The genesis of H2S in the Weiyuan Gas Field, Sichuan Basin and its evidence

The Sinian Dengying Formation gas pool in Weiyuan is the oldest large-scale sulfur-bearing gas field in China, which has a H2S content ranging from 0.8% to 1.4%. The Cambrian Xixiangchi Formation gas pool discovered recently above the Dengying Formation contains gas geochemical behaviors similar to those of Dengying Formation but different in sulfur isotopes of H2S. Investigations show that though these two Sinian and Cambrian gas pools are separate ones, they share the same Cambrian source rock. The higher dry coefficient, heavier carbon isotopes, sulfur isotopes of sulfide, lower filling of gas pools, formation water characteristics, reservoir properties and H2S distribution, indicate that H2S in both the Sinian and Cambrian gas pools originates from TSR. The sulfur isotopes of sulfates have shown that H2S was formed in respective pools, namely hydrocarbons charged into the pools reacted with the Dengying Formation and the Xixiangchi Formation gypsum （TSR）, respectively, to form H2S. Compared with sulfur isotopes of sulfates in each pool, δ^34S values of H2S are 8‰ lighter for the Dengying Formation pool and 12‰ lighter for the Xixiangchi Formation pool, respectively, which is attributed to the difference in temperatures of TSR occurrence. The reservoir temperature of the Xixiangchi Formation pool is about 40℃ lower than that of the Dengying Formation pool. Temperature plays a controlling role in both the sulfur isotopic fractionation and amounts of H2S generation during TSR.     

Investigation on the coordinate structures of the rare earth metal complexes with edta and cydta ligands

0　IntroductionThegreatattentionhasbeenpaidtorareearthorradioactiverareearthmetalcomplexesfortheirvariousbiologicactivi ties[1 3] .Forexamples,theradioactiverareearthmetal1 53SmⅢ com plexeswerewidelyusedfortumourtherapyofbrain ,liver,lung ,heartandbonetissues[4 5] ;forrareearthmetalEuⅢandTbⅢemitinguniquefluorescence ,theircompoundswereappliedfordiagnosesofvariousdiseases[6 ,7] ;forrareearthmetalGdⅢcontainingthemosthigh spinsingleelectrons,itscomplexeswereusuallyusedforcontrastagentsofmag…     

Enolate chelating N-heterocyclic carbene complexes of Fe(II): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(II) complexes of L12Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(II) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same com- plexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.     

牛蹄塘组页岩气储层有机质微生物来源的证据

针对牛蹄塘组页岩气储层中有机质来源的问题,从微体古生物化石和有机地球化学两方面开展了研究。采
用环境扫描电镜–能谱系统（ESEM – XEDS）对岩芯中的微生物化石形态和化学组成进行了研究;此外,还采用气相色
谱–质谱法（GC – MS）对岩芯抽提物进行了检测。结果表明,牛蹄塘组页岩中发现的微生物化石C 和N 元素含量较
高（大于30%）,从外部形态大致可将其分为3 类：同心环状结构,表面光滑的球体以及细胞壁开口的球体。岩芯抽提
物检测结果表明,牛蹄塘组页岩nC12 ∼ nC32 的正构烷烃均有检出,且具有低碳数（主峰碳nC16）偶碳优势;此外,抽提
物中还检出了含量较高的类异戊二烯烃,包括,姥鲛烷、植烷和角鲨烯。这些微生物化石的发现和有机地球化学组成
特征为晚震旦-早寒武世扬子浅海微生物的繁盛和牛蹄塘组烃源物质的微生物起源提供了有力的证据。     

Synthesis, structure and ethylene polymerization behavior of titanium complexes [C3H6（N = CH-Ar-O）2]TiCl2

Early transition metal catalysts containing twophenoxy-imine ligands, called FI catalysts which havevery high potential to become a new generation of olefinpolymerization catalysts, are new-type catalysts whichhave attracted much attention in recent years[1—3]. Many ofthem display activities comparable to those of the metal-locene catalysts and, in some cases, behave as living po-lymerization catalysts of α-olefins. Brookhart and Gibsonet al.[4,5] recently reported separately series of Schi…     

Simulation for the primary electronic donor of photosystem IIin vitro

Histidine coordinated to Chi a is a distinct characteristic of Chl ain vivo. By using histidine analogue of 1-methylimidazole (C₄H₆N₂2) and measuring the UV/vis absorption, CD and MCD spectra of the interaction between C₄H₆N₂ and Chl a in CCI₄, we have obtained that: (i) In pure CCl₄ solvent, Chl a molecule is in five-coordinate state, and two Chl a molecules form an asymmetric compact-dimer with strong coupling interaction. We propose that the two Chl a molecules are connected by two unequally coordinated Mg-O bonds (the two oxygen atoms come from the C=O of C13¹ keto and C17 ester, respectively); (ii) when the molar ratio of C₄H₆N₂/Chl a is 0.5 or 1 (corresponding to 2Chl a · 1C₄H₆N₂ and 2Chl a · 2C₄H₆N₂, respectively), significant changes have been observed in the absorption, CD and MCD spectra, which indicate that the Chl a remains in dimer form, but the coupling interaction between them reduces greatly. We postulate that C₄H₆N₂ replaces the ligation of C=O of C17 ester and C13¹ keto to Mg atoms sequentially. The two Chl a molecules linked by two weakly interacted Mg…O bonds form a relaxed-dimer. The structure of the model is essentially similar to that of the primary electronic donor, P₆₈₀, of photosystem II in high plants and algae.     

Crystal structure and photoelectricity property of Fe(II/III) coordination supermolecules

Three new mixed-ligand Fe(II/III) complexes [Fe₂(μ₂–btec)(μ₂–H2btec)(phen)₂(H₂O)₂]_n (1), [Fe2(btec) (phen)₂(H₂O)₄] (2), and {[Fe(o-pha)(phen)(H₂O)]•H₂O}_n (3) (phen=1,10-phenanthroline, o-H₂pha=o-phthalic acid, H₄btec=1,2,4,5-benzenetetracarboxylic acid) have been hydrothermally synthesized and detected by single crystal X-ray diffraction, showing that complexes (1) and (2) are both bridged by the betc⁴⁻ ligands to form 1D chain and dinuclear structure and complex (3) is bridged by the o-pha groups to form 1D chain structure. The coordinated modes of the carboxyl groups adopt μ₂-η¹η¹ηη¹η¹ and μ₂-η²η¹ respectively in com-plexes (2) and (3). The betc groups in complex (1) show two different coordinated modes: μ₂-η¹η¹η¹η¹ and μ₂-η¹η¹. In addition, the hydrogen bonds and π…π type interactions make the complex molecule further connect to three-dimensional and two-dimensional networks respectively. These complexes are detected by IR, UV-Vis-NIR and surface photovoltage spectrum (SPS). The SPS of complexes (1)–(3) indicate that there are positive SPV responses in the range of 300–600 nm and show p-type semiconductor characteristic. Because the structure, the valence and the coordinative environment of the Fe ions are all different in the three complexes, the intensity, position and the number of the response bands are different obviously. The results of SPS are corresponding with UV-Vis-NIR spectra.     

Vermicular fossils in the Early Cambrian Xidashan Formation in the Quruqtagh region of Xinjiang, China

Large amounts of vermicular fossils and a minor amount of sponge animal fossils have been found in the Early Cambrian Xidashan Formation in the region of Quruqtagh, Xinjiang. Vermicular fossils are generally more than 50 mm long and 0.3?1.4 mm wide; their wrinkled lamellae are microfine with 3?10 pieces within the length of every each millimeter. The fossils are considered to be Sabellidites cambriensis Sokolov (1965). The Xidashan Formation is the highest stratum in which Sabellidites occur, as has been so far reported.     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

Theoretical investigation on mechanism of dissociation of furan

Conclusion  According to the calculated results for the dissociation mechanism of C₄H₄O⁺, we come to a conclusion as follows:

Spectroscopic characterization and stereodynamics of ferrocenylselenoethers Pt(II), Pd(II), Rh(III) complexes

Ferrocenlyselenides (C₅H₅FeC₅H₄SeR, Fe(C₅H₄SeR)₂) and their complexes of metal Pt, Pd, Rh (R=undecenyl, benzyl, phenyl) have been prepared. The spectroscopic characterization has been examined by mass spectrum, XPS, IR and NMR. IR, NMR spectra of C₅H₅Fe C₅H₄Se (CH₂)₉ CH=CH₂PtCl₂ reveal C=C double-bond in Fe(C₅H₄Se (CH₂)₉CH=CH₂)₂ Pt Cl₂ is free because of binding with Pt(II). The results obtained from^H,¹³C and⁷⁷Se NMR indicate that invertomers ofmeso anddl species existence. The ratio ofmeso/dl for BUnSeF Pt is ca 70/30, whereas four and three invertomers for BUnSeF Pt and BBSeFPd have been clearly observed from¹H NMR spectra. Tian Bingshou: born in Feb. 1938, Associate professor     

Structure and magnetism of carboxylate/EO-azido-mixed-ligands bridged CuII systems

Using two structurally related benzoates bearing different H-bond acceptors as co-ligands, three new azido-Cu^Ⅱ compounds, [Cu（L^1）（N3）（H2O）]n（1）, [Cu（L^1）（N3）（MeOH）]n （2）, and [CuL^2HL^2（N3）3（H2O）]n（3） （HL^1 = 4-nitrobenzoic acid; HL^2= 2-phenyl-4-quinolinecarboxylic acid）, have been synthesized and structurally characterized. 1 is a carboxylate/EO-azido bridged copper chain, forming 3D structure by H-bonds, and 2 has a similar chain structure as 1 but forming a 2D structure by H-bonds, while 3 is a 3D supramolecular network with ternary center H-bonds. Magnetic study indicates that domain ferromagnetic coupling interactions were found to exist in complexes 1 and 3.     

Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Coordination behavior between zinc salts and L-α-methionine

The solubility properties of ZnCl\-2/ZnAc\-2/ZnSO\-4_Met_H\-2O systems at 25℃ in the whole cocentration range have been investigated by phase equilibrium method. The results indicate that ZnAc\-2 and ZnSO\-4 systems are both simple systems, which do not exist any compound; there are 2 complexes formed in ZnCl\-2 system: Zn(Met)Cl\-2 and Zn(Met)\-2Cl\-2·2H\-2O. Under the direction of phase equilibrium result, 2 solid complexes have been prepared in water and characterized by chemical analysis, IR, X_ray diffraction. Their combustion energies have also been determined by means of a RBC_type_1 rotating_bomb calorimeter, and their standard enthalpies of formation, Δ f, coor(s)H O-, have been calculated which are (-828.32±3.00) kJ·mol -1 and (-1 117.08±6.15) kJ·mol -1, respectively.     

Pu(H2O)53+和Pu(H2O)54+ 团簇的相对论密度泛函研究

用TPSSTPSS密度泛函方法, Pu离子和H₂O分子分别采用相对论有效原子实势(RECP)和6-31g基组, 研究了Pu(H₂O)₅³⁺和Pu(H₂O)₅⁴⁺ 团簇溶剂化和非溶剂化效应中的几何结构及紫外可见吸收光谱. 计算结果表明: 水溶剂环境对Pu(H₂O)₅³⁺及Pu(H₂O)₅⁴⁺ 团簇的几何结构影响都比较明显. NBO电荷分析表明水分子与钚离子之间没有直接的电荷转移. 所研究团簇的未配对电子都占据5f轨道. 在气相及水溶剂环境下, 所研究团簇的紫外可见吸收光谱存在较大差距. 主要的吸收峰大都源于f电子之间的跃迁.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

Characteristics of electric double layer in different aqueous electrolyte solutions for supercapacitors

Aiming to find suitable electrolytes for electric double layer capacitor (EDLC),the relationship between the formation velocity of electric double layer and the specific capacitance in different electrolyte (H 2 SO 4,KOH,KCl,NH 4 Cl,and LiOH) solutions was investigated by cyclic voltammetry and AC impedance with varying frequency and potential,which was also analyzed based on Stern model and Gouy-Chapman diffusion layer model.It shows that the capacitance is positively correlated with the formation velocity of the electric double layers,which is affected by the type of ions applied,the concentration of the electrolyte solution,and the potential and frequencies as well.The electrolyte solutions of 6 mol/L KOH and 4 mol/L H 2 SO 4 provide the largest capacitance,reaching 214 and 186 μF/cm 2,respectively.Both 6 mol/L KOH and 4 mol/L H 2 SO 4 solutions are suitable electrolytes for EDLC applications using Pt as electrodes.     

Preliminary Mo isotope data of Phanerozoic clastic sediments from the northern margin of the Yangtze block and its implication for paleoenvironmental conditions

Mo isotopes along with Nd isotopes and other geochemical characteristics of the Phanerozoic clastic sediments from the northern margin of the Yangtze block were analyzed by MC-ICP-MS and some other techniques, spanning the period from Cambrian to Jurassic. The δ 98Mo values and εNd(t ) in these sedimets were observed to exhibit a large range of variation (?0.65‰―+1.87‰, ?1.46―?10.90, respec-tively). Specifically, the sample from Late Permian Maokou Formation has relatively positive values in both δ 98Mo and...     

Synthesis,characterization and photoluminescence of aluminum <Emphasis Type="Italic">N</Emphasis>-aryloxo functionalized <Emphasis Type="Italic">β</Emphasis>-ketoiminate complexes

The synthesis, characterization and luminescent properties of aluminum complexes containing a dianionic N-aryloxo functionalized β-ketoiminate ligand are presented. 4-(2-Hydroxy-5-R-phenyl)imino-2-pentanone (R = Me, L¹H₂; R = tert-butyl, L²H₂) ligands reacted with AlEt₃ in tetrahydrofuran to give the aluminum complexes (L¹AlEt)₂ (1) and (L²AlEt)₂ (2) in reasonable isolated yields. X-ray diffraction revealed that complexes 1 and 2 have solvent-free centrosymmetric dimeric structures, and each aluminum center has distorted trigonal bipyramidal geometry. At room temperature, complexes 1 and 2 exhibit blue photoluminescence in acetonitrile with maximum emission wavelengths of 419 and 413 nm, respectively.