separation of H2S from H2S/CH4 mixtures, dodecylamine was used to functionalize the CNT/AAO membrane with higher selectivity. The results showed that for amido-functionalized membrane, both upstream feed pressure and H2S partial pressure in the feed significantly increased H2S permeability, and selectivity for H2S being in the range of 3.0-5.57 respectively.

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

PubMed

Schlueter, John A; Geiser, Urs; Funk, Kylee A

2008-02-01

The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

2011-03-01

"H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

Synthesis, crystal structure and thermal study of the hybrid nickel sulfate: C6N2H16[Ni(H2O)6(SO4)2].2H2O

NASA Astrophysics Data System (ADS)

Ngopoh, F. A. I.; Hamdi, N.; Chaouch, S.; Lachkar, M.; da Silva, I.; El Bali, B.

2018-03-01

A new inorganic-organic hybrid open framework nickel sulfate C6N2H16[Ni(H2O)6(SO4)2].2H2O has been synthesized by slow evaporation in aqueous solution using trans-1,4-diaminocyclohexane as structure-directing agent. It was characterized by single-crystal X-ray diffraction, infrared spectroscopy and analyzed by TGA-DSC. The compound crystallizes in the monoclinic space group P21/n, with the unit cell parameters of a = 6.2586 Å, b = 12.3009 Å, c = 13.2451 Å, β = 98,047°, Z = 4. Its crystal structure consists of isolated polyhedrons [Ni(H2O)6]2+ and [SO4]2- and free water which connects through hydrogen bonds. This association results in the porous framework where the protonated organic molecule trans-1,4-diaminocyclohexane is located as a counter ion. The IR spectra Shows the bands corresponding to the sulfate anion, water molecule and diprotonated trans-1-4-diaminocyclohexane. Thermal study indicates the loss of water molecules and the degradation of trans-1-4-diaminocyclohexane.

High-resolution photoelectron spectroscopy of TiO3H2-: Probing the TiO2- + H2O dissociative adduct

NASA Astrophysics Data System (ADS)

DeVine, Jessalyn A.; Abou Taka, Ali; Babin, Mark C.; Weichman, Marissa L.; Hratchian, Hrant P.; Neumark, Daniel M.

2018-06-01

Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiO3H2- anions is used to probe the simplest titania/water reaction, TiO20/- + H2O. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH)2- geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO2- monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH)2. The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO2- indicates that reaction with water stabilizes neutral TiO2 more than the anion, providing insight into the fundamental chemical interactions between titania and water.

Functionalization of liquid-exfoliated two-dimensional 2H-MoS2.

PubMed

Backes, Claudia; Berner, Nina C; Chen, Xin; Lafargue, Paul; LaPlace, Pierre; Freeley, Mark; Duesberg, Georg S; Coleman, Jonathan N; McDonald, Aidan R

2015-02-23

Layered two-dimensional (2D) inorganic transition-metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS2 . We found that the reaction of liquid-exfoliated 2D MoS2 , with M(OAc)2 salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS2 -M(OAc)2 materials. Importantly, this method furnished the 2H-polytype of MoS2 which is a semiconductor. X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT-IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS2 surface sulfur atoms to the M(OAc)2 salt. Interestingly, functionalization of 2H-MoS2 allows for its dispersion/processing in more conventional laboratory solvents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

Diagnostic cyclisation reactions which follow phosphate transfer to carboxylate anion centres for energised [M-H]- anions of pTyr-containing peptides.

PubMed

Tran, T T Nha; Wang, Tianfang; Hack, Sandra; Bowie, John H

2011-09-15

The low-energy negative ion phosphoTyr to C-terminal -CO(2)PO(3)H(2) rearrangement occurs for energised peptide [M-H](-) anions even when there are seven amino acid residues between the pTyr and C-terminal amino acid residues. The rearranged C-terminal -CO(2)PO(2)H(O(-)) group effects characteristic S(N)i cyclisation/cleavage reactions. The most pronounced of these involves the electrophilic central backbone carbon of the penultimate amino acid residue. This reaction is aided by the intermediacy of an H-bonded intermediate in which the nucleophilic and electrophilic reaction centres are held in proximity in order for the S(N)i cyclisation/cleavage to proceed. The ΔG(reaction) is +184 kJ mol(-1) with the barrier to the S(N)i transition state being +240 kJ mol(-1) at the HF/6-31 + G(d)//AM1 level of theory. A similar phosphate rearrangement from pTyr to side chain CO(2)(-) (of Asp or Glu) may also occur for energised peptide [M-H](-) anions. The reaction is favourable: ΔG(reaction) is -44 kJ mol(-1) with a maximum barrier of +21 kJ mol(-1) (to the initial transition state) when Asp and Tyr are adjacent. The rearranged species R(1)-Tyr-NHCH(CH(2)CO(2)PO(3)H(-))COR(2) (R(1)  = CHO; R(2)  = OCH(3)) may undergo an S(N)i six-centred cyclisation/cleavage reaction to form the product anion R(1)-Tyr(NH(-)). This process has a high energy requirement [ΔG(reaction)  = +224 kJ mol(-1), with the barrier to the S(N)i transition state being +299 kJ mol(-1)]. Copyright © 2011 John Wiley & Sons, Ltd.

Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

NASA Technical Reports Server (NTRS)

Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

1991-01-01

Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Lyons, M.; Siegel, E.

2010-03-01

``Water water everywhere; ne'er a drop to drink''[Coleridg(1798)]; now:``Hydrogen hydrogen everywhere;STILL ne'er a drop to drink'': ONLY H2 can be ``FLYING-WATER''/``chemical-rain-in-pipelines''/ ``Hindenberg-effect (H2-UP;H2O-DOWN): atomic-weights ratio: O/H2O=[16]/[18]˜90%; O already in air uphill; NO H2O pumping need! In water-starved glacial-melting world, rescue ONLY by Siegel[3rd Intl.Conf.Alt.Energy,Hemisphere/Springer(1980)- vol.5/ p.459]Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating- system. Rosenfeld[Sci.315,1396(3/9/2007)]-Biello[Sci.Am.(3/9/ 2007)]crucial geomorphology which ONLY maximal-buoyancy light- est-element H2 can exploit, to again make ``Mountains into Fount- ains": Siegel ``terra-forming''(and ocean-rebasificaton!!!) long pre-``Holdren''-``Ciccerine" ``geo-enginering'', only via Siegel proprietary magnetic-hydrogen-valve permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Sci.300,1740(03)]global-pandemics (cancers/blindness/famine)dire-warning about H2-(ALONE)economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!

Effect of acetate and nitrate anions on the molecular structure of 3-(hydroxyimino)-2-butanone-2-(1H-benzimidazol-2-yl)hydrazone

NASA Astrophysics Data System (ADS)

Kamat, Vinayak; Naik, Krishna; Revankar, Vidyanand K.

2017-04-01

A novel Schiff base ligand 3-(hydroxyimino)-2-butanone-2-(1H-benzimidazol-2-yl)hydrazone has been synthesized by the condensation reaction of 2-Hydrazinobenzimidazole with diacetyl monoxime in presence of acetic acid catalyst. The ligand has crystallized as its acetate salt, due to the charge-assisted hydrogen bonding between protonated benzimidazole ring and acetate anion. Efforts to synthesize the zinc(II) complex of the title compound, has resulted in the formation of a nitrate salt of the ligand, instead of coordination complex of zinc(II). Acetate salt has crystallized in monoclinic P 21/n, while the nitrate salt has crystallized in a triclinic crystal system with P -1 space group. Hirshfeld surface analysis is presented for both of the crystal structures. Structures of synthesized molecules are even computationally optimized using DFT. A comparative structural approach between the synthesized molecules and DFT optimized structure of bare ligand without any counterions is analyzed in terms of bond parameters. Hydrogen bonding is explained keeping the anions as the central dogma. Mass fragmentation pattern of the organic molecule and comparative account of IR, 1H and 13C NMR chemical shifts are also presented. Compounds are screened for their antibacterial and antifungal potencies against few pathogenic microorganisms. The organic motif is found be an excellent antifungal agent.

Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

NASA Astrophysics Data System (ADS)

Sun, Shichen; Awadallah, Osama; Cheng, Zhe

2018-02-01

It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

Broadening of spectral lines of CO2, N2O , H2CO, HCN, and H2S by pressure of gases dominant in planetary atmospheres (H2, He and CO2)

NASA Astrophysics Data System (ADS)

Samuels, Shanelle; Gordon, Iouli; Tan, Yan

2018-01-01

HITRAN1,2 is a compilation of spectroscopic parameters that a variety of computer codes use to predict and simulate the transmission and emission of light in planetary atmospheres. The goal of this project is to add to the potential of the HITRAN database towards the exploration of the planetary atmospheres by including parameters describing broadening of spectral lines by H2, CO2, and He. These spectroscopic data are very important for the study of the hydrogen and helium-rich atmospheres of gas giants as well as rocky planets with volcanic activities, including Venus and Mars, since their atmospheres are dominated by CO2. First step in this direction was accomplished by Wilzewski et al.3 where this was done for SO2, NH3, HF, HCl, OCS and C2H2. The molecules investigated in this work were CO2, N2O, H2CO, HCN and H2S. Line-broadening coefficients, line shifts and temperature-dependence exponents for transitions of these molecules perturbed by H2, CO2 and He have been assembled from available peer-reviewed experimental and theoretical sources. The data was evaluated and the database was populated with these data and their extrapolations/interpolations using semi-empirical models that were developed to this end.Acknowledgements: Financial support from NASA PDART grant NNX16AG51G and the Smithsonian Astrophysical Observatory Latino Initiative Program from the Latino Initiatives Pool, administered by the Smithsonian Latino Center is gratefully acknowledged.References: 1. HITRAN online http://hitran.org/2. Gordon, I.E., Rothman, L.S., Hill, C., Kochanov, R.V., Tan, Y., et al., 2017. The HITRAN2016 Molecular Spectroscopic Database. J. Quant. Spectrosc. Radiat. Transf. doi:10.1016/j.jqsrt.2017.06.0383. Wilzewski, J.S., Gordon, I.E., Kochanov, R. V., Hill, C., Rothman, L.S., 2016. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2. J. Quant. Spectrosc. Radiat

Vibrational mode frequencies of H2S and H2O adsorbed on Ge(0 0 1)-(2 × 1) surfaces

NASA Astrophysics Data System (ADS)

Hartnett, M.; Fahy, S.

2015-02-01

The equilibrium geometry and vibrational modes of H2S and H2O-terminated Ge(0 0 1)-(2 × 1) surfaces are calculated in a supercell approach using first-principles density functional theory in the local density (LDA), generalized gradient (GGA) approximations and van der Waals (vdW) interactions. Mode frequencies are found using the frozen phonon method. For the H2S-passivated surface, the calculated frequencies in LDA (GGA) are 2429 cm-1 (2490) for the Hsbnd S stretch mode, 712 cm-1 (706) for the Hsbnd S bond bending mode, 377 cm-1 (36) for the Gesbnd S stretch mode and 328 cm-1 (337) for Hsbnd S wag mode. Frequencies for the H2O passivated surface are 3590 cm-1 (3600) for the Hsbnd O stretch mode, 921 cm-1 (947) for the bending mode, 609 cm-1 (559) for the Gesbnd O stretch, 1995 cm-1 (1991) for the Gesbnd H stretch mode, 498 cm-1 (478) for the Gesbnd H bending mode and 342 cm-1 (336) for the Hsbnd O wag mode. The differences between the functionals including vdW terms and the LDA or GGA are less than the differences between LDA and GGA for the vibrational mode frequencies.

Di­hydro­cyclam dimaleate [H2(cyclam)(maleate)2

PubMed Central

Mireille Ninon, Mbonzi Ombenga; Fahim, Mohammed; Lachkar, Mohammed; Marco Contelles, José Luis; Perles, Josefina; El Bali, Brahim

2013-01-01

The asymmetric unit of the title mol­ecular salt [systematic name: 1,4,8,11-tetraazacyclotetradecane-1,8-diium bis(3-carboxy­prop-2-enoate)], C10H26N4 2+·2C4H3O4 −, contains two half-cations (both completed by crystallographic inversion symmetry) and two maleate anions. The cyclam macrocycles adopt trans-III conformations, supported by two intra­molecular N—H⋯O hydrogen bonds. The O-bonded H atom of each maleate ion is disordered over two positions with an occupancy ratio of 0.61 (5):0.39 (5): each one generates an intra­molecular O—H⋯O hydrogen bond. In the crystal, the cations are linked to the anions by N—H⋯O hydrogen bonds, generating [001] chains. PMID:24098252

pH-sensitive interaction of HMG-CoA reductase inhibitors (statins) with organic anion transporting polypeptide 2B1.

PubMed

Varma, Manthena V; Rotter, Charles J; Chupka, Jonathan; Whalen, Kevin M; Duignan, David B; Feng, Bo; Litchfield, John; Goosen, Theunis C; El-Kattan, Ayman F

2011-08-01

The human organic anion transporting polypeptide 2B1 (OATP2B1, SLCO2B1) is ubiquitously expressed and may play an important role in the disposition of xenobiotics. The present study aimed to examine the role of OATP2B1 in the intestinal absorption and tissue uptake of 3-hydroxy-3-methylglutaryl-Coenzyme A (HMG-CoA) reductase inhibitors (statins). We first investigated the functional affinity of statins to the transporter as a function of extracellular pH, using OATP2B1-transfeced HEK293 cells. The results indicate that OATP2B1-mediated transport is significant for rosuvastatin, fluvastatin and atorvastatin, at neutral pH. However, OATP2B1 showed broader substrate specificity as well as enhanced transporter activity at acidic pH. Furthermore, uptake at acidic pH was diminished in the presence of proton ionophore, suggesting proton gradient as the driving force for OATP2B1 activity. Notably, passive transport rates are predominant or comparable to active transport rates for statins, except for rosuvastatin and fluvastatin. Second, we studied the effect of OATP modulators on statin uptake. At pH 6.0, OATP2B1-mediated transport of atorvastatin and cerivastatin was not inhibitable, while rosuvastatin transport was inhibited by E-3-S, rifamycin SV and cyclosporine with IC(50) values of 19.7 ± 3.3 μM, 0.53 ± 0.2 μM and 2.2 ± 0.4 μM, respectively. Rifamycin SV inhibited OATP2B1-mediated transport of E-3-S and rosuvastatin with similar IC(50) values at pH 6.0 and 7.4, suggesting that the inhibitor affinity is not pH-dependent. Finally, we noted that OATP2B1-mediated transport of E-3-S, but not rosuvastatin, is pH sensitive in intestinal epithelial (Caco-2) cells. However, uptake of E-3-S and rosuvastatin by Caco-2 cells was diminished in the presence of proton ionophore. The present results indicate that OATP2B1 may be involved in the tissue uptake of rosuvastatin and fluvastatin, while OATP2B1 may play a significant role in the intestinal absorption of several

Etude des mécanismes d'ionisation de H{2}O par interaction He^{*}(2 ^1S, 2 ^3S)/Ne^{*}(^3P{0}, ^3P{2})+H{2}O

NASA Astrophysics Data System (ADS)

Le Nadan, André; Sinou, Guillaume; Tuffin, Firmin

1993-06-01

Experimental observations of Penning ionisation of H{2}O by the helium metastables 21S and 23S and by the neon metastables ^3P{0} and ^3P{2} are reported. The kinetic energies of the ions created during the collision process (both parent and fragment) are analysed. Certain particularities of the experimental results are explained by involving the hypothesis of transfers of vibrational energy to kinetic energy. Furthermore, the forms of the energy distributions of the fragment ions are explained by th predissociation of the ^2B{2} state of H{2}O+. Nous avons étudié l'ionisation Penning de H{2}O par des métastables 21S et 23S de l'hélium, ainsi que ^3P{0} et ^3P{2} du néon. Nous avons analysé l'énergie cinétique des ions créés au cours de la collision (parents et fragments). Afin d'interpréter certaines particularités expérimentales, l'hypothèse de transferts d'énergie de vibration en énergie cinétique est proposées. Par ailleurs, les caractéristiques des distributions en énergie des ions fragments sont expliquées par la prédissociation de l'état ^2B{2} de H{2}O+.

H2S and polysulfide metabolism: Conventional and unconventional pathways.

PubMed

Olson, Kenneth R

2018-03-01

It is now well established that hydrogen sulfide (H 2 S) is an effector of a wide variety of physiological processes. It is also clear that many of the effects of H 2 S are mediated through reactions with cysteine sulfur on regulatory proteins and most of these are not mediated directly by H 2 S but require prior oxidation of H 2 S and the formation of per- and polysulfides (H 2 S n , n = 2-8). Attendant with understanding the regulatory functions of H 2 S and H 2 S n is an appreciation of the mechanisms that control, i.e., both increase and decrease, their production and catabolism. Although a number of standard "conventional" pathways have been described and well characterized, novel "unconventional" pathways are continuously being identified. This review summarizes our current knowledge of both the conventional and unconventional. Copyright © 2017 Elsevier Inc. All rights reserved.

Frequency Comb Assisted IR Measurements of H_3^+, H_2D^+ and D_2H^+ Transitions

NASA Astrophysics Data System (ADS)

Jusko, Pavol; Asvany, Oskar; Schlemmer, Stephan

2016-06-01

We present recent measurements of the fundamental transitions of H_3^+, H_2D^+ and D_2H^+ in a 4 K 22-pole trap by action spectroscopic techniques. Either Laser Induced Inhibition of Cluster Growth (He attachment at T≈4 K), endothermic reaction of H_3^+ with O_2, or deuterium exchange has been used as measurement scheme. We used a 3 μm optical parametric oscillator coupled to a frequency comb in order to achieve accuracy generally below 1 MHz. Five transitions of H_3^+, eleven of H_2D^+ and ten of D_2H^+ were recorder in our spectral range. We compare our H_3^+ results with two previous frequency comb assisted works. Moreover, accurate determination of the frequency allows us to predict pure rotational transitions for H_2D^+ and D_2H^+ in the THz range. P. Jusko, C. Konietzko, S. Schlemmer, O. Asvany, J. Mol. Spec. 319 (2016) 55 O. Asvany, S. Brünken, L. Kluge, S. Schlemmer, Appl. Phys. B 114 (2014) 203 O. Asvany, J. Krieg, S. Schlemmer, Rev. Sci. Instr. 83 (2012) 093110 J.N. Hodges, A.J. Perry, P.A. Jenkins, B.M. Siller, B.J. McCall, J. Chem. Phys. 139 (2013) 164201 H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, J.-T. Shy, Phys. Rev. Lett. 109 (2012) 263002

Quantum and quasiclassical dynamics of the multi-channel H + H2S reaction.

PubMed

Qi, Ji; Lu, Dandan; Song, Hongwei; Li, Jun; Yang, Minghui

2017-03-28

The prototypical multi-channel reaction H + H 2 S → H 2 + SH/H + H 2 S has been investigated using the full-dimensional quantum scattering and quasi-classical trajectory methods to unveil the underlying competition mechanism between different product channels and the mode specificity. This reaction favors the abstraction channel over the exchange channel. For both channels, excitations in the two stretching modes promote the reaction with nearly equal efficiency and are more efficient than the bending mode excitation. However, they are all less efficient than the translational energy. In addition, the experimentally observed non-Arrhenius temperature dependence of the thermal rate constants is reasonably reproduced by the quantum dynamics calculations, confirming that the non-Arrhenius behavior is caused by the pronounced quantum tunneling.

Specific IgE to peanut 2S albumin Ara h 7 has a discriminative ability comparable to Ara h 2 and 6.

PubMed

Blankestijn, M A; Otten, H G; Suer, W; Weimann, A; Knol, E F; Knulst, A C

2018-01-01

Little is known on the clinical relevance of peanut 2S albumin Ara h 7. To investigate the discriminative ability of Ara h 7 in peanut allergy and assess the role of cross-reactivity between Ara h 2, 6 and Ara h 7 isoforms. Sensitization to recombinant peanut storage proteins Ara h 1, 2, 3, 6, and 7 was assessed using a line blot in sera from 40 peanut-tolerant and 40 peanut-allergic patients, based on food challenge outcome. A dose-dependent ELISA inhibition experiment was performed with recombinant Ara h 2, 6 and Ara h 7 isoforms. For Ara h 7.0201, an area under the ROC curve was found of 0.83, comparable to Ara h 2 (AUC 0.81) and Ara h 6 (AUC 0.85). Ara h 7 intensity values strongly correlated with those from Ara h 2 and 6 (r s = 0.81). Of all patients sensitized to 2S albumins Ara h 2, 6, or 7, the majority was co-sensitized to all three (n = 24, 68%), although mono-sensitization to either 2S albumin was also observed in selected patients (Ara h 2: n = 6, 17%; Ara h 6: n = 2, 6%; Ara h 7: n = 2, 6%). Binding to Ara h 7.0101 could be strongly inhibited by Ara h 7.0201, but not the other way around. Specific IgE against Ara h 7.0201 has a predictive ability for peanut allergy similar to Ara h 2 and 6 and possesses unique IgE epitopes as well as epitopes shared between the other Ara h 7 isoform and Ara h 2 and 6. While co-sensitization to all three 2S albumins is most common, mono-sensitization to either Ara h 2, 6, or 7 occurs in selected patients, leading to a risk of misdiagnosis when testing for a single 2S albumin. © 2017 John Wiley & Sons Ltd.

Endogenous mitigation of H2S inside of the landfills.

PubMed

Fang, Yuan; Zhong, Zhong; Shen, Dongsheng; Du, Yao; Xu, Jing; Long, Yuyang

2016-02-01

Vast quantities of hydrogen sulfide (H2S) emitted from landfill sites require urgent disposal. The current study focused on source control and examined the migration and conversion behavior of sulfur compounds in two lab-scale simulated landfills with different operation modes. It aimed to explore the possible strategies and mechanisms for H2S endogenous mitigation inside of landfills during decomposition. It was found that the strength of H2S emissions from the landfill sites was dependent on the municipal solid waste (MSW) degradation speed and vertical distribution of sulfide. Leachate recirculation can shorten both the H2S influence period and pollution risk to the surrounding environment. H2S endogenous mitigation may be achieved by chemical oxidation, biological oxidation, adsorption, and/or precipitation in different stages. Migration and conversion mainly affected H2S release behavior during the initial stabilization phase in the landfill. Microbial activities related to sulfur, nitrogen, and iron can further promote H2S endogenous mitigation during the high reducing phase. Thus, H2S endogenous mitigation can be effectively enhanced via control of the aforementioned processes.

Rapid fluctuations in the northern Baltic Sea H2S layer

NASA Astrophysics Data System (ADS)

Kankaanpää, Harri T.; Virtasalo, Joonas J.

2017-12-01

Hydrogen sulfide (H2S) is linked to water quality deterioration in the Baltic Sea, with widespread seafloor hypoxia. We examined the vertical and temporal variability of in situ [H2S], oxygen concentration ([O2]), temperature (T) and pH at weekly, hourly and minute intervals at 13 locations in the western Gulf of Finland in 2013-2014. The main target was the 60-100 m water depth range, containing 3.2-290 μM O2 and 6.3-22.6 μM H2S. Where gas was detected by acoustic surveys, the structure of the H2S layer was more complex compared to stations devoid of gas. Local minima and maxima in pH frequently occurred near the H2S upper boundary (redox transition zone). Except for the homogeneous, tranquil zone above the seafloor at some stations, substantial rapid changes in hydrographic conditions were common. Typically, a layer of marked temporal T variability was present atop or within the topmost H2S layers. The largest temporal changes over a weekly period were - 0.44 °C/- 10.8 μM H2S/- 0.12 pH units (at seafloor level), + 0.18 °C/+7.9 μM H2S between casts (1 h) and + 0.03 °C/- 2.5 μM H2S per minute (high resolution logging). Abrupt [H2S] changes were recorded at two stations with sediments containing free gas. The T and [H2S] changes were synchronous at several layers, reflecting water movement. We conclude that rapid changes occur in hydrographic conditions in the near-bottom H2S layer in the northern Baltic Sea, especially at locations where free gas is present in the underlying sediments.

First-principles characterization of potassium intercalation in the hexagonal 2H-MoS2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.

2012-01-12

Periodic density functional theory calculations were performed to study the structural and electronic properties of potassium intercalated into hexagonal MoS{sub 2} (2H-MoS{sub 2}). Metallic potassium (K) atoms are incrementally loaded in the hexagonal sites of the interstitial spaces between MoS2 sheets of the 2H-MoS{sub 2} bulk structure generating 2H-KxMoS2 (0.125 {<=} x {<=} 1.0) structures. To accommodate the potassium atoms, the interstitial spacing c parameter in the 2H-MoS{sub 2} bulk expands from 12.816 {angstrom} in 2H-MoS{sub 2} to 16.086 {angstrom} in 2H-K{sub 0.125}MoS{sub 2}. The second lowest potassium loading concentration (K{sub 0.25}MoS{sub 2}) results in the largest interstitial spacing expansionmore » (to c = 16.726 {angstrom}). Our calculations show that there is a small gradual contraction of the interstitial spacing as the potassium loading increases with c = 14.839 {angstrom} for KMoS{sub 2}. This interstitial contraction is correlated with an in-plane expansion of the MoS{sub 2} sheets, which is in good agreement with experimental X-ray diffraction (XRD) measurements. The electronic analysis shows that potassium readily donates its 4s electron to the conduction band of the 2H-K{sub x}MoS{sub 2}, and is largely ionic in character. As a result of the electron donation, the 2H-K{sub x}MoS{sub 2} system changes from a semiconductor to a more metallic system with increasing potassium intercalation. For loadings 0.25 {<=} x {<=} 0.625, triangular Mo-Mo-Mo moieties are prominent and tend to form rhombitrihexagonal motifs. Intercalation of H{sub 2}O molecules that solvate the K atoms is likely to occur in catalytic conditions. The inclusion of two H{sub 2}O molecules per K atom in the K{sub 0.25}MoS{sub 2} structure shows good agreement with XRD measurements.« less

[H{sub 2}en]{sub 2}{l_brace}La{sub 2}M(SO{sub 4}){sub 6}(H{sub 2}O){sub 2}{r_brace} (M=Co, Ni): First organically templated 3d-4f mixed metal sulfates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan Yanping; Wang Ruiyao; Kong Deyuan

2005-06-15

The first organically templated 3d-4f mixed metal sulfates, [H{sub 2}en]{sub 2}{l_brace}La{sub 2}M(SO{sub 4}){sub 6}(H{sub 2}O){sub 2}{r_brace} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediaminemore » cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions)« less

Hydrogen sulfide (H 2S) in urban ambient air

NASA Astrophysics Data System (ADS)

Kourtidis, K.; Kelesis, A.; Petrakakis, M.

Despite indications of high hydrogen sulfide levels in some urban environments, only sparse measurements have been reported in the literature. Here we present one full year of hydrogen sulfide measurements in an urban traffic site in the city of Thessaloniki, Greece. In this 1-million-population city the H 2S concentrations were surprisingly high, with a mean annual concentration of 8 μg m -3 and wintertime mean monthly concentrations up to 20 μg m -3 (12.9 ppb). Daily mean concentrations in the winter were up to 30 μg m -3 (19.3 ppb), while hourly concentrations were up to 54 μg m -3 (34.8 ppb). During calm (wind velocity < 0.5 m s -1) conditions, mainly encountered during night-time hours, hourly values of H 2S were highly correlated with those of CO ( r2 = 0.75) and SO 2 ( r2 = 0.70), pointing to a common traffic source from catalytic converters. Annual mean concentrations are above the WHO recommendation for odor annoyance; hence, H 2S might play a role to the malodorous episodes that the city occasionally experiences. The high ambient H 2S levels might also be relevant to the implementation of preservation efforts for outdoor marble and limestone historical monuments that have been targeting SO 2 emissions as an atmospheric acidity source, since the measurements presented here suggest that about 19% of the annual sulfur (SO 2 + H 2S) emissions in Thessaloniki are in the form of H 2S.

Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid D{sub 2}-H{sub 2} and HD-H{sub 2} mixtures: An electron-spin-resonance study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumada, Takayuki

2006-03-07

Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid HD-H{sub 2} and D{sub 2}-H{sub 2} mixtures were studied in the temperature range between 4 and 8 K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30 s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within {approx}300more » s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H{sub 2} molecules, D(H{sub 2}){sub n}(HD){sub 12-n}{yields}H(H{sub 2}){sub n-1}(HD){sub 13-n} or D(H{sub 2}){sub n}(D{sub 2}){sub 12-n}{yields}H(HD)(H{sub 2}){sub n-1}(D{sub 2}){sub 12-n} for 12{>=}n{>=}1. Rate constant for the D+H{sub 2} reaction between neighboring D atom-H{sub 2} molecule pair is determined to be (7.5{+-}0.7)x10{sup -3} s{sup -1} in solid HD-H{sub 2} and (1.3{+-}0.3)x10{sup -2} s{sup -1} in D{sub 2}-H{sub 2} at 4.1 K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7 K within experimental error of {+-}30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D{sub 2} molecules, D(HD){sub 12} or D(D{sub 2}){sub 12}. This D atom undergoes the D+DH reaction with one of its nearest-neighboring HD molecules in solid HD-H{sub 2} or diffuses to the neighbor of H{sub 2} molecules to allow the D+H{sub 2} reaction in solid HD-H{sub 2} and D{sub 2}-H{sub 2}. The former is the main channel in solid HD-H{sub 2} below 6 K where D atoms diffuse very slowly, whereas the latter dominates

Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11H 12 and NaCB 11H 12

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E.

The disordered phases ofLiCB 11H 12 and NaCB 11H 12 possess superb superionic conductivities that make them suitable as solid electrolytes. In these materials, cation diffusion correlates with high orientational mobilities of the CB 11H 12 - anions; however, the precise relationship has yet to be demonstrated. In this work, ab initio molecular dynamics and quasielastic neutron scattering are combined to probe anion reorientations and their mechanistic connection to cation mobility over a range of timescales and temperatures. It is found that anions do not rotate freely, but rather transition rapidly between orientations defined by the cation sublattice symmetry. Themore » symmetry-breaking carbon atom in CB 11H 12 - also plays a critical role by perturbing the energy landscape along the instantaneous orientation of the anion dipole, which couples fluctuations in the cation probability density directly to the anion motion. Anion reorientation rates exceed 3 x 10 10 s -1, suggesting the underlying energy landscape fluctuates dynamically on diffusion-relevant timescales. Furthermore, carbon is found to modify the orientational preferences of the anions and aid rotational mobility, creating additional symmetry incompatibilities that inhibit ordering. The results suggest that synergy between the anion reorientational dynamics and the carbon-modified cation-anion interaction accounts for the higher ionic conductivity in CB 11H 12 - salts compared with B 12H 12 2-.« less

Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11H 12 and NaCB 11H 12

DOE PAGES

Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E.; ...

2018-02-20

The disordered phases ofLiCB 11H 12 and NaCB 11H 12 possess superb superionic conductivities that make them suitable as solid electrolytes. In these materials, cation diffusion correlates with high orientational mobilities of the CB 11H 12 - anions; however, the precise relationship has yet to be demonstrated. In this work, ab initio molecular dynamics and quasielastic neutron scattering are combined to probe anion reorientations and their mechanistic connection to cation mobility over a range of timescales and temperatures. It is found that anions do not rotate freely, but rather transition rapidly between orientations defined by the cation sublattice symmetry. Themore » symmetry-breaking carbon atom in CB 11H 12 - also plays a critical role by perturbing the energy landscape along the instantaneous orientation of the anion dipole, which couples fluctuations in the cation probability density directly to the anion motion. Anion reorientation rates exceed 3 x 10 10 s -1, suggesting the underlying energy landscape fluctuates dynamically on diffusion-relevant timescales. Furthermore, carbon is found to modify the orientational preferences of the anions and aid rotational mobility, creating additional symmetry incompatibilities that inhibit ordering. The results suggest that synergy between the anion reorientational dynamics and the carbon-modified cation-anion interaction accounts for the higher ionic conductivity in CB 11H 12 - salts compared with B 12H 12 2-.« less

Pressure-induced superconductivity in H2-containing hydride PbH4(H2)2

PubMed Central

Cheng, Ya; Zhang, Chao; Wang, Tingting; Zhong, Guohua; Yang, Chunlei; Chen, Xiao-Jia; Lin, Hai-Qing

2015-01-01

High pressure structure, stability, metallization, and superconductivity of PbH4(H2)2, a H2-containing compound combining one of the heaviest elements with the lightest element, are investigated by the first-principles calculations. The metallic character is found over the whole studied pressure range, although PbH4(H2)2 is metastable and easily decompose at low pressure. The decomposition pressure point of 133 GPa is predicted above which PbH4(H2)2 is stable both thermodynamically and dynamically with the C2/m symmetry. Interestedly, all hydrogen atoms pairwise couple into H2 quasi-molecules and remain this style up to 400 GPa in the C2/m structure. At high-pressure, PbH4(H2)2 tends to form the Pb-H2 alloy. The superconductivity of Tc firstly rising and then falling is observed in the C2/m PbH4(H2)2. The maximum of Tc is about 107 K at 230 GPa. The softening of intermediate-frequency phonon induced by more inserted H2 molecules is the main origin of the high Tc. The results obtained represent a significant step toward the understanding of the high pressure behavior of metallic hydrogen and hydrogen-rich materials, which is helpful for obtaining the higher Tc. PMID:26559369

Predicting possible effects of H2S impurity on CO2 transportation and geological storage.

PubMed

Ji, Xiaoyan; Zhu, Chen

2013-01-02

For CO(2) geological storage, permitting impurities, such as H(2)S, in CO(2) streams can lead to a great potential for capital and energy savings for CO(2) capture and separation, but it also increases costs and risk management for transportation and storage. To evaluate the cost-benefits, using a recently developed model (Ji, X.; Zhu, C. Geochim. Cosmochim. Acta 2012, 91, 40-59), this study predicts phase equilibria and thermodynamic properties of the system H(2)S-CO(2)-H(2)O-NaCl under transportation and storage conditions and discusses potential effects of H(2)S on transportation and storage. The prediction shows that inclusion of H(2)S in CO(2) streams may lead to two-phase flow. For H(2)S-CO(2) mixtures, at a given temperature, the bubble and dew pressures decrease with increasing H(2)S content, while the mass density increases at low pressures and decreases at high pressures. For the CO(2)-H(2)S-H(2)O system, the total gas solubility increases while the mass density of the aqueous solution with dissolved gas decreases. For the CO(2)-H(2)S-H(2)O-NaCl system, at a given temperature, pressure and NaCl concentration, the solubility of the gas mixture in aqueous phase increases with increasing H(2)S content and then decreases, while the mass density of aqueous solution decreases and may be lower than the mass density of the solution without gas dissolution.

Corrosion of 310 stainless steel in H2-H2O-H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

NASA Technical Reports Server (NTRS)

Rao, D. B.; Jacob, K. T.; Nelson, H. G.

1981-01-01

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 x 10 to the minus 13th power/cu Nm and sulfur potentials ranging from 0.19 x 10 to the minus 2nd power/cu Nm to 33 x 10 to the minus 2nd power/cu Nm. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (p sub S sub 2 less than or equal to 2.7 x 10 to the minus 2nd power/cu Nm) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfication. At low sulfur potentials (P sub S sub 2 less than or equal to 0.19 x 10 to the minus 2nd power/cu Nm) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases.

H{sub 2}S does not regulate proliferation via T-type Ca{sup 2+} channels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elies, Jacobo; Johnson, Emily; Boyle, John P.

T-type Ca{sup 2+} channels (Cav3.1, 3.2 and 3.3) strongly influence proliferation of various cell types, including vascular smooth muscle cells (VSMCs) and certain cancers. We have recently shown that the gasotransmitter carbon monoxide (CO) inhibits T-type Ca{sup 2+} channels and, in so doing, attenuates proliferation of VSMC. We have also shown that the T-type Ca{sup 2+} channel Cav3.2 is selectively inhibited by hydrogen sulfide (H{sub 2}S) whilst the other channel isoforms (Cav3.1 and Cav3.3) are unaffected. Here, we explored whether inhibition of Cav3.2 by H{sub 2}S could account for the anti-proliferative effects of this gasotransmitter. H{sub 2}S suppressed proliferation inmore » HEK293 cells expressing Cav3.2, as predicted by our previous observations. However, H{sub 2}S was similarly effective in suppressing proliferation in wild type (non-transfected) HEK293 cells and those expressing the H{sub 2}S insensitive channel, Cav3.1. Further studies demonstrated that T-type Ca{sup 2+} channels in the smooth muscle cell line A7r5 and in human coronary VSMCs strongly influenced proliferation. In both cell types, H{sub 2}S caused a concentration-dependent inhibition of proliferation, yet by far the dominant T-type Ca{sup 2+} channel isoform was the H{sub 2}S-insensitive channel, Cav3.1. Our data indicate that inhibition of T-type Ca{sup 2+} channel-mediated proliferation by H{sub 2}S is independent of the channels’ sensitivity to H{sub 2}S. - Highlights: • T-type Ca{sup 2+} channels regulate proliferation and are sensitive to the gasotransmitters CO and H{sub 2}S. • H{sub 2}S reduced proliferation in HEK293 cells expressing the H{sub 2}S sensitive Cav3.2 channel. • H{sub 2}S also inhibited proliferation in non-transfected cells and HEK293 cells expressing Cav3.1. • Native smooth muscle cells primarily express Cav3.1. Their proliferation was also inhibited by H{sub 2}S. • Unlike CO, H{sub 2}S does not regulate smooth muscle proliferation via T-type Ca

Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

NASA Technical Reports Server (NTRS)

Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

2013-01-01

We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

[Effect of endogenous H2S on platelet L-Arg transport].

PubMed

Duan, Wen-zhuo; Wang, Yi-peng; Gong, Hai-min

2010-05-01

To observe the effect of novel air neuromodulator H2S on platelet function of L-Arg transport for discussing H2S of effect on platelet function. Saturate H2S solution as donate made rat rich platelet plasma and pre-incubation rat platelet with different density of H2S. To measure the velocity of L-Arg transport in platelet by radioactivity technique. At different concentrations of H2S (6.25, 12.5, 25, 50, 100 micromol/L), the velocity of L-Arg transport was lower than that in control. H2S reduced rapidly the Vmax and velocity of L-Arg transport in platelet (P < 0.05) and this effect had no effect to Km. H2S can affect platelet function by changing rapidly platelet L-Arg transport system function.

2S protein Ara h 7.0201 has unique epitopes compared to other Ara h 7 isoforms and is comparable to 2S proteins Ara h 2 and 6 in basophil degranulation capacity.

PubMed

Hayen, S M; Ehlers, A M; den Hartog Jager, C F; Garssen, J; Knol, E F; Knulst, A C; Suer, W; Willemsen, L E M; Otten, H G

2018-07-01

Screening for specific IgE against 2S albumin proteins Ara h 2 and 6 has good positive predictive value in diagnosing peanut allergy. From the third 2S member Ara h 7, 3 isoforms have been identified. Their allergenicity has not been elucidated. This study investigated the allergenicity of Ara h 7 isoforms compared to Ara h 2 and 6. Sensitization of 15 DBPCFC-confirmed peanut-allergic patients to recombinant Ara h 2.0201, Ara h 6.01 and isoforms of recombinant Ara h 7 was determined by IgE immunoblotting strips. A basophil activation test (BAT) was performed in 9 patients to determine IgE-cross-linking capacities of the allergens. Sensitivity to the allergens was tested in 5 patients who were sensitized to at least 1 Ara h 7 isoform, by a concentration range in the BAT. 3D prediction models and sequence alignments were used to visualize differences between isoforms and to predict allergenic epitope regions. Sensitization to Ara h 7.0201 was most frequent (80%) and showed to be equally potent as Ara h 2.0201 and 6.01 in inducing basophil degranulation. Sensitization to Ara h 7.0201 together with Ara h 2.0201 and/or 6.01 was observed, indicating the presence of unique epitopes compared to the other 2 isoforms. Differences between the 3 Ara h 7 isoforms were observed in C-terminal cysteine residues, pepsin and trypsin cleavage sites and 3 single amino acid substitutions. The majority of peanut-allergic patients are sensitized to isoform Ara h 7.0201, which is functionally as active as Ara h 2.0201 and 6.01. Unique epitopes are most likely located in the C-terminus or an allergenic loop region which is a known allergenic epitope region for Ara h 2.0201 and 6.01. Due to its unique epitopes and allergenicity, it is an interesting candidate to improve the diagnostic accuracy for peanut allergy. © 2018 The Authors. Clinical & Experimental Allergy Published by John Wiley & Sons Ltd.

A Novel Dimeric Ni-Substituted beta-Keggin Silicotungstate: Structure and Magnetic Properties of K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O.

PubMed

Kortz, Ulrich; Jeannin, Yves P.; Tézé, André; Hervé, Gilbert; Isber, Samih

1999-08-09

The novel dimeric polyoxometalate [{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)](12)(-) (1) has been synthesized and characterized by IR spectroscopy, polarography, elemental analysis, thermogravimetric analysis, and magnetic measurements. An X-ray single-crystal analysis was carried out on K(12)[{beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)}(2)].20H(2)O, which crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.701(4) Å, b = 24.448(11) Å, c = 13.995(5) Å, beta = 99.62(3) degrees, and Z = 4. The anion consists of two [beta-SiNi(2)W(10)O(36)(OH)(2)(H(2)O)] Keggin moieties linked via two OH bridging groups, leading to a planar Ni(2)(OH)(2) unit. The two half-units are related by an inversion center and each contain one Ni atom in the rotated triad. The formation of the new anion involves insertion, isomerization, and dimerization. Magnetic measurements show that the central Ni(4) unit exhibits ferromagnetic (J' = 4.14 cm(-)(1)) as well as weak antiferromagnetic (J = -0.65 cm(-)(1)) Ni-Ni exchange interactions.

Emission of hydrogen sulfide (H2S) at a waterfall in a sewer: study of main factors affecting H2S emission and modeling approaches.

PubMed

Jung, Daniel; Hatrait, Laetitia; Gouello, Julien; Ponthieux, Arnaud; Parez, Vincent; Renner, Christophe

2017-11-01

Hydrogen sulfide (H 2 S) represents one of the main odorant gases emitted from sewer networks. A mathematical model can be a fast and low-cost tool for estimating its emission. This study investigates two approaches to modeling H 2 S gas transfer at a waterfall in a discharge manhole. The first approach is based on an adaptation of oxygen models for H 2 S emission at a waterfall and the second consists of a new model. An experimental set-up and a statistical data analysis allowed the main factors affecting H 2 S emission to be studied. A new model of the emission kinetics was developed using linear regression and taking into account H 2 S liquid concentration, waterfall height and fluid velocity at the outlet pipe of a rising main. Its prediction interval was estimated by the residual standard deviation (15.6%) up to a rate of 2.3 g H 2 S·h -1 . Finally, data coming from four sampling campaigns on sewer networks were used to perform simulations and compare predictions of all developed models.

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

PubMed Central

Cortese-Krott, Miriam M.; Kuhnle, Gunter G. C.; Dyson, Alex; Fernandez, Bernadette O.; Grman, Marian; DuMond, Jenna F.; Barrow, Mark P.; McLeod, George; Nakagawa, Hidehiko; Ondrias, Karol; Nagy, Péter; King, S. Bruce; Saavedra, Joseph E.; Keefer, Larry K.; Singer, Mervyn; Kelm, Malte; Butler, Anthony R.; Feelisch, Martin

2015-01-01

Experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide (H2S) signaling pathways are intimately intertwined, with mutual attenuation or potentiation of biological responses in the cardiovascular system and elsewhere. The chemical basis of this interaction is elusive. Moreover, polysulfides recently emerged as potential mediators of H2S/sulfide signaling, but their biosynthesis and relationship to NO remain enigmatic. We sought to characterize the nature, chemical biology, and bioactivity of key reaction products formed in the NO/sulfide system. At physiological pH, we find that NO and sulfide form a network of cascading chemical reactions that generate radical intermediates as well as anionic and uncharged solutes, with accumulation of three major products: nitrosopersulfide (SSNO−), polysulfides, and dinitrososulfite [N-nitrosohydroxylamine-N-sulfonate (SULFI/NO)], each with a distinct chemical biology and in vitro and in vivo bioactivity. SSNO− is resistant to thiols and cyanolysis, efficiently donates both sulfane sulfur and NO, and potently lowers blood pressure. Polysulfides are both intermediates and products of SSNO− synthesis/decomposition, and they also decrease blood pressure and enhance arterial compliance. SULFI/NO is a weak combined NO/nitroxyl donor that releases mainly N2O on decomposition; although it affects blood pressure only mildly, it markedly increases cardiac contractility, and formation of its precursor sulfite likely contributes to NO scavenging. Our results unveil an unexpectedly rich network of coupled chemical reactions between NO and H2S/sulfide, suggesting that the bioactivity of either transmitter is governed by concomitant formation of polysulfides and anionic S/N-hybrid species. This conceptual framework would seem to offer ample opportunities for the modulation of fundamental biological processes governed by redox switching and sulfur trafficking. PMID:26224837

Ruthenium(II) 2,2'-bibenzimidazole complex as a second-sphere receptor for anions interaction and colorimeter.

PubMed

Cui, Ying; Niu, Yan-Li; Cao, Man-Li; Wang, Ke; Mo, Hao-Jun; Zhong, Yong-Rui; Ye, Bao-Hui

2008-07-07

A ruthenium(II) complex [Ru(bpy) 2(H 2bbim)](PF 6) 2 ( 1) as anions receptor has been exploited, where Ru(II)-bpy moiety acts as a chromophore and the H 2bbim ligand as an anion binding site. A systematic study suggests that 1 interacts with the Cl (-), Br (-), I (-), NO 3 (-), HSO 4 (-), and H 2PO 4 (-) anions via the formation of hydrogen bonds. Whereas 1 undergoes a stepwise process with the addition of F (-) and OAc (-) anions: formation of the monodeprotonated complex [Ru(bpy) 2(Hbbim)] with a low anion concentration, followed by the double-deprotonated complex [Ru(bpy) 2(bbim)], in the presence of a high anion concentration. These stepwise processes concomitant with the changes of vivid colors from yellow to orange brown and then to violet can be used for probing the F (-) and OAc (-) anions by naked eye. The deprotonation processes are not only determined by the basicity of the anion but also related to the strength of hydrogen bonding, as well as the stability of the formed compounds. Moreover, a double-deprotonated complex [Ru(bpy) 2(bbim)].CH 3OH.H 2O ( 3) has been synthesized, and the structural changes induced by the deprotonation has also been investigated. In addition, complexes [Ru(bpy) 2(Hbbim)] 2(HOAc) 3Cl 2.12H 2O ( 2), [Ru(bpy) 2(Hbbim)](HCCl 3CO 2)(CCl 3CO 2).2H 2O ( 4), and [Ru(bpy) 2(H 2bbim)](CF 3CO 2) 2.4H 2O ( 5) have been synthesized to observe the second sphere coordination between the Ru(II)-H 2bbim moiety and carboxylate groups via hydrogen bonds in the solid state.

H2S, a novel therapeutic target in renal-associated diseases?

PubMed

Pan, Wen-Jun; Fan, Wen-Jing; Zhang, Chi; Han, Dan; Qu, Shun-Lin; Jiang, Zhi-Sheng

2015-01-01

For more than a century, hydrogen sulfide (H2S) has been regarded as a toxic gas. Recently, the understanding of the biological effects of H2S has been changed. This review surveys the growing recognition of H2S as an endogenous signaling molecule in mammals, with emphasis on its physiological and pathological pathways in the urinary system. This article reviews recent progress of basic and pharmacological researches related to endogenous H2S in urinary system, including the regulatory effects of H2S in the process of antioxidant, inflammation, cellular matrix remodeling and ion channels, and the role of endogenous H2S pathway in the pathogenesis of renal and urogenital disorders. Copyright © 2014. Published by Elsevier B.V.

Experimental investigation on thermochemical sulfate reduction by H2S initiation

USGS Publications Warehouse

Zhang, T.; Amrani, A.; Ellis, G.S.; Ma, Q.; Tang, Y.

2008-01-01

Hydrogen sulfide (H2S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 ??C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO4 in the presence of variable H2S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H2S occurred under acidic conditions (at pH ???3-3.5). However, sulfate reduction at pH ???5.0 was undetectable even at high initial H2S concentrations. To investigate whether the reaction of H2S(aq) and HSO4- occurs at pH ???3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO4 and variable H2S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO4 reduction was not measurable in the absence of paraffin even with high H2S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H2S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H2S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82, 1911-1916). Quantification of labile organosulfur compounds (LSC), such as thiols

Catalytic activity of Cu4-cluster to adsorb H2S gas: h-BN nanosheet

NASA Astrophysics Data System (ADS)

Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh

2018-05-01

We have investigated the electronic properties, adsorptions strength and charge transfer using first principles calculations using density functional theory (DFT). The hexagonal boron nitride (h-BN) substrate shows metallic behavior, which helps to enhance the absorption process. The adsorption of three different orientations (S, D and T) of the H2S gas molecules to analyze the maximum adsorption strength from them onto a copper cluster (Cu4) based on h-BN nanosheet. The maximum adsorption energy of the H2S gas molecule is -1.50 eV for the S orientation and for D and U, it is -0.71 eV and -0.78 eV, respectively. The results show that Cu4 cluster helps to capture H2S gas from the environment and results are useful for the cleaning environment from the toxic gases.

Collisional Quenching of Highly-Excited H2 due to H2 Collisions

NASA Astrophysics Data System (ADS)

Wan, Yier; Yang, Benhui H.; Stancil, Phillip C.; Naduvalath, Balakrishnan; Forrey, Robert C.; This work was partially support by Hubble grant HST-AT-13899. We thank Kyle Walkerassistance with vrrmm.

2017-06-01

Collision-induced energy transfer involving H2 molecules are of significant interest, since H2 is the most abundant molecular species in the universe. Collisional de-excitation rate coefficients of the H2-H2 system are necessary to produce accurate models of astrophysical environments. However, accurate calculations of collisional energy transfer are still a challenging problem, especially for highly-excited H2 because a large number of levels must be included in the calculation.Currently, most data are limited to initial rotational levels j up to 8 or initial vibrational levels up to 3. The vast majority of these results involve some form of a reduced-dimensional approach which may be of questionable accuracy. A reliable and accurate four-dimensional PES computed by Patkowski et al. is used in this work along with two quantum scattering programs (MOLSCAT and vrrmm). Another accurate full-dimensional PES has been reported for the H2-H2 system by Hinde.Not all transitions will be explicitly calculated. A zero-energy scaling technique (ZEST) is used to estimate some intermediate transitions from calculated rate coefficients. New inelastic quenching cross section for para-H2+para-H2 collisions with initial level j= 10, 12, 14, 18, 24 are calculated. Calculations for other de-excitation transitions from higher initial levels and collisions involving other spin isomer of hydrogen, ortho-H2+para-H2, ortho-H2+ortho-H2 and para-H2+ortho-H2 are in progress. The coupled- states approximation is also applied to obtain cross sections at high energy.K. Patkowski, et al., J. Chem. Phys. 129, 094304 (2008).J. M. Hutson and S. Green, MOLSCAT Computer code, v14 (1994).K. Walker, 2013, VRRMM: Vibrational/Rotational Rich Man’s MOLSCAT v3.1.K. Walker, Song, L., Yang, B. H.,et al. 2015, ApJ, \\811,27.S. Green, J. Chem. Phys. 62, 2271 (1975).Flower, D. R., Roueff, E. 1998, J. Phys. B, 31, 2935.T. -G. Lee, N. Balakrishnan, R. C. Forrey, P. C. Stancil, G. Shaw, D. R. Schultz, and G. J

H2S-mediated thermal and photochemical methane activation.

PubMed

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric V

2013-12-02

Sustainable, low-temperature methods for natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) mixed with methane, deemed altogether as sub-quality or "sour" gas. We propose a unique method of activation to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3 , and an energy carrier such as H2. For this purpose, we investigated the H2S-mediated methane activation to form a reactive CH3SH species by means of direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4 + H2S complex resulted in a barrierless relaxation by a conical intersection to form a ground-state CH3SH + H2 complex. The resulting CH3SH could further be coupled over acidic catalysts to form higher hydrocarbons, and the resulting H2 used as a fuel. This process is very different from conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced control over the conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the current industrial steam methane reforming (SMR). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Factors affecting UV/H2O2 inactivation of Bacillus atrophaeus spores in drinking water.

PubMed

Zhang, Yongji; Zhang, Yiqing; Zhou, Lingling; Tan, Chaoqun

2014-05-05

This study aims at estimating the performance of the Bacillus atrophaeus spores inactivation by the UV treatment with addition of H2O2. The effect of factors affecting the inactivation was investigated, including initial H2O2 dose, UV irradiance, initial cell density, initial solution pH and various inorganic anions. Under the experimental conditions, the B. atrophaeus spores inactivation followed both the modified Hom Model and the Chick's Model. The results revealed that the H2O2 played dual roles in the reactions, while the optimum reduction of 5.88lg was received at 0.5mM H2O2 for 10min. The inactivation effect was affected by the UV irradiance, while better inactivation effect was achieved at higher irradiance. An increase in the initial cell density slowed down the inactivation process. A slight acid condition at pH 5 was considered as the optimal pH value. The inactivation effect within 10min followed the order of pH 5>pH 7>pH 9>pH 3>pH 11. The effects of three added inorganic anions were investigated and compared, including sulfate (SO4(2)(-)), nitrate (NO3(-)) and carbonate (CO3(2)(-)). The sequence of inactivation effect within 10min followed the order of control group>SO4(2)(-)>NO3(-)>CO3(2)(-). Copyright © 2014 Elsevier B.V. All rights reserved.

Rate Coefficients of C2H with C2H4, C2H6, and H2 from 150 to 359 K

NASA Technical Reports Server (NTRS)

Opansky, Brian J.; Leone, Stephen R.

1996-01-01

Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.

Na2S, a fast-releasing H2S donor, given as suppository lowers blood pressure in rats.

PubMed

Tomasova, Lenka; Drapala, Adrian; Jurkowska, Halina; Wróbel, Maria; Ufnal, Marcin

2017-10-01

Hydrogen sulfide (H 2 S) is involved in blood pressure control. The available slow-releasing H 2 S-donors are poorly soluble in water and their ability to release H 2 S in biologically relevant amounts under physiological conditions is questionable. Therefore, new slow-releasing donors or new experimental approaches to fast-releasing H 2 S donors are needed. Hemodynamics and ECG were recorded in male, anesthetized Wistar Kyoto rats (WKY) and in Spontaneously hypertensive rats (SHR) at baseline and after: 1) intravenous (iv) infusion of vehicle or Na 2 S; 2) administration of vehicle suppositories or Na 2 S suppositories. Intravenously administered vehicle and vehicle suppositories did not affect mean arterial blood pressure (MABP) and heart rate (HR). Na 2 S administered iv caused a significant, but transient (2-5min) decrease in MABP. Na 2 S suppositories produced a dose-dependent hypotensive response that lasted ∼45min in WKY and ∼75-80min in SHR. It was accompanied by a decrease in HR in WKY, and an increase in HR in SHR. Na 2 S suppositories did not produce a significant change in corrected QT, an indicator of cardiotoxicity. Na 2 S suppositories increased blood level of thiosulfates, products of H 2 S oxidation. Na 2 S administered in suppositories exerts a prolonged hypotensive effect in rats, with no apparent cardiotoxic effect. SHR and WKY differ in hemodynamic response to the H 2 S donor. Suppository formulation of fast-releasing H 2 S donors may be useful in research, if a reference slow-releasing H 2 S donor is not available. Copyright © 2017 Institute of Pharmacology, Polish Academy of Sciences. Published by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

H2S: a universal defense against antibiotics in bacteria.

PubMed

Shatalin, Konstantin; Shatalina, Elena; Mironov, Alexander; Nudler, Evgeny

2011-11-18

Many prokaryotic species generate hydrogen sulfide (H(2)S) in their natural environments. However, the biochemistry and physiological role of this gas in nonsulfur bacteria remain largely unknown. Here we demonstrate that inactivation of putative cystathionine β-synthase, cystathionine γ-lyase, or 3-mercaptopyruvate sulfurtransferase in Bacillus anthracis, Pseudomonas aeruginosa, Staphylococcus aureus, and Escherichia coli suppresses H(2)S production, rendering these pathogens highly sensitive to a multitude of antibiotics. Exogenous H(2)S suppresses this effect. Moreover, in bacteria that normally produce H(2)S and nitric oxide, these two gases act synergistically to sustain growth. The mechanism of gas-mediated antibiotic resistance relies on mitigation of oxidative stress imposed by antibiotics.

Fluoride anion sensing mechanism of 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded supramolecular assembly: photoinduced electron transfer and partial configuration change.

PubMed

Chen, Jun-Sheng; Zhou, Pan-Wang; Li, Guang-Yue; Chu, Tian-Shu; He, Guo-Zhong

2013-05-02

The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.

Metal Oxide/Zeolite Combination Absorbs H2S

NASA Technical Reports Server (NTRS)

Voecks, Gerald E.; Sharma, Pramod K.

1989-01-01

Mixed copper and molybdenum oxides supported in pores of zeolite found to remove H2S from mixture of gases rich in hydrogen and steam, at temperatures from 256 to 538 degree C. Absorber of H2S needed to clean up gas streams from fuel processors that incorporate high-temperature steam reformers or hydrodesulfurizing units. Zeolites chosen as supporting materials because of their high porosity, rigidity, alumina content, and variety of both composition and form.

Ion chemistry of 1H-1,2,3-triazole.

PubMed

Ichino, Takatoshi; Andrews, Django H; Rathbone, G Jeffery; Misaizu, Fuminori; Calvi, Ryan M D; Wren, Scott W; Kato, Shuji; Bierbaum, Veronica M; Lineberger, W Carl

2008-01-17

A combination of experimental methods, photoelectron-imaging spectroscopy, flowing afterglow-photoelectron spectroscopy and the flowing afterglow-selected ion flow tube technique, and electronic structure calculations at the B3LYP/6-311++G(d,p) level of density functional theory (DFT) have been employed to study the mechanism of the reaction of the hydroxide ion (HO-) with 1H-1,2,3-triazole. Four different product ion species have been identified experimentally, and the DFT calculations suggest that deprotonation by HO- at all sites of the triazole takes place to yield these products. Deprotonation of 1H-1,2,3-triazole at the N1-H site gives the major product ion, the 1,2,3-triazolide ion. The 335 nm photoelectron-imaging spectrum of the ion has been measured. The electron affinity (EA) of the 1,2,3-triazolyl radical has been determined to be 3.447 +/- 0.004 eV. This EA and the gas-phase acidity of 2H-1,2,3-triazole are combined in a negative ion thermochemical cycle to determine the N-H bond dissociation energy of 2H-1,2,3-triazole to be 112.2 +/- 0.6 kcal mol-1. The 363.8 nm photoelectron spectroscopic measurements have identified the other three product ions. Deprotonation of 1H-1,2,3-triazole at the C5 position initiates fragmentation of the ring structure to yield a minor product, the ketenimine anion. Another minor product, the iminodiazomethyl anion, is generated by deprotonation of 1H-1,2,3-triazole at the C4 position, followed by N1-N2 bond fission. Formation of the other minor product, the 2H-1,2,3-triazol-4-ide ion, can be rationalized by initial deprotonation of 1H-1,2,3-triazole at the N1-H site and subsequent proton exchanges within the ion-molecule complex. The EA of the 2H-1,2,3-triazol-4-yl radical is 1.865 +/- 0.004 eV.

H2S mediated thermal and photochemical methane activation

PubMed Central

Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric

2013-01-01

Sustainable, low temperature methods of natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) in mixture with methane, CH4, altogether deemed as sub-quality or “sour” gas. We propose a unique method for activating this “sour” gas to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3, and an energy carrier, such as H2. For this purpose, we computationally investigated H2S mediated methane activation to form a reactive CH3SH species via direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4+H2S complex results in a barrier-less relaxation via a conical intersection to form a ground state CH3SH+H2 complex. The resulting CH3SH can further be heterogeneously coupled over acidic catalysts to form higher hydrocarbons while the H2 can be used as a fuel. This process is very different from a conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced controllability over the process conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the currently industrially used methane steam reforming (SMR). PMID:24150813

H2+, HeH and H2: Approximating potential curves, calculating rovibrational states

NASA Astrophysics Data System (ADS)

Olivares-Pilón, Horacio; Turbiner, Alexander V.

2018-06-01

Analytic consideration of the Bohr-Oppenheimer (BO) potential curves for diatomic molecules is proposed: accurate analytic interpolation for a potential curve consistent with its rovibrational spectra is found. It is shown that in the BO approximation for four lowest electronic states 1 sσg and 2 pσu, 2 pπu and 3 dπg of H2+, the ground state X2Σ+ of HeH and the two lowest states 1 Σg+ and 3 Σu+ of H2, the potential curves can be analytically interpolated in full range of internuclear distances R with not less than 4-5-6 s.d. Approximation based on matching the Laurant-type expansion at small R and a combination of the multipole expansion with one-instanton type contribution at large distances R is given by two-point Padé approximant. The position of minimum, when exists, is predicted within 1% or better. For the molecular ion H2+ in the Lagrange mesh method, the spectra of vibrational, rotational and rovibrational states (ν , L) associated with 1 sσg and 2 pσu, 2 pπu and 3 dπg potential curves are calculated. In general, it coincides with spectra found via numerical solution of the Schrödinger equation (when available) within six s.d. It is shown that 1 sσg curve contains 19 vibrational states (ν , 0) , while 2 pσu curve contains a single one (0 , 0) and 2 pπu state contains 12 vibrational states (ν , 0) . In general, 1 sσg electronic curve contains 420 rovibrational states, which increases up to 423 when we are beyond BO approximation. For the state 2 pσu the total number of rovibrational states (all with ν = 0) is equal to 3, within or beyond Bohr-Oppenheimer approximation. As for the state 2 pπu within the Bohr-Oppenheimer approximation the total number of the rovibrational bound states is equal to 284. The state 3 dπg is repulsive, no rovibrational state is found. It is confirmed in Lagrange mesh formalism the statement that the ground state potential curve of the heteronuclear molecule HeH does not support rovibrational states. Accurate

Theoretical study of radiative electron attachment to CN, C{sub 2}H, and C{sub 4}H radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Douguet, Nicolas; Fonseca dos Santos, S.; Orel, Ann E.

A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN{sup −}, C{sub 4}H{sup −}, and C{sub 2}H{sup −}. Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiativemore » decay. We have shown that the contribution of the indirect pathway to the formation of CN{sup −} is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10{sup −16} cm{sup 3}/s for CN{sup −}, 7 × 10{sup −17} cm{sup 3}/s for C{sub 2}H{sup −}, and 2 × 10{sup −16} cm{sup 3}/s for C{sub 4}H{sup −}. These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments.« less

High light harvesting efficiency CuInS2 quantum dots/TiO2/MoS2 photocatalysts for enhanced visible light photocatalytic H2 production.

PubMed

Yuan, Yong-Jun; Fang, Gaoliang; Chen, Daqin; Huang, Yanwei; Yang, Ling-Xia; Cao, Da-Peng; Wang, Jingjing; Yu, Zhen-Tao; Zou, Zhi-Gang

2018-04-24

Expanding the photoresponse range of TiO2-based photocatalysts is of great interest for photocatalytic H2 production. Herein, noble-metal-free CuInS2 quantum dots were employed as a novel inorganic dye to expand the visible light absorption of TiO2/MoS2 for solar H2 generation. The as-prepared CuInS2/TiO2/MoS2 photocatalysts exhibit broad absorption from the ultraviolet to near-infrared region. Under visible light irradiation (λ > 420 nm), the CuInS2/TiO2/MoS2 photocatalyst with 0.6 mmol g-1 CuInS2 and 0.5 wt% MoS2 showed the highest H2 evolution rate with a value of 1034 μmol h-1 g-1. Moreover, a considerable H2 evolution rate of 141 μmol h-1 g-1 was obtained under the irradiation of the optimized CuInS2/TiO2/MoS2 photocatalyst with >500 nm light. The reaction mechanism of the CuInS2/TiO2/MoS2 photocatalyst for photocatalytic H2 evolution was investigated in detail by photoluminescence decay study, and the results showed that the photoexcited electrons of CuInS2 can be transferred efficiently through TiO2 to MoS2 and then react with the absorbed protons to generate H2. The reported sensitization strategy tremendously improves the visible light absorption capacity and the photocatalytic performance of TiO2-based photocatalysts.

Inhibitory effect of selective cyclooxygenase-2 inhibitor etoricoxib on human organic anion transporter 3 (hOAT3).

PubMed

Honjo, Hiroaki; Uwai, Yuichi; Iwamoto, Kikuo

2011-04-01

It is well known that nonsteroidal anti-inflammatory drugs (NSAIDs) delay the elimination of methotrexate. One of the mechanisms is thought to be inhibition of methotrexate uptake via human organic anion transporter 3 (hOAT3, SLC22A8) in the renal proximal tubule by NSAIDs. In this study, we evaluated the inhibitory effects of selective cyclooxygenase-2 inhibitor etoricoxib on hOAT3 by uptake experiments using Xenopus laevis oocytes. The injection of hOAT3 cRNA stimulated the uptake of methotrexate into the oocytes, and its transport was inhibited by etoricoxib. Etoricoxib inhibited estrone sulfate uptake by hOAT3 dose dependently, and the 50% inhibitory concentration was estimated to be 9.8 µM. Eadie-Hofstee plot analysis showed that etoricoxib inhibited hOAT3 in a competitive manner. These findings show that etoricoxib has inhibitory effect on hOAT3, and that the potential is comparable to that of traditional NSAIDs. ©2011 Bentham Science Publishers Ltd.

[Degradation of Organic Sunscreens 2-hydroxy-4-methoxybenzophenone by UV/ H2O2 Process: Kinetics and Factors].

PubMed

Feng, Xin-xin; Du, Er-deng; Guo, Ying-qing; Li, Hua-jie; Liu, Xiang; Zhou, Fang

2015-06-01

Organic sunscreens continue to enter the environment through people's daily consumption, and become a kind of emerging contaminants. The photochemical degradation of benzophenone-3 (BP-3) in water by UV/H2O2 process was investigated. Several factors, including the initial BP-3 concentration, H2O2 concentration, UV light intensity, coexisting cations and anions, humic acid and tert-butyl alcohol, were also discussed. The results showed that BP-3 degradation rate constant decreased with increasing initial BP-3 concentration, while increased with increasing H2O2 dosage and UV intensity. Coexisting anions could reduce the degradation rate, while coexisting ferric ions could stimulate the production of OH through Fenton-like reaction, further significantly accelerated BP-3 degradation process. The BP-3 degradation would be inhibited by humic acid or tert-butyl alcohol. The electrical energy per order (E(Eo)) values were also calculated to evaluate the cost of BP-3 degradation by UV/H2O2 process. The addition of ferric ions significantly reduced the value of E(Eo). The investigation of processing parameter could provide a reference for the practical engineering applications of benzophenone compounds removal by UV/H2O2 process.

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

NASA Astrophysics Data System (ADS)

Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

1991-03-01

The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

H2S Loss through Nalophan™ Bags: Contributions of Adsorption and Diffusion

PubMed Central

2017-01-01

Hydrogen-sulfide (H2S) is a molecule of small dimensions typically present in the odor emissions from different plants. The European Standard EN 13725:2003 set a maximum storage time allowed of 30 hours, during which the sampling bag has to maintain the mixture of odorants with minimal changes. This study investigates the H2S losses through Nalophan bags and it shows that nonnegligible losses of H2S can be observed. The percent H2S loss after 30 hrs with respect to the initial concentration is equal to 33%  ± 3% at a relative humidity of 20% and equal to 22%  ± 1% at a relative humidity of 60%. The average quantity of adsorbed H2S at 30 h is equal to 2.17 105 gH2S/gNalophan at a storage humidity of 20% and equal to 1.79 105 gH2S/gNalophan at a storage humidity of 60%. The diffusion coefficients of H2S through Nalophan, for these two humidity conditions tested, are comparable (i.e., 7.5 10−12 m2/sec at 20% humidity and 6.6 10−12 m2/sec at 60% humidity). PMID:28740857

H2S-induced S-sulfhydration of pyruvate carboxylase contributes to gluconeogenesis in liver cells.

PubMed

Ju, YoungJun; Untereiner, Ashley; Wu, Lingyun; Yang, Guangdong

2015-11-01

Cystathionine gamma-lyase (CSE)-derived hydrogen sulfide (H(2)S) possesses diverse roles in the liver, affecting lipoprotein synthesis, insulin sensitivity, and mitochondrial biogenesis. H(2)S S-sulfhydration is now proposed as a major mechanism for H(2)S-mediated signaling. Pyruvate carboxylase (PC) is an important enzyme for gluconeogenesis. S-sulfhydration regulation of PC by H(2)S and its implication in gluconeogenesis in the liver have been unknown. Gene expressions were analyzed by real-time PCR and western blotting, and protein S-sulfhydration was assessed by both modified biotin switch assay and tag switch assay. Glucose production and PC activity was measured with coupled enzyme assays, respectively. Exogenously applied H(2)S stimulates PC activity and gluconeogenesis in both HepG2 cells and mouse primary liver cells. CSE overexpression enhanced but CSE knockout reduced PC activity and gluconeogenesis in liver cells, and blockage of PC activity abolished H(2)S-induced gluconeogenesis. H(2)S had no effect on the expressions of PC mRNA and protein, while H(2)S S-sulfhydrated PC in a dithiothreitol-sensitive way. PC S-sulfhydration was significantly strengthened by CSE overexpression but attenuated by CSE knockout, suggesting that H(2)S enhances glucose production through S-sulfhydrating PC. Mutation of cysteine 265 in human PC diminished H(2)S-induced PC S-sulfhydration and activity. In addition, high-fat diet feeding of mice decreased both CSE expression and PC S-sulfhydration in the liver, while glucose deprivation of HepG2 cells stimulated CSE expression. CSE/H(2)S pathway plays an important role in the regulation of glucose production through S-sulfhydrating PC in the liver. Tissue-specific regulation of CSE/H(2)S pathway might be a promising therapeutic target of diabetes and other metabolic syndromes. Copyright © 2015 Elsevier B.V. All rights reserved.

H2O2 levels in rainwater collected in south Florida and the Bahama Islands

NASA Technical Reports Server (NTRS)

Zika, R.; Saltzman, E.; Chameides, W. L.; Davis, D. D.

1982-01-01

Measurements of H2O2 in rainwater collected in Miami, Florida, and the Bahama Islands area indicate the presence of H2O2 concentration levels ranging from 100,000 to 700,000 M. No systematic trends in H2O2 concentration were observed during an individual storm, in marked contrast to the behavior of other anions for example, NO3(-), SO4(-2), and Cl(-). The data suggest that a substantial fraction of the H2O2 found in precipitation is generated by aqueous-phase reactions within the cloudwater rather than via rainout and washout of gaseous H2O2.

Anti-H-Y responses of H-2b mutant mice.

PubMed

Simpson, E; Gordon, R D; Chandler, P R; Bailey, D

1978-10-01

Two strains of H-2b mutant mice, H-2ba and H-2bf, in which the mutational event took place at H-2K, make anti-H-Y cytotoxic T cell responses which are H-2-restricted, Db-associated and indistinguishable in target cell specificity from those of H-2b mice. Thus, alteration of the H-2K molecule affects neither the Ir gene controlling the response, nor the associative antigen. On the other hand, one H-2Db mutant strain, H-2bo, although it makes a good anti-H-Y cytotoxic response, shows target cell specificity restricted to its own Dbo antigen(s), and neither H-2b, H-2ba or H-2bf anti-H-Y cytotoxic cells kill H-2bo male target cells. Thus, the alteration of the H-2Db molecule does not affect the Ir gene of H-2b mice, but it does alter the H-2Db-associative antigen.

Low-lying electronic structure of EuH, EuOH, and EuO neutrals and anions determined by anion photoelectron spectroscopy and DFT calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kafader, Jared O.; Ray, Manisha; Jarrold, Caroline Chick, E-mail: cjarrold@indiana.edu

2015-07-21

The anion photoelectron (PE) spectra of EuH{sup −} and the PE spectrum of overlapping EuOH{sup −} and EuO{sup −} anions are presented and analyzed with supporting results from density functional theory calculations on the various anions and neutrals. Results point to ionically bound, high-spin species. EuH and EuOH anions and neutrals exhibit analogous electronic structures: Transitions from {sup 8}Σ{sup −} anion ground states arising from the 4f{sup 7}σ{sub 6s}{sup 2} superconfiguration to the close-lying neutral {sup 9}Σ{sup −} and {sup 7}Σ{sup −} states arising from the 4f{sup 7}σ{sub 6s} superconfiguration are observed spaced by an energy interval similar to themore » free Eu{sup +} [4f{sup 7}6s] {sup 9}S - {sup 7}S splitting. The electron affinities (EAs) of EuH and EuOH are determined to be 0.771 ± 0.009 eV and 0.700 ± 0.011 eV, respectively. Analysis of spectroscopic features attributed to EuO{sup −} photodetachment is complicated by the likely presence of two energetically competitive electronic states of EuO{sup −} populating the ion beam. However, based on the calculated relative energies of the close-lying anion states arising from the 4f{sup 7}σ{sub 6s} and 4f{sup 6}σ{sub 6s}{sup 2} configurations and the relative energies of the one-electron accessible 4f{sup 7} and 4f{sup 6}σ{sub 6s} neutral states based on ligand-field theory [M. Dulick, E. Murad, and R. F. Barrow, J. Chem. Phys. 85, 385 (1986)], the remaining features are consistent with the 4f{sup 6}σ{sub 6s}{sup 2}  {sup 7}Σ{sup −} and 4f{sup 7}σ{sub 6s}{sup 7}Σ{sup −} anion states lying very close in energy (the former was calculated to be 0.15 eV lower in energy than the latter), though the true anion ground state and neutral EA could not be established unambiguously. Calculations on the various EuO anion and neutral states suggest 4f-orbital overlap with 2p orbitals in species with 4f{sup 6} occupancy.« less

Room-temperature NaI/H2O compression icing: solute-solute interactions.

PubMed

Zeng, Qingxin; Yao, Chuang; Wang, Kai; Sun, Chang Q; Zou, Bo

2017-10-11

In situ Raman spectroscopy revealed that transiting the concentrated NaI/H 2 O solutions to an ice VI phase and then into an ice VII phase at 298 K proceeds in a way different from that activated by the solute type. Unlike the solute type that raises both the critical pressures P C1 and P C2 , for the liquid-VI, the VI-VII transition simultaneously occurs in the Hofmeister series order: I > Br > Cl > F ∼ 0; concentration increase raises the P C1 faster than the P C2 that remains almost constant at higher NaI/H 2 O molecular number ratios. Concentration increase moves the P C1 along the liquid-VI phase boundary and it finally merges with P C2 at the triple-phase junction featured at 350 K and 3.05 GPa. The highly-deformed H-O bond is less sensitive to the concentration because of the involvement of anion-anion repulsion that weakens the electric field in the hydration shells. Observations confirm that the salt solvation lengthens the O:H nonbond and softens its phonon but relaxes the H-O bond contrastingly. Compression, however, has the opposite effect from that of salt solvation. Therefore, compression recovers the polarization-deformed O:H-O bond first and then proceeds to the phase transitions. The anion-anion interaction discriminates the effect of NaI/H 2 O concentration from that of the solute type at an identical concentration on the phase transitions.

A second polymorph with composition Co3(PO4)2·H2O

PubMed Central

Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

2008-01-01

Single crystals of Co3(PO4)2·H2O, tricobalt(II) bis­[ortho­phosphate(V)] monohydrate, were obtained under hydro­thermal conditions. The compound is the second polymorph of this composition and is isotypic with its zinc analogue, Zn3(PO4)2·H2O. Three independent Co2+ cations are bridged by two independent orthophosphate anions. Two of the metal cations exhibit a distorted tetra­hedral coordination while the third exhibits a considerably distorted [5 + 1] octa­hedral coordination environment with one very long Co—O distance of 2.416 (3) Å. The former cations are bonded to four different phosphate anions, and the latter cation is bonded to four anions (one of which is bidentate) and one water mol­ecule, leading to a framework structure. Additional hydrogen bonds of the type O—H⋯O stabilize this arrangement. PMID:21200979

Synthesis, DFT calculations of structure, vibrational and thermal decomposition studies of the metal complex Pb[Mn(C3H2O4)2(H2O)2].

PubMed

Gil, Diego M; Carbonio, Raúl E; Gómez, María Inés

2015-04-15

The metallo-organic complex Pb[Mn(C3H2O4)2(H2O)2] was synthesized and characterized by IR and Raman spectroscopy and powder X-ray diffraction methods. The cell parameters for the complex were determined from powder X-ray diffraction using the autoindexing program TREOR, and refined by the Le Bail method with the Fullprof program. A hexagonal unit cell was determined with a=b=13.8366(7)Å, c=9.1454(1)Å, γ=120°. The DFT calculated geometry of the complex anion [Mn(C3H2O4)2(H2O)2](2-) is very close to the experimental data reported for similar systems. The IR and Raman spectra and the thermal analysis of the complex indicate that only one type of water molecules is present in the structure. The thermal decomposition of Pb[Mn(C3H2O4)2(H2O)2] at 700 °C in air produces PbO and Pb2MnO4 as final products. The crystal structure of the mixed oxide is very similar to that reported for Pb3O4. Copyright © 2015 Elsevier B.V. All rights reserved.

Evidence for the η(b)(2S) and observation of h(b)(1P)→η(b)(1S)γ and h(b)(2P)→η(b)(1S)γ.

PubMed

Mizuk, R; Asner, D M; Bondar, A; Pedlar, T K; Adachi, I; Aihara, H; Arinstein, K; Aulchenko, V; Aushev, T; Aziz, T; Bakich, A M; Bay, A; Belous, K; Bhardwaj, V; Bhuyan, B; Bischofberger, M; Bonvicini, G; Bozek, A; Bračko, M; Brodzicka, J; Browder, T E; Chekelian, V; Chen, A; Chen, P; Cheon, B G; Chilikin, K; Chistov, R; Cho, I-S; Cho, K; Choi, S-K; Choi, Y; Dalseno, J; Danilov, M; Doležal, Z; Drásal, Z; Drutskoy, A; Eidelman, S; Epifanov, D; Fast, J E; Gaur, V; Gabyshev, N; Garmash, A; Golob, B; Haba, J; Hara, T; Hayasaka, K; Hayashii, H; Horii, Y; Hoshi, Y; Hou, W-S; Hsiung, Y B; Hyun, H J; Iijima, T; Ishikawa, A; Itoh, R; Iwabuchi, M; Iwasaki, Y; Iwashita, T; Jaegle, I; Julius, T; Kang, J H; Kapusta, P; Kawasaki, T; Kim, H J; Kim, H O; Kim, J H; Kim, K T; Kim, M J; Kim, Y J; Kinoshita, K; Ko, B R; Koblitz, S; Kodyš, P; Korpar, S; Kouzes, R T; Križan, P; Krokovny, P; Kuhr, T; Kumita, T; Kuzmin, A; Kwon, Y-J; Lange, J S; Lee, S-H; Li, J; Libby, J; Liu, C; Liu, Y; Liu, Z Q; Liventsev, D; Louvot, R; Matvienko, D; McOnie, S; Miyabayashi, K; Miyata, H; Mohanty, G B; Mohapatra, D; Moll, A; Muramatsu, N; Mussa, R; Nakao, M; Natkaniec, Z; Ng, C; Nishida, S; Nishimura, K; Nitoh, O; Nozaki, T; Ohshima, T; Okuno, S; Olsen, S L; Onuki, Y; Pakhlov, P; Pakhlova, G; Park, C W; Park, H; Pestotnik, R; Petrič, M; Piilonen, L E; Poluektov, A; Röhrken, M; Sakai, Y; Sandilya, S; Santel, D; Sanuki, T; Sato, Y; Schneider, O; Schwanda, C; Senyo, K; Seon, O; Sevior, M E; Shapkin, M; Shen, C P; Shibata, T-A; Shiu, J-G; Shwartz, B; Sibidanov, A; Simon, F; Smerkol, P; Sohn, Y-S; Sokolov, A; Solovieva, E; Stanič, S; Starič, M; Sumihama, M; Sumiyoshi, T; Tanida, K; Tatishvili, G; Teramoto, Y; Tikhomirov, I; Trabelsi, K; Tsuboyama, T; Uchida, M; Uehara, S; Uglov, T; Unno, Y; Uno, S; Vanhoefer, P; Varner, G; Varvell, K E; Vinokurova, A; Vorobyev, V; Wang, C H; Wang, M-Z; Wang, P; Wang, X L; Watanabe, M; Watanabe, Y; Williams, K M; Won, E; Yabsley, B D; Yamaoka, J; Yamashita, Y; Yuan, C Z; Zhang, Z P; Zhilich, V

2012-12-07

We report the first evidence for the η(b)(2S) using the h(b)(2P)→η(b)(2S)γ transition and the first observation of the h(b)(1P)→η(b)(1S)γ and h(b)(2P)→η(b)(1S)γ transitions. The mass and width of the η(b)(1S) and η(b)(2S) are measured to be m(η(b)(1S))=(9402.4±1.5±1.8) MeV/c(2), m(η(b)(2S))=(9999.0±3.5(-1.9)(+2.8)) MeV/c(2), and Γ(η(b)(1S))=(10.8(-3.7-2.0)(+4.0+4.5)) MeV. We also update the h(b)(1P) and h(b)(2P) mass measurements. We use a 133.4 fb(-1) data sample collected at energies near the Υ(5S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider.

Characteristics of H2S emission from aged refuse after excavation exposure.

PubMed

Shen, Dong-Sheng; Du, Yao; Fang, Yuan; Hu, Li-Fang; Fang, Cheng-Ran; Long, Yu-Yang

2015-05-01

Hydrogen sulfide (H2S(g)) emission from landfills is a widespread problem, especially when aged refuse is excavated. H2S(g) emission from aged refuse exposed to air was investigated and the results showed that large amounts of H2S(g) can be released, especially in the first few hours after excavation, when H2S(g) concentrations in air near refuse could reach 2.00 mg m(-3). Initial exposure to air did not inhibit the emission of H2S(g), as is generally assumed, but actually promoted it. The amounts of H2S(g) emitted in the first 2 d after excavation can be very dangerous, and the risks associated with the emission of H2S(g) could decrease significantly with time. Unlike a large number of sulfide existed under anaerobic conditions, the sulfide in aged municipal solid waste can be oxidized chemically to elemental sulfur (but not sulfate) under aerobic conditions, and its conversion rate was higher than 80%. Only microorganisms can oxidize the reduced sulfur species to sulfate, and the conversion rate could reach about 50%. Using appropriate techniques to enhance these chemical and biological transformations could allow the potential health risks caused by H2S(g) after refuse excavation to be largely avoided. Copyright © 2015 Elsevier Ltd. All rights reserved.

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C{sub 4}H{sub 2}O{sub 4})(OH{sub 2}{sub 3}) {center_dot}] H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diaz de Delgado, G.; Parra, P.P.; Briceno, A.

1995-05-01

(Sr(C{sub 4}H{sub 2}O{sub 4})(OH{sub 2}{sub 3}) {center_dot} H{sub 2}O is monoclinic, P2{sub 1}/n, with a = 11.476(2), b = 7.027(1), c = 12.344(2) {angstrom}, {beta} = 115.74(3){degrees}, V= 896.67 {angstrom}{sup 3}, Z = 4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr-O distances range from 2.546(2) to 2.808(2) {angstrom}. The C-O distances are equal within the standard deviation 1.263(3) to 1.258(3) {angstrom}). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9){degrees}. Both carboxylate groups deviate significantly from planarity. Themore » different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.« less

Fluid inclusion volatile analysis by gas chromatography with photoionization micro-thermal conductivity detectors: Applications to magmatic MoS 2 and other H 2O-CO 2 and H 2O-CH 4 fluids

NASA Astrophysics Data System (ADS)

Bray, C. J.; Spooner, E. T. C.

1992-01-01

Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated (~105°C) on-line crushing, helium carrier gas, a single porous polymer column (HayeSep R; 10' × 1/8″: 100/120#; Ni alloy tubing), two temperature programme conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID; 11.7 eV lamp), and off-line digital peak processing. In order of retention time these volatile peaks are: N 2, Ar, CO, CH 4, CO 2, C 2H 4, C 2H 6, C 2H 2, COS, C 3H 6, C 3H 8, C 3H 4 (propyne), H 2O (22.7 min at 80°C), SO 2, ± iso- C4H10 ± C4H8 (1-butene) ± CH3SH, C 4H 8 (iso-butylene), (?) C 4H 6 (1,3 butadiene) and ± n- C4H10 ± C4H8 (trans-2-butene) (80 and -70°C temperature programme conditions combined). H 2O is analysed directly. O 2 can be analysed cryogenically between N 2 and Ar, but has not been detected in natural samples to date in this study. H 2S, SO 2, NH 3, HCl, HCN, and H 2 ca nnot be analysed at present. Blanks determined by crushing heat-treated Brazilian quartz (800-900°C/4 h) are zero for 80°C temperature programme conditions, except for a large, unidentified peak at ~64 min, but contain H 2O, CO 2, and some low molecular weight hydrocarbons at -70°C temperature conditions due to cryogenic accumulation from the carrier gas and subsequent elution. TCD detection limits are ~30 ppm molar in inclusions; PID detection limits are ~ 1 ppm molar in inclusions and lower for unsaturated hydrocarbons (e.g., ~0.2 ppm for C 2H 4; ~ 1 ppb for C 2H 2; ~0.3 ppb for C 3H 6). Precisions (1σ) are ~ ±1-2% and ~ ± 13% for H 2O in terms of total moles detected; the latter value is equivalent to ±0.6 mol% at the 95 mol% H 2O level. Major fluid inclusion volatile species have been successfully analysed on a ~50 mg fluid inclusion section chip (~7 mm × ~10 mm × ~100 μm). Initial inclusion volatile analyses of fluids of interpreted magmatic origin from

Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

PubMed

Monegan, Jessie D; Bunge, Scott D

2009-04-06

The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

Oxothiomolybdenum derivatives of the superlacunary crown heteropolyanion {P8W48}: structure of [K4{Mo4O4S4(H2O)3(OH)2}2(WO2)(P8W48O184)]30– and studies in solution.

PubMed

Korenev, Vladimir S; Floquet, Sébastien; Marrot, Jérôme; Haouas, Mohamed; Mbomekallé, Israël-Martyr; Taulelle, Francis; Sokolov, Maxim N; Fedin, Vladimir P; Cadot, Emmanuel

2012-02-20

Reaction of the cyclic lacunary [H(7)P(8)W(48)O(184)](33-) anion (noted P(8)W(48)) with the [Mo(2)S(2)O(2)(H(2)O)(6)](2+) oxothiocation led to two compounds, namely, [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) (denoted 1) and [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) (denoted 2), which were characterized in the solid state and solution. In the solid state, the structure of [K(4){Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(WO(2))(P(8)W(48)O(184))](30-) reveals the presence of two disordered {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) "handles" connected on both sides of the P(8)W(48) ring. Such a disorder is consistent with the presence of two geometrical isomers where the relative disposition of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles are arranged in a perpendicular or parallel mode. Such an interpretation is fully supported by (31)P and (183)W NMR solution studies. The relative stability of both geometrical isomers appears to be dependent upon the nature of the internal alkali cations, i.e., Na(+) vs K(+), and increased lability of the two {Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2+) handles, compared to the oxo analogous, was clearly identified by significant broadening of the (31)P and (183)W NMR lines. Solution studies carried out by UV-vis spectroscopy showed that formation of the adduct [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) occurs in the 1.5-4.7 pH range and corresponds to a fast and quantitative condensation process. Furthermore, (31)P NMR titrations in solution reveal formation of the "monohandle" derivative [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(P(8)W(48)O(184))](38-) as an intermediate prior to formation of the "bishandle" derivatives. Furthermore, the electrochemical behavior of [{Mo(4)O(4)S(4)(H(2)O)(3)(OH)(2)}(2)(P(8)W(48)O(184))](36-) was studied in aqueous medium and compared with the parent anion P(8)W(48).

An Investigation of Armenite, BaCa2Al6Si9O302H2O.H2O Molecules and H Bonding in Microporous Silicates

NASA Astrophysics Data System (ADS)

Geiger, C. A.; Gatta, G.; Xue, X.; McIntyre, G.

2012-12-01

The crystal chemistry of armenite, ideally BaCa2Al6Si9O30.2H2O, a double-ring structure belonging to the milarite group, was studied to better understand the nature of extra-framework "Ca-oxygen-anion-H2O-molecule quasi-clusters" and H bonding behavior in microporous silicates. Neutron and X-ray single-crystal diffraction and IR powder and 1H NMR spectroscopic measurements were made. Four crystallographically independent Ca and H2O molecule sites were refined from the diffraction data, whereby both sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming a quasi cluster around it. The neutron results give the first static description of the protons in armenite, allowing bond distances and angles relating to the H2O molecules and H bonds to be determined. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two broad bands at roughly 3470 and 3410 cm-1 and by a single H2O bending mode at 1654 cm-1. At 10 K four intense OH bands are located at 3479, 3454, 3401 and 3384 cm-1 and two H2O bending modes at 1650 and 1606 cm-1. The 1H MAS NMR spectrum shows a single strong resonance near 5.3 ppm and a smaller one near 2.7 ppm. The former can be assigned to H2O molecules bonded to Ca and the latter to weakly bonded H2O located at a site at the center of the structural double ring and it is partially occupied. The nature of H bonding in the microporous Ca-bearing zeolites scolecite, wairakite and epistilbite are also analyzed. The average OH stretching wavenumber shown by the IR spectra of armenite (~3435 cm-1) and scolecite (~3430 cm-1) are similar, while the average OH wavenumbers for wairakite (~3475 cm-1) and epistilbite (~3500 cm-1) are greater. In all cases the average OH stretching wavenumber is more similar to that of liquid water (~3400 cm-1) than of ice (~3220 cm-1). The

Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

NASA Technical Reports Server (NTRS)

Carter, H. G.; Bullock, R. E.

1972-01-01

Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production.

PubMed

Pang, Huan; Wei, Chengzhen; Li, Xuexue; Li, Guochang; Ma, Yahui; Li, Sujuan; Chen, Jing; Zhang, Jiangshan

2014-01-06

Uniform NiS2 nanocubes are successfully synthesized with a microwave-assisted method. Interestingly, NiS2 nanocubes, nanospheres and nanoparticles are obtained by controlling microwave reaction time. NiS2 nanomaterials are primarily applied to supercapacitors and cocatalytic enhancing photocatalytic H2 production. Different morphologies of NiS2 nanostructures show different electrochemical and cocatalytic enhancing H2 production activities. Benefited novel nanostructures, NiS2 nanocube electrodes show a large specific capacitance (695 F g(-1) at 1.25 A g(-1)) and excellent cycling performance (the retention 93.4% of initial specific capacitance after 3000 cycles). More importantly, NiS2 nanospheres show highly cocatalytic enhancing photocatalytic for H2 evolution, in which the photocatalytic H2 production is up to 3400 μmol during 12 hours under irradiation of visible light (λ>420 nm) with an average H2 production rate of 283 μmol h(-1).

Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production

NASA Astrophysics Data System (ADS)

Pang, Huan; Wei, Chengzhen; Li, Xuexue; Li, Guochang; Ma, Yahui; Li, Sujuan; Chen, Jing; Zhang, Jiangshan

2014-01-01

Uniform NiS2 nanocubes are successfully synthesized with a microwave-assisted method. Interestingly, NiS2 nanocubes, nanospheres and nanoparticles are obtained by controlling microwave reaction time. NiS2 nanomaterials are primarily applied to supercapacitors and cocatalytic enhancing photocatalytic H2 production. Different morphologies of NiS2 nanostructures show different electrochemical and cocatalytic enhancing H2 production activities. Benefited novel nanostructures, NiS2 nanocube electrodes show a large specific capacitance (695 F g-1 at 1.25 A g-1) and excellent cycling performance (the retention 93.4% of initial specific capacitance after 3000 cycles). More importantly, NiS2 nanospheres show highly cocatalytic enhancing photocatalytic for H2 evolution, in which the photocatalytic H2 production is up to 3400 μmol during 12 hours under irradiation of visible light (λ>420 nm) with an average H2 production rate of 283 μmol h-1.

di Synthesis and Characterization of the Platinum-Substituted Keggin Anion alpha-H2SiPtW11O404-

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klonowski, P; Goloboy, JC; Uribe-Romo, FJ

2014-12-15

Acidification of an aqueous solution of K8SiW11O39 and K2Pt(OH)(6) to pH 4 followed by addition of excess tetramethylammonium (TMA) chloride yielded a solid mixture of TMA salts of H2SiPtW11O404- (1) and SiW12O404- (2). The former was separated from the latter by extraction into an aqueous solution and converted into tetra-n-butylammonium (TBA) and potassium salts TBA-1 and K-1. The a-H2SiPtW11O404- was identified as a monosubstituted Keggin anion using elemental analysis, IR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, Pt-195 NMR spectroscopy, (183)W NMR spectroscopy, and W-183-W-183 2D INADEQUATE NMR spectroscopy. Both TBA-1 and K-1 readily cocrystallized with their unsubstituted Keggin anionmore » salts, TBA-2 and K-2, respectively, providing an explanation for the historical difficulty of isolating certain platinum-substituted heteropolyanions in pure form.« less

Anion-selective interaction and colorimeter by an optical metalloreceptor based on ruthenium(II) 2,2'-biimidazole: hydrogen bonding and proton transfer.

PubMed

Cui, Ying; Mo, Hao-Jun; Chen, Jin-Can; Niu, Yan-Li; Zhong, Yong-Rui; Zheng, Kang-Cheng; Ye, Bao-Hui

2007-08-06

A new anion sensor [Ru(bpy)2(H2biim)](PF6)2 (1) (bpy = 2,2'-bipyridine and H2biim = 2,2'-biimidazole) has been developed, in which the Ru(II)-bpy moiety acts as a chromophore and the H2biim ligand as an anion receptor via hydrogen bonding. A systematic investigation shows that 1 is an eligible sensor for various anions. It donates protons for hydrogen bonding to Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, and OAc- anions and further actualizes monoproton transfer to the OAc- anion, changing color from yellow to orange brown. The fluoride ion has a high affinity toward the N-H group of the H2biim ligand for proton transfer, rather than hydrogen bonding, because of the formation of the highly stable HF2- anion, resulting in stepwise deprotonation of the two N-H fragments. These processes are signaled by vivid color changes from yellow to orange brown and then to violet because of second-sphere donor-acceptor interactions between Ru(II)-H2biim and the anions. The significant color changes can be distinguished visually. The processes are not only determined by the basicity of anion but also by the strength of hydrogen bonding and the stability of the anion-receptor complexes. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of anion sensors.

Crystal and molecular structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H{sub 2}L)(NO{sub 3}){sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Egorova, O. A.; Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Sergienko, V. S.

2016-07-15

The crystal structure of 2,2’-(quinoxaline-2,3-diyl)dipyridinium dinitrate (H{sub 2}L)(NO{sub 3}){sub 2} is studied by X-ray diffraction (T = 150 K, R1 = 0.0467). The H{sub 2}L{sup 2+} cation is located on the twofold rotation axis and connected with two NO{sub 3}{sup −} anions by strong N–H···O hydrogen bonds. Planar quinoxaline fragments of cations form stacks with the interplanar spacing of 3.308 Å. The structure of the diprotonated H{sub 2}L{sup 2+} cation is compared with those of the monoprotonated H{sub 2}L{sup 2+} cation and neutral L molecule.

Electronic properties of in-plane phase engineered 1T'/2H/1T' MoS2

NASA Astrophysics Data System (ADS)

Thakur, Rajesh; Sharma, Munish; Ahluwalia, P. K.; Sharma, Raman

2018-04-01

We present the first principles studies of semi-infinite phase engineered MoS2 along zigzag direction. The semiconducting (2H) and semi-metallic (1T') phases are known to be stable in thin-film MoS2. We described the electronic and structural properties of the infinite array of 1T'/2H/1T'. It has been found that 1T'phase induced semi-metallic character in 2H phase beyond interface but, only Mo atoms in 2H phase domain contribute to the semi-metallic nature and S atoms towards semiconducting state. 1T'/2H/1T' system can act as a typical n-p-n structure. Also high holes concentration at the interface of Mo layer provides further positive potential barriers.

Synthesis and characterization of polymer eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O as well as the interaction of [Y III(pdta)(H 2O)] 22- with BSA

NASA Astrophysics Data System (ADS)

Liu, Bin; Wang, Jun; Wang, Xin; Liu, Bing-Mi; He, Ling-Ling; Xu, Shu-Kun

2010-12-01

The eight-coordinate (enH 2)[Y III(pdta)(H 2O)] 2·10H 2O (en = ethylenediamine and H 4pdta = 1,3-propylenediamine- N, N, N', N'-tetraacetic acid) was synthesized, meanwhile its molecular and crystal structures were determined by single-crystal X-ray diffraction technology. The interaction between [Y III(pdta)(H 2O)] 22- and bovine serum albumin (BSA) was investigated by UV-vis and fluorescence spectra. The results indicate that [Y III(pdta)(H 2O)] 22- quenched effectively the intrinsic fluorescence of BSA via a static quenching process with the binding constant ( Ka) of the order of 10 4. Meanwhile, the binding and damaging sites to BSA molecules were also estimated by synchronous fluorescence. Results indicate that the hydrophobic environments around Trp and Tyr residues were all slightly changed. The thermodynamic parameters (Δ G = -25.20 kJ mol -1, Δ H = -26.57 kJ mol -1 and Δ S = -4.58 J mol -1 K -1) showed that the reaction was spontaneous and exothermic. What is more, both Δ H and Δ S were negative values indicated that hydrogen bond and Van der Waals forces were the predominant intermolecular forces between [Y III(pdta)(H 2O)] 22- and BSA.

The Jovian atmospheric window at 2.7 microns: A search for H2S

NASA Technical Reports Server (NTRS)

Larson, H. P.; Davis, D. S.; Hofmann, R.; Bjoraker, G. L.

1984-01-01

The atmospheric transmission window at 2.7 microns in Jupiter's atmosphere was observed at a spectral resolution of 0.1/cm from the Kuiiper Airborne Observatory. From an analysis of the CH4 abundance (80 m-am) and the H2O abundance ( 0.0125 cm-am) it was determined that the penetration depth of solar flux at 2.7 microns is near the base of the NH3 cloud layer. The upper limit to H2O at 2.7 microns and other results suggest that photolytic reactions in Jupiter's lower troposphere may not be as significant as was previously thought. A search for H2S in Jupiter's atmosphere yielded an upper limit of 0.1 cm-am. The corresponding limit to the element abundance ratio S/H was approx. 1.7x10(-8), about 10(-3) times the solar value. Upon modeling the abundance and distribution of H2S in Jupiter's atmosphere it was concluded that, contrary to expectations, sulfur-bearing chromophores are not present in significant amounts in Jupiter's visible clouds. Rather, it appears that most of Jupiter's sulfur is locked up as NH4SH in a lower cloud layer. Alternatively, the global abundance of sulfur in Jupiter may be significantly depleted.

Protein kinase G–regulated production of H2S governs oxygen sensing

PubMed Central

Yuan, Guoxiang; Vasavda, Chirag; Peng, Ying-Jie; Makarenko, Vladislav V.; Raghuraman, Gayatri; Nanduri, Jayasri; Gadalla, Moataz M.; Semenza, Gregg L.; Kumar, Ganesh K.; Snyder, Solomon H.; Prabhakar, Nanduri R.

2015-01-01

Reflexes initiated by the carotid body, the principal O2-sensing organ, are critical for maintaining cardio-respiratory homeostasis during hypoxia. O2 sensing by the carotid body requires carbon monoxide (CO) generation by heme oxygenase-2 (HO-2) and hydrogen sulfide (H2S) synthesis by cystathionine-γ-lyase (CSE). We report that O2 stimulated the generation of CO, but not that of H2S, and required two cysteine residues in the heme regulatory motif (Cys265 and Cys282) of HO-2. CO stimulated protein kinase G (PKG)–dependent phosphorylation of Ser377 of CSE, inhibiting the production of H2S. Hypoxia decreased the inhibition of CSE by reducing CO generation resulting in increased H2S, which stimulated carotid body neural activity. In carotid bodies from mice lacking HO-2, compensatory increased abundance of nNOS (neuronal nitric oxide synthase) mediated O2 sensing through PKG-dependent regulation of H2S by nitric oxide. These results provide a mechanism for how three gases work in concert in the carotid body to regulate breathing. PMID:25900831

H2 blockers

MedlinePlus

Peptic ulcer disease - H2 blockers; PUD - H2 blockers; Gastroesophageal reflux - H2 blockers; GERD - H2 blockers ... provider about your symptoms. If you have a peptic ulcer, your provider may prescribe H2 blockers along with ...

H 2 Desorption from MgH 2 Surfaces with Steps and Catalyst-Dopants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reich, Jason M.; Wang, Lin-Lin; Johnson, Duane D.

2014-03-10

Light-metal hydrides, like MgH 2, remain under scrutiny as prototypes for reversible H-storage materials. For MgH 2, we assess hydrogen desorption/adsorption properties (enthalpy and kinetic barriers) for stepped, catalyst-doped surfaces occurring, e.g., from ball-milling in real samples. Employing density functional theory and simulated annealing in a slab model, we studied initial H 2 desorption from stepped surfaces with(out) titanium (Ti) catalytic dopant. Extensive simulated annealing studies were performed to find the dopant’s site preferences. For the most stable initial and final (possibly magnetic) states, nudged elastic band (NEB) calculations were performed to determine the H 2-desorption activation energy. We usedmore » a moment-transition NEB method to account for the dopant’s transition to the lowest-energy magnetic state at each image along the band. We identify a dopant-related surface-desorption mechanism that reloads via bulk H diffusion. While reproducing the observed bulk enthalpy of desorption, we find a decrease of 0.24 eV (a 14% reduction) in the activation energy on doped stepped surface; together with a 22% reduction on a doped flat surface, this brackets the assessed 18% reduction in kinetic barrier for ball-milled MgH 2 samples with low concentration of Ti from experiment.« less

Structures, physicochemical and cytoprotective properties of new oxidovanadium(IV) complexes -[VO(mIDA)(dmbipy)]·1.5H2O and [VO(IDA)(dmbipy)]·2H2O

NASA Astrophysics Data System (ADS)

Drzeżdżon, Joanna; Jacewicz, Dagmara; Wyrzykowski, Dariusz; Inkielewicz-Stępniak, Iwona; Sikorski, Artur; Tesmar, Aleksandra; Chmurzyński, Lech

2017-09-01

New oxidovanadium(IV) complexes with a modification of the ligand in the VO2+ coordination sphere were synthesized. [VO(mIDA)(dmbipy)]•1.5H2O and [VO(IDA)(dmbipy)]•2H2O were obtained as dark green crystals and grey-green powder, respectively (mIDA = N-methyliminodiacetic anion, IDA = iminodiacetic anion, dmbipy = 4,4‧-dimethoxy-2,2‧-dipyridyl). The crystal structure of [VO(mIDA)(dmbipy)]·1.5H2O has been determined by the X-ray diffraction method. The studies of structure of [VO(mIDA)(dmbipy)]•1.5H2O have shown that this compound occurs in the crystal as two rotational conformers. Furthermore, the stability constants of [VO(mIDA)(dmbipy)]•1.5H2O and [VO(IDA)(dmbipy)]•2H2O complexes in aqueous solutions were studied by using the potentiometric titration method and, consequently, determined using the Hyperquad2008 program. Moreover, the title complexes were investigated as antioxidant substances. The impact of the structure modification in the VO2+ complexes on the radical scavenging activity has been studied. The ability to scavenge the superoxide radical by two complexes - [VO(mIDA)(dmbipy)]·1.5H2O and [VO(IDA)(dmbipy)]·2H2O was studied by cyclic voltammetry (CV) and nitrobluetetrazolium (NBT) methods. The title complexes were also examined by the spectrophotometric method as scavengers of neutral organic radical - 1,1-diphenyl-2-picrylhydrazyl (DPPH•) and radical cation - 2,2'-azinobis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS•+). Furthermore, the biological properties of two oxidovanadium(IV) complexes were investigated in relation to its cytoprotective properties by the MTT and LDH tests based on the hippocampal HT22 neuronal cell line during the oxidative damage induced by hydrogen peroxide. Finally, the results presented in this paper have shown that the both new oxidovanadium(IV) complexes with the 4,4‧-dimethoxy-2,2‧-dipyridyl ligand can be treated as the cytoprotective substances.

Studies on two-gap superconductivity in 2H-NbS2

NASA Astrophysics Data System (ADS)

Kačmarčík, J.; Pribulová, Z.; Marcenat, C.; Klein, T.; Rodière, P.; Cario, L.; Samuely, P.

2010-12-01

We present the ac-calorimetry measurements of superconducting 2H-NbS2 in the temperature range down to 0.6 K and magnetic fields up to 8 T. The temperature and magnetic field dependence of the electronic specific heat consistently indicate existence of two superconducting energy gaps in the system - one of them with the coupling ratio below the BCS weak-coupling limit and the other above that value. These results support previous findings by scanning tunneling microscopy and spectroscopy measurements [I. Guillamón, H. Suderow, S. Vieira, L. Cario, et al., Phys. Rev. Lett. 101 (2008) 166407] of two pronounced features in density of states related to a two-gap superconductivity in this system.

Variability of O2, H2S, and pH in intertidal sediments measured on a highly resolved spatial and temporal scale

NASA Astrophysics Data System (ADS)

Walpersdorf, E.; Werner, U.; Bird, P.; de Beer, D.

2003-04-01

We investigated the variability of O_2, pH, and H_2S in intertidal sediments to assess the time- and spatial scales of changes in environmental conditions and their effects on bacterial activities. Measurements were performed over the tidal cycle and at different seasons by the use of microsensors attached to an autonomous in-situ measuring device. This study was carried out at a sand- and a mixed flat in the backbarrier area of Spiekeroog (Germany) within the frame of the DFG research group "Biogeochemistry of the Wadden Sea". Results showed that O_2 variability was not pronounced in the coastal mixed flat, where only extreme weather conditions could increase O_2 penetration. In contrast, strong dynamics in O_2 availability, pH and maximum penetration depths of several cm were found at the sandflat. In these highly permeable sediments, we directly observed tidal pumping: at high tide O_2-rich water was forced into the plate and at low tide anoxic porewater drained off the sediment. From the lower part of the plate where organic rich clayey layers were embedded in the sediment anoxic water containing H_2S leaked out during low tide. Thus advective processes, driven by the tidal pump, waves and currents, control O_2 penetration and depth distribution of H_2S and pH. The effects of the resulting porewater exchange on mineralization rates and microbial activities will be discussed.

Laser photoelectron spectroscopy of MnH - 2, FeH - 2, CoH - 2, and NiH - 2: Determination of the electron affinities for the metal dihydrides

NASA Astrophysics Data System (ADS)

Miller, Amy E. S.; Feigerle, C. S.; Lineberger, W. C.

1986-04-01

The laser photoelectron spectra of MnH-2, FeH-2, CoH-2, and NiH-2 and the analogous deuterides are reported. Lack of vibrational structure in the spectra suggests that all of the dihydrides and their negative ions have linear geometries, and that the transitions observed in the spectra are due to the loss of nonbonding d electrons. The electron affinities for the metal dihydrides are determined to be 0.444±0.016 eV for MnH2, 1.049±0.014 eV for FeH2, 1.450±0.014 eV for CoH2, and 1.934±0.008 eV for NiH2. Electronic excitation energies are provided for excited states of FeH2, CoH2, and NiH2. Electron affinities and electronic excitation energies for the dideuterides are also reported. A limit on the electron affinity of CrH2 of ≥2.5 eV is determined. The electron affinities of the dihydrides directly correlate with the electron affinities of the high-spin states of the monohydrides, and with the electron affinities of the metal atoms. These results are in agreement with a qualitative model developed for bonding in the monohydrides.

H2S induced hypometabolism in mice is missing in sedated sheep.

PubMed

Haouzi, Philippe; Notet, Véronique; Chenuel, Bruno; Chalon, Bernard; Sponne, Isabelle; Ogier, Virginie; Bihain, Bernard

2008-01-01

On the basis of studies performed in mice that showed H(2)S inhalation decreasing dramatically the metabolic rate, H(2)S was proposed as a means of protecting vital organs from traumatic or ischemic episodes in humans. Hypoxia has in fact also long been shown to induce hypometabolism. However, this effect is observed solely in small-sized animals with high VO2 kg(-1), and not in large mammals. Thus, extrapolating the hypometabolic effect of H(2)S to large mammals is questionable and could be potentially dangerous. We measured metabolism in conscious mice (24 g) exposed to H(2)S (60 ppm) at an ambient temperature of 23-24 degrees C. H(2)S caused a rapid and large (50%) drop in gas exchange rate, which occurred independently of the change in body temperature. The metabolic response occurred within less than 3 min. In contrast, sheep, sedated with ketamine and weighing 74 kg did not exhibit any decrease in metabolic rate during a similar challenge at an ambient temperature of 22 degrees C. While a part of H(2)S induced hypometabolism in the mice is related to the reduction in activity, we speculate that the difference between sheep and mice may rely on the nature and the characteristics of the relationship between basal metabolic rate and body weight thus on the different mechanisms controlling resting metabolic rate according to body mass. Therefore, the proposed use of H(2)S administration as a way of protecting vital organs should be reconsidered in view of the lack of hypometabolic effect in a large sedated mammal and of H(2)S established toxicity.

Microwave-assisted synthesis of NiS2 nanostructures for supercapacitors and cocatalytic enhancing photocatalytic H2 production

PubMed Central

Pang, Huan; Wei, Chengzhen; Li, Xuexue; Li, Guochang; Ma, Yahui; Li, Sujuan; Chen, Jing; Zhang, Jiangshan

2014-01-01

Uniform NiS2 nanocubes are successfully synthesized with a microwave-assisted method. Interestingly, NiS2 nanocubes, nanospheres and nanoparticles are obtained by controlling microwave reaction time. NiS2 nanomaterials are primarily applied to supercapacitors and cocatalytic enhancing photocatalytic H2 production. Different morphologies of NiS2 nanostructures show different electrochemical and cocatalytic enhancing H2 production activities. Benefited novel nanostructures, NiS2 nanocube electrodes show a large specific capacitance (695 F g−1 at 1.25 A g−1) and excellent cycling performance (the retention 93.4% of initial specific capacitance after 3000 cycles). More importantly, NiS2 nanospheres show highly cocatalytic enhancing photocatalytic for H2 evolution, in which the photocatalytic H2 production is up to 3400 μmol during 12 hours under irradiation of visible light (λ>420 nm) with an average H2 production rate of 283 μmol h−1. PMID:24389929

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce, Nd.

PubMed

De Almeida, Lucie; Grandjean, Stéphane; Rivenet, Murielle; Patisson, Fabrice; Abraham, Francis

2014-03-28

New hydrazinium lanthanide oxalates N2H5[Ln2(C2O4)4(N2H5)]·4H2O, Ln = Ce (Ce-HyOx) and Nd (Nd-HyOx), were synthesized by hydrothermal reaction at 150 °C between lanthanide nitrate, oxalic acid and hydrazine solutions. The structure of the Nd compound was determined from single-crystal X-ray diffraction data, space group P2₁/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Å, β = 116.638(4)°, V = 2021.4(7) Å(3), Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO9 and NdO8N, an oxygen of one monodentate oxalate in the former being replaced by a nitrogen atom of a coordinated hydrazinium ion in the latter. The infrared absorption band at 1005 cm(-1) confirms the coordination of N2H5(+) to the metal. These polyhedra are connected through μ2 and μ3 oxalate ions to form an anionic three-dimensional neodymium-oxalate arrangement. A non-coordinated charge-compensating hydrazinium ion occupies, with water molecules, the resulting tunnels. The N-N stretching frequencies of the infrared spectra demonstrate the existence of the two types of hydrazine ions. Thermal reactivity of these hydrazinium oxalates and of the mixed isotypic Ce/Nd (CeNd-HyOx) oxalate were studied by using thermogravimetric and differential thermal analyses coupled with gas analyzers, and high temperature X-ray diffraction. Under air, fine particles of CeO2 and Ce(0.5)Nd(0.5)O(1.75) are formed at low temperature from Ce-HyOx and CeNd-HyOx, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxymonocyanamides Ln2O2CN2 are formed.

Pressure-Stabilized Cubic Perovskite Oxyhydride BaScO2H.

PubMed

Goto, Yoshihiro; Tassel, Cédric; Noda, Yasuto; Hernandez, Olivier; Pickard, Chris J; Green, Mark A; Sakaebe, Hikari; Taguchi, Noboru; Uchimoto, Yoshiharu; Kobayashi, Yoji; Kageyama, Hiroshi

2017-05-01

We report a scandium oxyhydride BaScO 2 H prepared by solid state reaction under high pressure. Rietveld refinements against powder synchrotron X-ray and neutron diffraction data revealed that BaScO 2 H adopts the ideal cubic perovskite structure (Pm3̅m), where oxide (O 2- ) and hydride (H - ) anions are disordered. 1 H nuclear magnetic resonance (NMR) spectroscopy provides a positive chemical shift of about +4.4 ppm, which can be understood by the distance to the nearest (and possibly the next nearest) cation from the H nucleus. A further analysis of the NMR data and calculations based on ab initio random structure searches suggest a partial cis preference in ScO 4 H 2 octahedra. The present oxyhydride, if compositionally or structurally tuned, may become a candidate for H - conductors.

A fluorescent turn-on H2S-responsive probe: design, synthesis and application.

PubMed

Zhang, Yufeng; Chen, Haiyan; Chen, Dan; Wu, Di; Chen, Xiaoqiang; Liu, Sheng Hua; Yin, Jun

2015-10-14

Hydrogen sulfide (H2S) is considered as the third signaling molecule in vivo and it plays an important role in various physiological processes and pathological processes in vivo, such as vasodilation, apoptosis, neurotransmission, ischemia/reperfusion-induced injury, insulin secretion and inflammation. Developing a highly selective and sensitive method that can detect H2S in the biological system is very important. In this work, a colorimetric and "turn-on" fluorescent probe is developed. Furthermore, this probe displays a highly selective response to H2S in aqueous solution and possesses good capability for bioimaging H2S without interference in living cells. The results suggest that a H2S-selective probe has good water-solubility, biocompatibility and cell-penetrability and can serve as an efficient tool for probing H2S in the cell level.

Impact of ozonation, anion exchange resin and UV/H2O2 pre-treatments to control fouling of ultrafiltration membrane for drinking water treatment.

PubMed

Pramanik, Biplob Kumar; Pramanik, Sagor Kumar; Sarker, Dipok Chandra; Suja, Fatihah

2017-06-01

The effects of ozonation, anion exchange resin (AER) and UV/H 2 O 2 were investigated as a pre-treatment to control organic fouling (OF) of ultrafiltration membrane in the treatment of drinking water. It was found that high molecular weight (MW) organics such as protein and polysaccharide substances were majorly responsible for reversible fouling which contributed to 90% of total fouling. The decline rate increased with successive filtration cycles due to deposition of protein content over time. All pre-treatment could reduce the foulants of a Ultrafiltration membrane which contributed to the improvement in flux, and there was a greater improvement of flux by UV/H 2 O 2 (61%) than ozonation (43%) which in turn was greater than AER (23%) treatment. This was likely due to the effective removal/breakdown of high MW organic content. AER gave greater removal of biofouling potential components (such as biodegradable dissolved organic carbon and assimilable organic carbon contents) compared to UV/H 2 O 2 and ozonation treatment. Overall, this study demonstrated the potential of pre-treatments for reducing OF of ultrafiltration for the treatment of drinking water.

Degradation of n-butylparaben and 4- tert-octylphenol in H 2O 2/UV system

NASA Astrophysics Data System (ADS)

BŁędzka, Dorota; Gryglik, Dorota; Olak, Magdalena; Gębicki, Jerzy L.; Miller, Jacek S.

2010-04-01

The degradation of two endocrine disrupting compounds: n-butylparaben (BP) and 4- tert-octylphenol (OP) in the H 2O 2/UV system was studied. The effect of operating variables: initial hydrogen peroxide concentration, initial substrate concentration, pH of the reaction solution and photon fluency rate of radiation at 254 nm on reaction rate was investigated. The influence of hydroxyl radical scavengers, humic acid and nitrate anion on reaction course was also studied. A very weak scavenging effect during BP degradation was observed indicating reactions different from hydroxyl radical oxidation. The second-order rate constants of BP and OP with OH radicals were estimated to be 4.8×10 9 and 4.2×10 9 M -1 s -1, respectively. For BP the rate constant equal to 2.0×10 10 M -1 s -1was also determined using water radiolysis as a source of hydroxyl radicals.

H2S adsorption and dissociation on NH-decorated graphene: A first principles study

NASA Astrophysics Data System (ADS)

Faye, Omar; Eduok, Ubong; Szpunar, Jerzy; Samoura, Almoustapha; Beye, Aboubaker

2018-02-01

The removal of H2S gas poses an emerging environmental concern because of the lack of knowledge of an efficient adsorbent. A detailed theoretical study of H2S adsorption and dissociation on NH-doped graphene (GNH) has been carried out by means of density theory calculations. Our results reveal that the adsorption of H2S molecule on GNH composite is enhanced by the presence of active site such as the NH radicals. These NH radical sites formed NHsbnd H bonds and increase the charge transfer from H2S to GNH. The dissociation of the adsorbed H2S molecule leads the chemisorption of SH radical via H-transfer to GNH, while the formation of GNH2 at a weight percent of 3.76 wt% of NH radical is an endothermic process with an energy of 0.299 eV and 0.358 eV for ortho and para-position respectively. However, at 7.25 wt% NH radical, we observed a complete dissociation of H2S molecule with an energy released of 0.711 eV for the chemisorbed S atom on GN2H4. Moreover, the H-transfer of the second H atom of H2S molecule at 3.76 wt% was energetic unfavorable. The trend of predicted results within this study reveals that NH-doped graphene (GNH) successfully adsorbed and eliminated of H2S molecule; this work unveils definitive theoretical procedures which can be tested and validated experimentally.

Co3(PO4)2·4H2O

PubMed Central

Lee, Young Hoon; Clegg, Jack K.; Lindoy, Leonard F.; Lu, G. Q. Max; Park, Yu-Chul; Kim, Yang

2008-01-01

Single crystals of Co3(PO4)2·4H2O, tricobalt(II) bis­[ortho­phosphate(V)] tetra­hydrate, were obtained under hydro­thermal conditions. The title compound is isotypic with its zinc analogue Zn3(PO4)2·4H2O (mineral name hopeite) and contains two independent Co2+ cations. One Co2+ cation exhibits a slightly distorted tetra­hedral coordination, while the second, located on a mirror plane, has a distorted octa­hedral coordination environment. The tetra­hedrally coordinated Co2+ is bonded to four O atoms of four PO4 3− anions, whereas the six-coordinate Co2+ is cis-bonded to two phosphate groups and to four O atoms of four water mol­ecules (two of which are located on mirror planes), forming a framework structure. In addition, hydrogen bonds of the type O—H⋯O are present throughout the crystal structure. PMID:21200978

Synthesis, structural and electrical properties of [C{sub 2}H{sub 10}N{sub 2}][(SnCl(NCS){sub 2}]{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karoui, Sahel; Kamoun, Slaheddine, E-mail: slah.kamoun@gmail.com; Jouini, Amor

2013-01-15

Synthesis, structural and electrical properties are given for a new organic stannous pseudo halide material. The structure of the [C{sub 2}H{sub 10}N{sub 2}][(SnCl(NCS){sub 2}]{sub 2} reveals that the adjacent Sn(II) centres are bridged by a pair of SCN{sup -} anions to form a 1-D array giving rise to the anionic chains (SnCl(NCS){sub 2}){sub n}{sup n-}. These chains are themselves interconnected by means of N-H Horizontal-Ellipsis Cl(S) hydrogen bonds originating from the organic cation [(NH{sub 3}){sub 2}(CH{sub 2}){sub 2}]{sup 2+}. The AC impedance measurements were performed as a function of both frequency and temperature. The electrical conduction and dielectric relaxation havemore » been studied. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found close to that of the activation energy obtained for DC conductivity. The conduction mechanisms are attributed to the quantum mechanical tunneling model in phase I and to the proton hopping among hydrogen vacancies in phase II. - Graphical abstract: Atomic coordination in [C2H10N2][SnCl(NCS)2)2]. Highlights: Black-Right-Pointing-Pointer X-ray diffraction analysis shows the 1D network character of the structure. Black-Right-Pointing-Pointer DSC experiments show a phase transition at 336 K. Black-Right-Pointing-Pointer The AC conductivity is interpreted in terms of Jonsher's law. Black-Right-Pointing-Pointer Two conduction mechanisms are proposed for phase I and II.« less

Modes of physiologic H2S signaling in the brain and peripheral tissues.

PubMed

Paul, Bindu D; Snyder, Solomon H

2015-02-10

Hydrogen sulfide (H2S), once associated with rotten eggs and sewers, is now recognized as a gasotransmitter that is synthesized in vivo in a regulated fashion. This ancient gaseous molecule has been retained throughout evolution to perform various roles in different life forms. H2S modulates important signaling functions in diverse cellular processes ranging from regulation of blood pressure to redox homeostasis. One of the modes by which H2S signals is by post-translational modification of reactive cysteine residues in a process designated as sulfhydration, resulting in conversion of the -SH groups of target cysteine residues to -SSH. Using the modified biotin-switch assay and a fluorescent maleimide-based analysis, sulfhydration of several proteins has been detected in various cell types. Aberrant sulfhydration patterns occur in neurodegenerative conditions such as Parkinson's disease. The exact concentration, source of H2S, and conditions under which various stores of H2S are utilized have not been fully elucidated. Currently, available inhibitors of the biosynthetic enzymes of H2S lack sufficient specificity to shed light on detailed mechanisms of H2S action. Probes with a higher sensitivity that can reliably detect cellular and tissue H2S levels are yet to be developed. Availability of advanced probes and biosynthesis inhibitors would help in the measurement of real-time changes of endogenous H2S levels in an in vivo context. The study of the dynamics of sulfhydration and nitrosylation of critical cysteine residues of regulatory proteins involved in physiology and pathophysiology is an area of interest for the future.

Swine influenza virus vaccine serologic cross-reactivity to contemporary U.S. swine H3N2 and efficacy in pigs infected with an H3N2 similar to 2011-2012 H3N2v

USDA-ARS?s Scientific Manuscript database

Background: Swine influenza A virus (IAV) reassortment with 2009 H1N1 pandemic (H1N1pdm09) virus has been documented and new genotypes and sub-clusters of H3N2 have since expanded in the U.S. swine population. An H3N2 variant (H3N2v) virus with the H1N1pdm09 matrix gene and the remaining genes of sw...

Mechanistic Study of the Stereoselective Hydroxylation of [2-2 H1 ,3-2 H1 ]Butanes Catalyzed by Cytochrome P450 BM3 Variants.

PubMed

Yang, Chung-Ling; Lin, Cheng-Hung; Luo, Wen-I; Lee, Tsu-Lin; Ramu, Ravirala; Ng, Kok Yaoh; Tsai, Yi-Fang; Wei, Guor-Tzo; Yu, Steve S-F

2017-02-21

Engineered bacterial cytochrome P450s are noted for their ability in the oxidation of inert small alkanes. Cytochrome P450 BM3 L188P A328F (BM3 PF) and A74E L188P A328F (BM3 EPF) variants are able to efficiently oxidize n-butane to 2-butanol. Esterification of the 2-butanol derived from this reaction mediated by the aforementioned two mutants gives diastereomeric excesses (de) of -56±1 and -52±1 %, respectively, with the preference for the oxidation occurring at the C-H S bond. When tailored (2R,3R)- and (2S,3S)-[2- 2 H 1 ,3- 2 H 1 ]butane probes are employed as substrates for both variants, the obtained de values from (2R,3R)-[2- 2 H 1 ,3- 2 H 1 ]butane are -93 and -92 % for BM3 PF and EPF, respectively; whereas the obtained de values from (2S,3S)-[2- 2 H 1 ,3- 2 H 1 ]butane are 52 and 56 % in the BM3 PF and EPF systems, respectively. The kinetic isotope effects (KIEs) for the oxidation of (2R,3R)-[2- 2 H 1 ,3- 2 H 1 ]butane are 7.3 and 7.8 in BM3 PF and EPF, respectively; whereas KIEs for (2S,3S)-[2- 2 H 1 ,3- 2 H 1 ]butanes are 18 and 25 in BM3 PF and EPF, respectively. The discrepancy in KIEs obtained from the two substrates supports the two-state reactivity (TSR) that is proposed for alkane oxidation in cytochrome P450 systems. Moreover, for the first time, experimental evidence for tunneling in the oxidation mediated by P450 is given through the oxidation of the C-H R bond in (2S,3S)-[2- 2 H 1 ,3- 2 H 1 ]butane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnO-carbon nanofibers for stable, high response, and selective H2S sensors.

PubMed

Zhang, Jitao; Zhu, Zijian; Chen, Changmiao; Chen, Zhi; Cai, Mengqiu; Qu, Baihua; Wang, Taihong; Zhang, Ming

2018-07-06

Hydrogen sulfide (H 2 S), as a typical atmospheric pollutant, is neurotoxic and flammable even at a very low concentration. In this study, we design stable H 2 S sensors based on ZnO-carbon nanofibers. Nanofibers with 30.34 wt% carbon are prepared by a facial electrospinning route followed by an annealing treatment. The resulting H 2 S sensors show excellent selectivity and response compared to the pure ZnO nanofiber H 2 S sensors, particularly the response in the range of 102-50 ppm of H 2 S. Besides, they exhibited a nearly constant response of approximately 40-20 ppm of H 2 S over 60 days. The superior performance of these H 2 S sensors can be attributed to the protection of carbon, which ensures the high stability of ZnO, and oxygen vacancies that improve the response and selectivity of H 2 S. The good performance of ZnO-carbon H 2 S sensors suggests that composites with oxygen vacancies prepared by a facial electrospinning route may provide a new research strategy in the field of gas sensors, photocatalysts, and semiconductor devices.

H2S adsorption on chromium, chromia, and gold/chromia surfaces: Photoemission studies

NASA Astrophysics Data System (ADS)

Rodriguez, J. A.; Chaturvedi, S.; Kuhn, M.; van Ek, J.; Diebold, U.; Robbert, P. S.; Geisler, H.; Ventrice, C. A., Jr.

1997-12-01

The reaction of H2S with chromium, chromia, and Au/chromia films grown on a Pt(111) crystal has been investigated using synchrotron-based high-resolution photoemission spectroscopy. At 300 K, H2S completely decomposes on polycrystalline chromium producing a chemisorbed layer of S that attenuates the Cr 3d valence features. No evidence was found for the formation of CrSx species. The dissociation of H2S on Cr3O4 and Cr2O3 films at room temperature produces a decrease of 0.3-0.8 eV in the work function of the surface and significant binding-energy shifts (0.2-0.6 eV) in the Cr 3p core levels and Cr 3d features in the valence region. The rate of dissociation of H2S increases following the sequence: Cr2O3H2S than the valence and conduction bands of the chromium oxides. This leads to a large dissociation probability for H2S on the metal, and a low dissociation probability for the molecule on the oxides. In the case of Cr3O4 and Cr2O3, there is a correlation between the size of the band gap in the oxide and its reactivity toward H2S. The uptake of sulfur by the oxides significantly increases when they are "promoted" with gold. The Au/Cr2O3 surfaces exhibit a unique electronic structure in the valence region and a larger ability to dissociate H2S than polycrystalline Au or pure Cr2O3. The results of ab initio SCF calculations for the adsorption of H2S on AuCr4O6 and AuCr10O15 clusters show a shift of electrons from the gold toward the oxide unit that enhances the strength of the Au(6s)↔H2S(5a1,2b1) bonding interactions and facilitates the decomposition of the molecule.

Characterization of H2S removal and microbial community in landfill cover soils.

PubMed

Xia, Fang-Fang; Zhang, Hong-Tao; Wei, Xiao-Meng; Su, Yao; He, Ruo

2015-12-01

H2S is a source of odors at landfills and poses a threat to the surrounding environment and public health. In this work, compared with a usual landfill cover soil (LCS), H2S removal and biotransformation were characterized in waste biocover soil (WBS), an alternative landfill cover material. With the input of landfill gas (LFG), the gas concentrations of CH4, CO2, O2, and H2S, microbial community and activity in landfill covers changed with time. Compared with LCS, lower CH4 and H2S concentrations were detected in the WBS. The potential sulfur-oxidizing rate and sulfate-reducing rate as well as the contents of acid-volatile sulfide, SO4(2-), and total sulfur in the WBS and LCS were all increased with the input of LFG. After exposure to LFG for 35 days, the sulfur-oxidizing rate of the bottom layer of the WBS reached 82.5 μmol g dry weight (d.w.)(-1) day(-1), which was 4.3-5.4 times of that of LCS. H2S-S was mainly deposited in the soil covers, while it escaped from landfills to the atmosphere. The adsorption, absorption, and biotransformation of H2S could lead to the decrease in the pH values of landfill covers; especially, in the LCS with low pH buffer capacity, the pH value of the bottom layer dropped to below 4. Pyrosequencing of 16S ribosomal RNA (rRNA) gene showed that the known sulfur-metabolizing bacteria Ochrobactrum, Paracoccus, Comamonas, Pseudomonas, and Acinetobacter dominated in the WBS and LCS. Among them, Comamonas and Acinetobacter might play an important role in the metabolism of H2S in the WBS. These findings are helpful to understand sulfur bioconversion process in landfill covers and to develop techniques for controlling odor pollution at landfills.

Ternary recombination of H3+, H2D+, HD2+, and D3+ with electrons in He/Ar/H2/D2 gas mixtures

NASA Astrophysics Data System (ADS)

Kalosi, Abel; Dohnal, Petr; Plasil, Radek; Johnsen, Rainer; Glosik, Juraj

2016-09-01

The temperature dependence of the ternary recombination rate coefficients of H2D+ and HD2+ ions has been studied in the temperature range of 80-150 K at pressures from 500 to 1700 Pa in a stationary afterglow apparatus equipped with a cavity ring-down spectrometer. Neutral gas mixtures consisting of He/Ar/H2/D2 (with typical number densities 1017 /1014 /1014 /1014 cm-3) were employed to produce the desired ionic species and their fractional abundances were monitored as a function of helium pressure and the [D2]/[H2] ratio of the neutral gas. In addition, the translational and the rotational temperature and the ortho to para ratio were monitored for both H2D+ and HD2+ ions. A fairly strong pressure dependence of the effective recombination rate coefficient was observed for both ion species, leading to ternary recombination rate coefficients close to those previously found for (helium assisted) ternary recombination of H3+ and D3+. Work supported by: Czech Science Foundation projects GACR 14-14649P, GACR 15-15077S, GACR P209/12/0233, and by Charles University in Prague Project Nr. GAUK 692214.

Synthesis of TiO2-CNT hybrid nanocatalyst and its application in direct oxidation of H2S to S

NASA Astrophysics Data System (ADS)

Daraee, Maryam; Baniadam, Majid; Rashidi, Alimorad; Maghrebi, Morteza

2018-07-01

In this study, a TiO2-CNT hybrid catalyst has been synthesized and its catalytic activity in the oxidation of H2S to S has been investigated and compared with those of TiO2 nanoparticles and pyrolyzed TiO2-CNT hybrid (P-TiO2-CNT). The optimum catalyst amount was determined using central composite design (CCD) method. Catalysts were characterized by various analytical techniques. The H2S conversion, sulfur selectivity and yield at the optimal temperature of 200 °C and O2/H2S ratio of 0.5 were 98.3, 99.5 and 97%, respectively. TiO2-CNT16% catalyst has a higher surface area than TiO2 nanoparticles and P-TiO2-CNT. In addition, the former catalyst gives a high conversion of H2S and sulfur selectivity at 200 °C and O2/H2S ratio of 0.5 compared with the latter two catalysts. The superior conversion (over 10%) of TiO2-CNT16% hybrid compared to TiO2 nanoparticles can be attributed to the synergistic effects of TiO2 and CNT, the reduced band gap of TiO2-CNT16% hybrid and high specific surface area of the catalyst.

Preparation of polyaniline/PbS core-shell nano/microcomposite and its application for photocatalytic H2 electrogeneration from H2O.

PubMed

Rabia, Mohamed; Mohamed, H S H; Shaban, Mohamed; Taha, S

2018-01-18

Lead sulfide (PbS) and polyaniline (PANI) nano/microparticles were prepared. Then, PANI/PbS core-shell nano/microcomposites (I, II, and III) were prepared by oxidative polymerization of different aniline concentrations (0.01, 0.03, and 0.05 M), respectively, in the presence of 0.05 M PbS. FT-IR, XRD, SEM, HR-TEM, and UV-Vis analyses were carried out to characterize the samples. From the FT-IR data, there are redshifts in PbS and PANI nano/microparticles bands in comparison with PANI/PbS nano/microcomposites. The average crystallite sizes of PANI/PbS core-shell nano/microcomposites (I, II, and III) from XRD analyses were 46.5, 55, and 42.16 nm, respectively. From the optical analyses, nano/microcomposite (II) has the optimum optical properties with two band gaps values of 1.41 and 2.79 eV. Then, the nano/microcomposite (II) membrane electrode supported on ITO glass was prepared and applied on the photoelectrochemical (PEC) H 2 generation from H 2 O. The characteristics current-voltage and current-time behaviors were measured at different wavelengths from 390 to 636 nm. Also, the incident photon-to-current conversion efficiency (IPCE) under monochromatic illumination condition was calculated. The optimum values for IPCE were 36.5 and 35.2% at 390 and 405 nm, respectively. Finally, a simple mechanism for PEC H 2 generation from H 2 O using the nano/microcomposite (II) membrane electrode was mentioned.

H2S Injection and Sequestration into Basalt - The SulFix Project

NASA Astrophysics Data System (ADS)

Gudbrandsson, S.; Moola, P.; Stefansson, A.

2014-12-01

Atmospheric H2S emissions are among major environmental concern associated with geothermal energy utilization. It is therefore of great importance for the geothermal power sector to reduce H2S emissions. Known solutions for H2S neutralization are both expensive and include production of elemental sulfur and sulfuric acid that needs to be disposed of. Icelandic energy companies that utilize geothermal power for electricity production have decided to try to find an environmentally friendly and economically feasible solution to reduce the H2S emission, in a joint venture called SulFix. The aim of SulFix project is to explore the possibilities of injecting H2S dissolved in water into basaltic formations in close proximity to the power plants for permanent fixation as sulfides. The formation of sulfides is a natural process in geothermal systems. Due to basalt being rich in iron and dissolving readily at acidic conditions, it is feasible to re-inject the H2S dissolved in water, into basaltic formations to form pyrite. To estimate the mineralization rates of H2S, in the basaltic formation, flow through experiments in columns were conducted at various H2S concentrations, temperatures (100 - 240°C) and both fresh and altered basaltic glass. The results indicate that pyrite rapidly forms during injection into fresh basalt but the precipiation in altered basalt is slower. Three different alteration stages, as a function of distance from inlet, can be observed in the column with fresh basaltic glass; (1) dissolution features along with precipitation, (2) precipitation increases, both sulfides and other secondary minerals and (3) the basalt looks to be unaltered and little if any precipitation is observed. The sulfur has precipitated in the first half of the column and thereafter the solution is possibly close to be supersaturated with respect to the rock. These results indicate that the H2S sequestration into basalt is possible under geothermal conditions. The rate limiting

Immobilization of Alkali Metal Fluorides via Recrystallization in a Cationic Lamellar Material, [Th(MoO4)(H2O)4Cl]Cl·H2O.

PubMed

Lin, Jian; Bao, Hongliang; Qie, Meiying; Silver, Mark A; Yue, Zenghui; Li, Xiaoyun; Zhu, Lin; Wang, Xiaomei; Zhang, Linjuan; Wang, Jian-Qiang

2018-06-05

Searching for cationic extended materials with a capacity for anion exchange resulted in a unique thorium molybdate chloride (TMC) with the formula of [Th(MoO 4 )(H 2 O) 4 Cl]Cl·H 2 O. The structure of TMC is composed of zigzagging cationic layers [Th(MoO 4 )(H 2 O) 4 Cl] + with Cl - as interlamellar charge-balancing anions. Instead of performing ion exchange, alkali thorium fluorides were formed after soaking TMC in AF (A = Na, K, and Cs) solutions. The mechanism of AF immobilization is elucidated by the combination of SEM-EDS, PXRD, FTIR, and EXAFS spectroscopy. It was observed that four water molecules coordinating with the Th 4+ center in TMC are vulnerable to competition with F - , due to the formation of more favorable Th-F bonds compared to Th-OH 2 . This leads to a single crystal-to-polycrystalline transformation via a pathway of recrystallization to form alkali thorium fluorides.

Reactivity and dynamics of H2S, NO, and O2 interacting with hemoglobins from Lucina pectinata.

PubMed

Ramos-Alvarez, Cacimar; Yoo, Byung-Kuk; Pietri, Ruth; Lamarre, Isabelle; Martin, Jean-Louis; Lopez-Garriga, Juan; Negrerie, Michel

2013-10-08

Hemoglobin HbI from the clam Lucina pectinata is involved in H2S transport, whereas homologous heme protein HbII/III is involved in O2 metabolism. Despite similar tertiary structures, HbI and HbII/III exhibit very different reactivity toward heme ligands H2S, O2, and NO. To investigate this reactivity at the heme level, we measured the dynamics of ligand interaction by time-resolved absorption spectroscopy in the picosecond to nanosecond time range. We demonstrated that H2S can be photodissociated from both ferric and ferrous HbI. H2S geminately rebinds to ferric and ferrous out-of-plane iron with time constants (τgem) of 12 and 165 ps, respectively, with very different proportions of photodissociated H2S exiting the protein (24% in ferric and 80% in ferrous HbI). The Gln(E7)His mutation considerably changes H2S dynamics in ferric HbI, indicating the role of Gln(E7) in controling H2S reactivity. In ferric HbI, the rate of diffusion of H2S from the solvent into the heme pocket (kentry) is 0.30 μM(-1) s(-1). For the HbII/III-O2 complex, we observed mainly a six-coordinate vibrationally excited heme-O2 complex with O2 still bound to the iron. This explains the low yield of O2 photodissociation and low koff from HbII/III, compared with those of HbI and Mb. Both isoforms behave very differently with regard to NO and O2 dynamics. Whereas the amplitude of geminate rebinding of O2 to HbI (38.5%) is similar to that of myoglobin (34.5%) in spite of different distal heme sites, it appears to be much larger for HbII/III (77%). The distal Tyr(B10) side chain present in HbII/III increases the energy barrier for ligand escape and participates in the stabilization of bound O2 and NO.

Functionalized UO[sub 2] salenes. Neutral receptors for anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudkevich, D.M.; Verboom, W.; Brzozka, Z.

1994-05-18

A novel class of neutral receptors for anions that contain a unique combination of an immobilized Lewis acidic binding site (UO[sub 2][sup 2+]) and additional amide C(O)NH groups, which can form a favorable H-bond with a coordinated anion guest, has been developed. The unique combination of a Lewis acidic UO[sub 2] center and amide C(O)NH groups in one receptor leads to highly specific H[sub 2]PO[sub 4[sup [minus

Effects of microsolvation on uracil and its radical anion: Uracil.(H2O)n (n=1-5)

NASA Astrophysics Data System (ADS)

Kim, Sunghwan; Schaefer, Henry F.

2006-10-01

Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYP /DZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24eV) was higher than that of thymine by 0.04eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil•(H2O)5, namely, 0.96eV. The VDEs range from 0.76to1.78eV.

Effects of microsolvation on uracil and its radical anion: uracil(H2O)n (n = 1-5).

PubMed

Kim, Sunghwan; Schaefer, Henry F

2006-10-14

Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYPDZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24 eV) was higher than that of thymine by 0.04 eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil(H2O)5, namely, 0.96 eV. The VDEs range from 0.76 to 1.78 eV.

The structure directing effect of organic cations onto the crystal structures of layered thioantimonates(III): Solvothermal synthesis and crystal structures of five new compounds containing the 2∞[Sb 8S 13] 2- anion

NASA Astrophysics Data System (ADS)

Puls, Angela; Näther, Christian; Kiebach, Ragnar; Bensch, Wolfgang

2006-09-01

The five new thioantimonates(III) ( iprH) 2[Sb 8S 13] ( I), (1,2-dapH) 2[Sb 8S 13] ( II), (1,3-dapH 2)[Sb 8S 13] ( III), (dienH 2)[Sb 8S 13]ṡ1.5H 2O ( IV), and (C 6H 9N 2)[Sb 8S 13]ṡ2.5H 2O ( V) were synthesised under solvothermal conditions ( ipr = iso-propylamine; 1,2-dap = 1,2-diaminopropane; 1,3-dap = 1,3-diaminopropane; dien = diethylentriamine; C 6H 9N 2 = 3-(aminoethyl)-pyridine). The structures of compounds I and II are topological very similar and a central motif is a Sb 10S 10 ring. On both sides of this ring Sb 5S 5 rings are condensed. These rings are connected via Sb 4S 4 rings leading to the sequence Sb 10S 10-Sb 5S 5-Sb 4S 4-Sb 5S 5-Sb 10Sb 10 in the [010] direction. Further interconnection into the two-dimensional [Sb 8S 13] 2- anion produces a large central Sb 18S 18 ring with dimensions of 11ṡ11 Å in both compounds. The two atoms thick layers are linear and stacked along the a axis generating large channels running along [010]. The layered anion of compound III is constructed by interconnection of the SbS 3 and SbS 4 units yielding Sb 19S 19, Sb 14S 14, Sb 13S 13, and Sb 8S 8 rings. The linear layers are two atoms thick and are stacked perpendicular to [001] to form channels running along the same direction. The last two compounds IV and V show a similar network topology. The layered anion is constructed by SbS 3 trigonal pyramids and SbS 4 units. The layer contains a Sb 12S 12 rings as the main structural motif. The corrugated layers extending in the (100) plane are two atoms thick and are stacked in a manner that large tunnels run along [100]. The total potential solvent areas are large and range from 20.7% for III to 35% for II.

VUV photoionization cross sections of HO2, H2O2, and H2CO.

PubMed

Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

2015-02-26

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

Quantum-tunneling isotope-exchange reaction H2+D-→HD +H-

NASA Astrophysics Data System (ADS)

Yuen, Chi Hong; Ayouz, Mehdi; Endres, Eric S.; Lakhamanskaya, Olga; Wester, Roland; Kokoouline, Viatcheslav

2018-02-01

The tunneling reaction H2+D-→HD +H- was studied in a recent experimental work at low temperatures (10, 19, and 23 K) by Endres et al. [Phys. Rev. A 95, 022706 (2017), 10.1103/PhysRevA.95.022706]. An upper limit of the rate coefficient was found to be about 10-18cm3 /s. In the present study, reaction probabilities are determined using the ABC program developed by Skouteris et al. [Comput. Phys. Commun. 133, 128 (2000), 10.1016/S0010-4655(00)00167-3]. The probabilities for ortho-H2 and para-H2 in their ground rovibrational states are obtained numerically at collision energies above 50 meV with the total angular momentum J =0 -15 and extrapolated below 50 meV using a WKB approach. Thermally averaged rate coefficients for ortho- and para-H2 are obtained; the largest one, for ortho-H2, is about 3.1 ×10-20cm3 /s, which agrees with the experimental results.

Two's company, three's a crowd: can H2S be the third endogenous gaseous transmitter?

PubMed

Wang, Rui

2002-11-01

Bearing the public image of a deadly "gas of rotten eggs," hydrogen sulfide (H2S) can be generated in many types of mammalian cells. Functionally, H2S has been implicated in the induction of hippocampal long-term potentiation, brain development, and blood pressure regulation. By acting specifically on KATP channels, H2S can hyperpolarize cell membranes, relax smooth muscle cells, or decrease neuronal excitability. The endogenous metabolism and physiological functions of H2S position this gas well in the novel family of endogenous gaseous transmitters, termed "gasotransmitters." It is hypothesized that H2S is the third endogenous signaling gasotransmitter, besides nitric oxide and carbon monoxide. This positioning of H2S will open an exciting field-H2S physiology-encompassing realization of the interaction of H2S and other gasotransmitters, sulfurating modification of proteins, and the functional role of H2S in multiple systems. It may shed light on the pathogenesis of many diseases related to the abnormal metabolism of H2S.

Analysis of cardiovascular responses to the H2S donors Na2S and NaHS in the rat

PubMed Central

Yoo, Daniel; Jupiter, Ryan C.; Pankey, Edward A.; Reddy, Vishwaradh G.; Edward, Justin A.; Swan, Kevin W.; Peak, Taylor C.; Mostany, Ricardo

2015-01-01

Hydrogen sulfide (H2S) is an endogenous gaseous molecule formed from L-cysteine in vascular tissue. In the present study, cardiovascular responses to the H2S donors Na2S and NaHS were investigated in the anesthetized rat. The intravenous injections of Na2S and NaHS 0.03–0.5 mg/kg produced dose-related decreases in systemic arterial pressure and heart rate, and at higher doses decreases in cardiac output, pulmonary arterial pressure, and systemic vascular resistance. H2S infusion studies show that decreases in systemic arterial pressure, heart rate, cardiac output, and systemic vascular resistance are well-maintained, and responses to Na2S are reversible. Decreases in heart rate were not blocked by atropine, suggesting that the bradycardia was independent of parasympathetic activation and was mediated by an effect on the sinus node. The decreases in systemic arterial pressure were not attenuated by hexamethonium, glybenclamide, Nw-nitro-l-arginine methyl ester hydrochloride, sodium meclofenamate, ODQ, miconazole, 5-hydroxydecanoate, or tetraethylammonium, suggesting that ATP-sensitive potassium channels, nitric oxide, arachidonic acid metabolites, cyclic GMP, p450 epoxygenase metabolites, or large conductance calcium-activated potassium channels are not involved in mediating hypotensive responses to the H2S donors in the rat and that responses are not centrally mediated. The present data indicate that decreases in systemic arterial pressure in response to the H2S donors can be mediated by decreases in vascular resistance and cardiac output and that the donors have an effect on the sinus node independent of the parasympathetic system. The present data indicate that the mechanism of the peripherally mediated hypotensive response to the H2S donors is uncertain in the intact rat. PMID:26071540

Fragmentations of [M-H]- anions of peptides containing Ser sulfate. A joint experimental and theoretical study.

PubMed

Tran, T T Nha; Wang, Tianfang; Hack, Sandra; Bowie, John H

2013-11-15

To determine the negative-ion cleavages from [M-H](-) ions of Ser sulfate-containing peptides using experiment and theory in concert. Fragmentations were explored using a Waters QTOF2 mass spectrometer in negative-ion electrospray mode, together with calculations at the CAM-B3LYP/6-311++g(d,p) level of theory. Peptides used in this study were: GS(SO3H)(OH) 1 GS(SO3H)(OCH3) 1a GAVS(SO3H)(OH) 2 GAVS(SO3H)(OCH3) 2a GLS(SO3H)(GVA(OH) 3 GLS(SO3H)GDA(OH) 4 GLS(SO3H)GS(SO3H)A(OH) 5. Previously, it has been shown that a peptide containing a Tyr sulfate group shows [(M-H)(-) -SO3] as the base peak. Only a small peak was observed corresponding to HOSO3(-) (formed following rearrangement of the sulfate). A Ser sulfate-containing peptide, in contrast, shows pronounced peaks due to cleavage product anions [(M-H)(-)-SO3] and HOSO3(-). Theoretical calculations at the CAM-B3LYP/6-311++g(d,p) level of theory suggest that rearrangement of a Ser sulfate to give C-terminal CO2SO3H is energetically unfavourable in comparison with fragmentation of the intact Ser sulfate to yield [(M-H)(-)-SO3] and HOSO3(-). [(M-H)(-)-H2SO4] anions are not observed in the spectra of peptides containing Ser sulfate, presumably because HOSO3(-) is a relatively weak gas-phase base (ΔGacid = 1265 kJ mol(-1)). Experimental and theoretical data suggest that [(M-H)(-)-SO3] and HOSO3(-) product anions (from a peptide with a C-terminal Ser sulfate) are formed from the serine sulfate anion accompanied by specific proton transfer. CID MS/MS/MS data for an [(M-H)(-)-SO3] ion of an underivatised sulfate-containing peptide will normally allow the determination of the amino acid sequence of that peptide. The one case we have studied where that is not the case is GLS(SO3H)GDA(OH), where the peptide contains Ser sulfate and Asp, where the diagnostic Asp cleavages are competitive with the Ser sulfate cleavages. Copyright © 2013 John Wiley & Sons, Ltd.

Exogenous H2S facilitating ubiquitin aggregates clearance via autophagy attenuates type 2 diabetes-induced cardiomyopathy

PubMed Central

Wu, Jichao; Tian, Zhiliang; Sun, Yu; Lu, Cuicui; Liu, Ning; Gao, Zhaopeng; Zhang, Linxue; Dong, Shiyun; Yang, Fan; Zhong, Xin; Xu, Changqing; Lu, Fanghao; Zhang, Weihua

2017-01-01

Diabetic cardiomyopathy (DCM) is a serious complication of diabetes. Hydrogen sulphide (H2S), a newly found gaseous signalling molecule, has an important role in many regulatory functions. The purpose of this study is to investigate the effects of exogenous H2S on autophagy and its possible mechanism in DCM induced by type II diabetes (T2DCM). In this study, we found that sodium hydrosulphide (NaHS) attenuated the augment in left ventricular (LV) mass and increased LV volume, decreased reactive oxygen species (ROS) production and ameliorated H2S production in the hearts of db/db mice. NaHS facilitated autophagosome content degradation, reduced the expression of P62 (a known substrate of autophagy) and increased the expression of microtubule-associated protein 1 light chain 3 II. It also increased the expression of autophagy-related protein 7 (ATG7) and Beclin1 in db/db mouse hearts. NaHS increased the expression of Kelch-like ECH-associated protein 1 (Keap-1) and reduced the ubiquitylation level in the hearts of db/db mice. 1,4-Dithiothreitol, an inhibitor of disulphide bonds, increased the ubiquitylation level of Keap-1, suppressed the expression of Keap-1 and abolished the effects of NaHS on ubiquitin aggregate clearance and ROS production in H9C2 cells treated with high glucose and palmitate. Overall, we concluded that exogenous H2S promoted ubiquitin aggregate clearance via autophagy, which might exert its antioxidative effect in db/db mouse myocardia. Moreover, exogenous H2S increased Keap-1 expression by suppressing its ubiquitylation, which might have an important role in ubiquitin aggregate clearance via autophagy. Our findings provide new insight into the mechanisms responsible for the antioxidative effects of H2S in the context of T2DCM. PMID:28796243

Visible light-driven photocatalytic H{sub 2}-generation activity of CuS/ZnS composite particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Liang; Chen, Hua; Huang, Jianhua, E-mail: jhhuang@zstu.edu.cn

2015-04-15

Highlights: • Preparation of CuS/ZnS composite photocatalyst by cation-exchange reaction. • Visible light photocatalytic activity for H{sub 2} evolution without cocatalyst. • The H{sub 2}-evolution rate from water splitting depends on the CuS content. • The highest rate of H{sub 2} evolution is obtained with CuS (0.5 mol%)/ZnS composite. - Abstract: CuS/ZnS composite particles with diameter of 200–400 nm were successfully prepared by a simple cation-exchange reaction using ZnS spheres as a precursor. CuS nanoparticles with a few nanometers in diameter were observed on the surface of composite particles. The synthesized CuS/ZnS composite particles showed photocatalytic property effective for H{submore » 2} evolution from an aqueous Na{sub 2}S and Na{sub 2}SO{sub 3} solution under visible light irradiation without any cocatalysts. The rate of H{sub 2} generation was found to be strongly dependent on the CuS content. The highest rate of H{sub 2} evolution reached 695.7 μmol h{sup −1} g{sup −1}, which was almost 7 times as high as that of the mechanical mixture of CuS and ZnS. The enhancement in the photocatalytic activity of CuS/ZnS composite particles is supposed to be due to the direct interfacial charge transfer of the CuS/ZnS heterojunction.« less

Superconducting order from disorder in 2H-TaSe 2-xS x

DOE PAGES

Li, Lijun; Deng, Xiaoyu; Wang, Zhen; ...

2017-02-24

Here, we report on the emergence of robust superconducting order in single crystal alloys of TaSe 2$ -$x S x (0 ≤ × ≤2). The critical temperature of the alloy is surprisingly higher than that of the two end compounds TaSe2 and TaS2. The evolution of superconducting critical temperature T c(x) correlates with the full width at half maximum of the Bragg peaks and with the linear term of the high-temperature resistivity. The conductivity of the crystals near the middle of the alloy series is higher or similar than that of either one of the end members 2H-TaSe 2 and/ormore » 2H-TaS 2. It is known that in these materials superconductivity is in close competition with charge density wave order. We interpret our experimental findings in a picture where disorder tilts this balance in favor of superconductivity by destroying the charge density wave order.« less

The role of electric field in enhancing separation of gas molecules (H2S, CO2, H2O) on VIB modified g-C3N4 (0 0 1)

NASA Astrophysics Data System (ADS)

Wang, Fang; Li, Penghui; Wei, Shiqian; Guo, Jiaxing; Dan, Meng; Zhou, Ying

2018-07-01

In this study, the first-principles calculations were performed to investigate the adsorption behaviors of gas molecules H2S, CO2 and H2O on Cr, Mo and W modified g-C3N4 (0 0 1) surface. The results show that H2S, CO2 and H2O are physically adsorbed on the pristine g-C3N4, while the adsorption becomes chemisorbed due to the introduction of transition metals which significantly improve the interfacial electron transfer and narrow the band gap of g-C3N4 (0 0 1). Furthermore, it is found that the adsorption behaviors can be greatly influenced by the applied electric field. The adsorption energy is generally arranged in the order of Eads(H2S) > Eads(H2O) > Eads(CO2), and W/g-C3N4 (0 0 1) exhibits the best separation capability. The study could provide a versatile approach to selectively capture and separate the mixed gases in the catalytic reactions by controlling the applied intensity of electric field.

Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).

PubMed

Wu, Xiao-Peng; Sun, Xiao-Ming; Wei, Xi-Guang; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

2009-06-09

The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.

MICROWAVE SPECTRA AND GEOMETRIES OF C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}

NASA Astrophysics Data System (ADS)

Stephens, Susanna L.; Tew, David Peter; Walker, Nick; Legon, Anthony

2015-06-01

A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}. These complexes are generated via laser ablation at 532 nm of a silver surface in the presence of CF3I and either C2H_{2} or C2H_{4} and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ and ΔJK) of each molecule have been determined as well the nuclear electric quadrupole coupling constants the iodine atom (χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H_{2} or C2H_{4} subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently studied H2S\\cdots AgI, OC\\cdotsAgI, H3N\\cdots AgI and (CH3)_{3N\\cdots AgI}. S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, 1-12 (2012) S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), 064306 (2012) D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.

Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Homayoon, Zahra; Conte, Riccardo; Qu, Chen

2015-08-28

New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are comparedmore » to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.« less

Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Liuyang; University of Chinese Academy of Sciences, Beijing 100049; Shao, Kejie

2016-05-21

This work performs a time-dependent wavepacket study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H{sub 2} + C{sub 2}H↔H + C{sub 2}H{sub 2}, H + C{sub 2}H{sub 2} → HCCH{sub 2}, and HCCH{sub 2} radial isomerization reaction regions. The reaction dynamics of H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} are investigated using full-dimensional quantum dynamics method. The initial-state selected reactionmore » probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H{sub 2} vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C{sub 2}H slightly inhibits the reaction. The excitations of two stretching modes of C{sub 2}H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.« less

Low-T magnetometry study of S = 1 Q2D [Ni(pyz) 2(H 2O) 2](BF 4) 2 (pyz = pyrazine)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manson, J. L.; Villa, D. Y.; Blackmore, W. J. A.

2017-02-13

[Ni(pyz) 2(H 2O) 2](BF 4) 2 (pyz = N 2C 4H 4) was synthesized by a solvent-free technique and its structure solved by synchrotron X-ray powder diffraction.1 The compound contains S = 1 Ni(II) ions and has tetragonal symmetry. Two-D [Ni(pyz) 2(H 2O) 2] 2+ square lattices propagate in the ab-plane and stack along the c-axis (Fig. 1). Water ligands occupy axial sites and form H-bonds with interlayer BF 4 - ions. SQUID magnetometry shows a possible transition to long-range magnetic order near 3 K. We measured the magnetization of [Ni(pyz) 2(H 2O) 2](BF 4) 2 as a function ofmore » temperature to search for field-induced phase transitions and briefly report those findings here.« less

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

NASA Astrophysics Data System (ADS)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

Dihydroxo-bridged dimeric Cu(II) system containing sandwiched non-coordinating phenylacetate anion: Crystal structure, spectroscopic, anti-bacterial, anti-fungal and DNA-binding studies of [(phen)(H2O)Cu(OH)2Cu(H2O)(phen)]2L.6H2O: (HL = phenylacetic acid; phen = 1,10-phenanthroline)

NASA Astrophysics Data System (ADS)

Iqbal, Muhammad; Ali, Saqib; Tahir, Muhammad Nawaz; Shah, Naseer Ali

2017-09-01

This paper reports the synthesis, X-ray crystal structure, DNA-binding, antibacterial and antifungal studies of a rare dihydroxo-bridged dinuclear copper(II) complex including 1,10-phenanthroline (Phen) ligands and phenylacetate (L) anions, [Cu2(Phen)2(OH)2(H2O)2].2L.6H2O. Structural data revealed distorted square-pyramidal geometry for each copper(II) atom with the basal plane formed by the two nitrogen atoms of the phenantroline ligand and the oxygen atoms of two bridging hydroxyl groups. The apical positions are filled by the oxygen atom from a water molecule. This forms a centrosymmetric cationic dimer where the uncoordinated phenylacetate ligands serve to balance the electrical charge. The dimers interact by means of hydrogen bonds aided by the coordinated as well as uncoordinated water molecules and phenyl-acetate moieties in the crystal lattice. The binding ability of the complex with salmon sperm DNA was determined using cyclic voltammetry and absorption spectroscopy yielding binding constants 2.426 × 104 M-1 and 1.399 × 104 M-1, respectively. The complex was screened against two Gram-positive (Micrococcus luteus and Bacillus subtilis) and one Gram-negative (Escherichia coli) bacterial strains exhibiting significant activity against all the three strains. The complex exhibited significant, moderate and no activity against fungal strains Mucor piriformis, Helminthosporium solani and Aspergillus Niger, respectively. These preliminary tests indicate the competence of the complex towards the development of a potent biological drug.

Role of Elemental Sulfur in Forming Latent Precursors of H2S in Wine.

PubMed

Jastrzembski, Jillian A; Allison, Rachel B; Friedberg, Elle; Sacks, Gavin L

2017-12-06

The level of hydrogen sulfide (H 2 S) can increase during abiotic storage of wines, and potential latent sources of H 2 S are still under investigation. We demonstrate that elemental sulfur (S 0 ) residues on grapes not only can produce H 2 S during fermentation but also can form precursors capable of generating additional H 2 S after bottle storage for 3 months. H 2 S could be released from S 0 -derived precursors by addition of a reducing agent (TCEP), but not by addition of strong brine to induce release of H 2 S from metal sulfide complexes. The size of the TCEP-releasable pool varied among yeast strains. Using the TCEP assay, multiple polar S 0 -derived precursors were detected following normal-phase preparative chromatography. Using reversed-phase liquid chromatography and high-resolution mass spectrometry, we detected an increase in the levels of diglutathione trisulfane (GSSSG) and glutathione disulfide (GSSG) in S 0 -fermented red wine and an increase in the levels of glutathione S-sulfonate (GSSO 3 - ) and tetrathionate (S 4 O 6 2- ) in S 0 -fermented white wine as compared to controls. GSSSG, but not S 4 O 6 2- , was shown to evolve H 2 S in the presence of TCEP. Pathways for the formation of GSSSG, GSSG, GSSO 3 - , and S 4 O 6 2- from S 0 are proposed.

H2@Scale Workshop Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pivovar, Bryan

2017-03-31

Final report from the H2@Scale Workshop held November 16-17, 2016, at the National Renewable Energy Laboratory in Golden, Colorado. The U.S. Department of Energy's National Renewable Energy Laboratory hosted a technology workshop to identify the current barriers and research needs of the H2@Scale concept. H2@Scale is a concept regarding the potential for wide-scale impact of hydrogen produced from diverse domestic resources to enhance U.S. energy security and enable growth of innovative technologies and domestic industries. Feedback received from a diverse set of stakeholders at the workshop will guide the development of an H2@Scale roadmap for research, development, and early stagemore » demonstration activities that can enable hydrogen as an energy carrier at a national scale.« less

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Novel 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivatives: a patent review (2008 - 2011).

PubMed

Ferreira, Vitor F; da Rocha, David R; da Silva, Fernando C; Ferreira, Patrícia G; Boechat, Núbia A; Magalhães, Jorge L

2013-03-01

The triazoles represent a class of five-membered heterocyclic compounds of great importance for the preparation of new drugs with diverse biological activities because they may present several structural variations with the same numbers of carbon and nitrogen atoms. Due to the success of various triazoles that entered the pharmaceutical market and are still being used in medicines, many companies and research groups have shown interest in developing new methods of synthesis and biological evaluation of potential uses for these compounds. In this review, the authors explored aspects of patents for the 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole families, including prototypes being considered in clinical studies between 2008 and 2011. The triazoles have been studied for over a century as an important class of heterocyclic compounds and still attract considerable attention due to their broad range of biological activities. More recently, there has been considerable interest in the development of novel triazoles with anti-inflammatory, antiplatelet, antimicrobial, antimycobacterial, antitumoral and antiviral properties and activity against several neglected diseases. This review emphasizes recent perspective and advances in the therapeutically active 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivative patents between 2008 and 2011, covering the development of new chemical entities and new pharmaceuticals. Many studies have focused on these compounds as target structures and evaluated them in several biological targets. The preparation of 1H-1,2,3-, 2H-1,2,3-, 1H-1,2,4- and 4H-1,2,4-triazole derivatives brings to light several issues. There is a need to find new, more efficient preparations for these triazoles that take into consideration current issues in green chemistry, energy saving and sustainability. New diseases are discovered and new viruses and bacteria continue to challenge mankind, so it is imperative to find new prototypes for these

Endothelium-derived hyperpolarizing factor and protein kinase G Iα activation: H2O2 versus S-nitrosothiols.

PubMed

Bautista-Niño, Paula K; van der Stel, Marien; Batenburg, Wendy W; de Vries, René; Roks, Anton J M; Danser, A H Jan

2018-05-15

Protein kinase G (PKG) Iα mediates the cyclic guanosine monophosphate-mediated vasodilatory effects induced by NO. Endothelium-derived hyperpolarizing factors (EDHFs), like H 2 O 2 can activate PKGIα in a cyclic guanosine monophosphate-independent manner, but whether this is true for all EDHFs (e.g., S-nitrosothiols) is unknown. Here, we investigated the contribution of PKGIα to bradykinin-, H 2 O 2 -, L-S-nitrosocysteine-, and light-induced relaxation in porcine coronary arteries, making use of the fact that thioredoxin reductase inhibition with auranofin or 1-chloro-2,4-dinitrobenzene potentiates PKGIα. Thioredoxin reductase inhibition potentiated bradykinin and H 2 O 2 , but not L-S-nitrosocysteine or light. The relaxations by the latter 2 and bradykinin, but not those by H 2 O 2 , were prevented by the soluble guanylyl cyclase (sGC) inhibitor 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one. Yet, after S-nitrosothiol depletion with ethacrynic acid, thioredoxin reductase inhibition also potentiated light-induced relaxation, and this was prevented by the Na + -K + ATPase inhibitor ouabain. This indicates that photorelaxation depends on sGC activation by S-nitrosothiols, while only after S-nitrosothiol depletion oxidized PKGIα comes into play, and acts via Na + -K + ATPase. In conclusion, both bradykinin- and light-induced relaxation of porcine coronary arteries depend, at least partially, on oxidized PKGIα, and this does not involve sGC. H 2 O 2 also acts via oxidized PKGIα in an sGC-independent manner. Yet, S-nitrosothiol-induced relaxation is PKGIα-independent. Clearly, PKG activation does not contribute universally to all EDHF responses, and targeting PKGIα may only mimick EDHF under certain conditions. It is therefore unlikely that PKGIα activators will be universal vasodilators. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemical H2O2 biosensor composed of myoglobin on MoS2 nanoparticle-graphene oxide hybrid structure.

PubMed

Yoon, Jinho; Lee, Taek; Bapurao G, Bharate; Jo, Jinhee; Oh, Byung-Keun; Choi, Jeong-Woo

2017-07-15

In this research, the electrochemical biosensor composed of myoglobin (Mb) on molybdenum disulfide nanoparticles (MoS 2 NP) encapsulated with graphene oxide (GO) was fabricated for the detection of hydrogen peroxide (H 2 O 2 ). Hybrid structure composed of MoS 2 NP and GO (GO@MoS 2 ) was fabricated for the first time to enhance the electrochemical signal of the biosensor. As a sensing material, Mb was introduced to fabricate the biosensor for H 2 O 2 detection. Formation and immobilization of GO@MoS 2 was confirmed by transmission electron microscopy, ultraviolet-visible spectroscopy, scanning electron microscopy, and scanning tunneling microscopy. Immobilization of Mb, and electrochemical property of biosensor were investigated by cyclic voltammetry and amperometric i-t measurements. Fabricated biosensor showed the electrochemical signal enhanced redox current as -1.86μA at an oxidation potential and 1.95μA at a reduction potential that were enhanced relative to those of electrode prepared without GO@MoS 2 . Also, this biosensor showed the reproducibility of electrochemical signal, and retained the property until 9 days from fabrication. Upon addition of H 2 O 2 , the biosensor showed enhanced amperometric response current with selectivity relative to that of the biosensor prepared without GO@MoS 2 . This novel hybrid material-based biosensor can suggest a milestone in the development of a highly sensitive detecting platform for biosensor fabrication with highly sensitive detection of target molecules other than H 2 O 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

NASA Technical Reports Server (NTRS)

Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

2011-01-01

Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

The H2A.Z/H2B dimer is unstable compared to the dimer containing the major H2A isoform.

PubMed

Placek, Brandon J; Harrison, L Nicole; Villers, Brooke M; Gloss, Lisa M

2005-02-01

The nucleosome, the basic fundamental repeating unit of chromatin, contains two H2A/H2B dimers and an H3/H4 tetramer. Modulation of the structure and dynamics of the nucleosome is an important regulation mechanism of DNA-based chemistries in the eukaryotic cell, such as transcription and replication. One means of altering the properties of the nucleosome is by incorporation of histone variants. To provide insights into how histone variants may impact the thermodynamics of the nucleosome, the stability of the heterodimer between the H2A.Z variant and H2B was determined by urea-induced denaturation, monitored by far-UV circular dichroism, intrinsic Tyr fluorescence intensity, and anisotropy. In the absence of stabilizing agents, the H2A.Z/H2B dimer is only partially folded. The stabilizing cosolute, trimethylamine-N-oxide (TMAO) was used to promote folding of the unstable heterodimer. The equilibrium stability of the H2A.Z/H2B dimer is compared to that of the H2A/H2B dimer. The equilibrium folding of both histone dimers is highly reversible and best described by a two-state model, with no detectable equilibrium intermediates populated. The free energies of unfolding, in the absence of denaturant, of H2A.Z/H2B and H2A/H2B are 7.3 kcal mol(-1) and 15.5 kcal mol(-1), respectively, in 1 M TMAO. The H2A.Z/H2B dimer is the least stable histone fold characterized to date, while H2A/H2B appears to be the most stable. It is speculated that this difference in stability may contribute to the different biophysical properties of nucleosomes containing the major H2A and the H2A.Z variant.

Dual-Reactable Fluorescent Probes for Highly Selective and Sensitive Detection of Biological H2 S.

PubMed

Wei, Chao; Wang, Runyu; Zhang, Changyu; Xu, Guoce; Li, Yanyan; Zhang, Qiang-Zhe; Li, Lu-Yuan; Yi, Long; Xi, Zhen

2016-05-06

Hydrogen sulfide (H2 S) is an important endogenous signaling molecule with a variety of biological functions. Development of fluorescent probes for highly selective and sensitive detection of H2 S is necessary. We show here that dual-reactable fluorescent H2 S probes could react with higher selectivity than single-reactable probes. One of the dual-reactable probes gives more than 4000-fold turn-on response when reacting with H2 S, the largest response among fluorescent H2 S probes reported thus far. In addition, the probe could be used for high-throughput enzymatic assays and for the detection of Cys-induced H2 S in cells and in zebrafish. These dual-reactable probes hold potential for highly selective and sensitive detection of H2 S in biological systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Formation and Spatiotemporal Progress of the pH Wave Induced by the Temperature Gradient in the Thin-Layer H2O2-Na2S2O3-H2SO4-CuSO4 Dynamical System.

PubMed

Jędrusiak, Mikołaj; Orlik, Marek

2016-03-31

The H2O2-S2O3(2-)-H(+)-Cu(2+) dynamical system exhibits sustained oscillations under flow conditions but reveals only a single initial peak of the indicator electrode potential and pH variation under batch isothermal conditions. Thus, in the latter case, there is no possibility of the coupling of the oscillations and diffusion which could lead to formation of sustained spatiotemporal patterns in this process. However, in the inhomogeneous temperature field, due to dependence of the local reaction kinetics on temperature, spatial inhomogeneities of pH distribution can develop which, in the presence of an appropriate indicator, thymol blue, manifest themselves as the color front traveling along the quasi-one-dimensional reactor. In this work, we describe the experimental conditions under which the above-mentioned phenomena can be observed and present their numerical model based on thermokinetic coupling and spatial coordinate introduced to earlier isothermal homogeneous kinetic mechanism.

Isolation and structures of sulfonium salts derived from thioethers: [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)].

PubMed

Jura, Marek; Levason, William; Reid, Gillian; Webster, Michael

2009-10-07

Two very unusual sulfonium salts, [{o-C(6)H(4)(CH(2)SMe)(2)}H][NbF(6)] and [{[9]aneS(3)}H][NbF(6)], obtained from reaction of the thioethers with NbF(5) in CH(2)Cl(2) solution, are reported and their structures described; the eight-coordinate tetrafluoro Nb(v) cation of the dithioether is obtained from the same reaction.

Non-covalent interactions in 2-methylimidazolium copper(II) complex (MeImH)2[Cu(pfbz)4]: Synthesis, characterization, single crystal X-ray structure and packing analysis

NASA Astrophysics Data System (ADS)

Sharma, Raj Pal; Saini, Anju; Kumar, Santosh; Kumar, Jitendra; Sathishkumar, Ranganathan; Venugopalan, Paloth

2017-01-01

A new anionic copper(II) complex, (MeImH)2 [Cu(pfbz)4] (1) where, MeImH = 2-methylimidazolium and pfbz = pentafluorobenzoate has been isolated by reacting copper(II) sulfate pentahydrate, pentafluorobenzoic acid and 2-methylimidazole in ethanol: water mixture in 1:2:2 molar ratio. This complex 1 has been characterized by elemental analysis, thermogravimetric analysis, spectroscopic techniques (UV-Vis, FT-IR) and conductance measurements. The complex salt crystallizes in monoclinic crystal system with space group C2/c. Single crystal X-ray structure determination revealed the presence of discrete ions: [Cu(pfbz)4]2- anion and two 2-methylimidazolium cation (C4H7N2)+. The crystal lattice is stabilized by strong hydrogen bonding and F⋯F interactions between cationic-anionic and the anionic-anionic moieties respectively, besides π-π interactions.

Electroactive Au@Ag nanoparticles driven electrochemical sensor for endogenous H2S detection.

PubMed

Zhao, Yuan; Yang, Yaxin; Cui, Linyan; Zheng, Fangjie; Song, Qijun

2018-05-26

In this work, a novel and facile electrochemical sensor is reported for the highly selective and sensitive detection of dissolved hydrogen sulfide (H 2 S), attributing to the redox reaction between Au@Ag core-shell nanoparticles (Au@Ag NPs) and H 2 S. Electroactive Au@Ag NPs not only possess excellent conductivity, but exhibit great electrochemical reactivity at 0.26 V due to the electrochemical oxidation from Ag° to Ag + . In the presence of H 2 S, the Ag shell of Au@Ag NPs can be oxidized to Ag 2 S, resulting in the decrease of differential pulse voltammetry (DPV) peak at 0.26 V. The electrochemical sensor exhibits a wide linear response range from 0.1 nM to 500 nM. The limit of detection (LOD) for H 2 S is as low as 0.04 nM. The developed sensor shows significant prospects in the study of pathological processes related to the mechanism of H 2 S production. Copyright © 2018. Published by Elsevier B.V.

Ratiometric fluorescent receptors for both Zn2+ and H2PO4(-) ions based on a pyrenyl-linked triazole-modified homooxacalix[3]arene: a potential molecular traffic signal with an R-S latch logic circuit.

PubMed

Ni, Xin-long; Zeng, Xi; Redshaw, Carl; Yamato, Takehiko

2011-07-15

A ratiometric fluorescent receptor with a C(3) symmetric structure based on a pyrene-linked triazole-modified homooxacalix[3]arene (L) was synthesized and characterized. This system exhibited an interesting ratiometric detection signal output for targeting cations and anions through switching the excimer emission of pyrene from the "on-off" to the "off-on" type in neutral solution. (1)H NMR titration results suggested that the Zn(2+) center of receptor L·Zn(2+) provided an excellent pathway of organizing anion binding groups for optimal host-guest interactions. It is thus believed that this receptor has potential application in sensing, detection, and recognition of both Zn(2+) and H(2)PO(4)(-) ions with different optical signals. In addition, the fluorescence emission changes by the inputs of Zn(2+) and H(2)PO(4)(-) ions can be viewed as a combinational R-S latch logic circuit at the molecular level.