水／离子液体两相体系中出芽短梗霉催化4-氯-乙酰乙酸乙酯不对称还原合成（S）-4-氯-3-羟基-丁酸乙酯

考察了水/离子液体两相体系中出芽短梗霉(Aureobasidium pullulansCGMCC1244)催化4-氯乙酰乙酸乙酯(COBE)不对称还原生成光学活性(S)-4-氯-3-羟基丁酸乙酯((S)-CHBE)的性能,并对反应条件如摇床转速、相体积比、温度、初始底物浓度和pH值等进行了优化.结果表明,在水/1-丁基-3-甲基咪唑六氟磷酸盐体系中,出芽短梗霉催化COBE不对称还原生成(S)-CHBE,在30℃,pH6·6,摇床转速180r/min和不对称反应8h条件下,反应物的转化率、产物ee值和浓度分别达到95·6%,98·5%和47·1g/L.在控制pH值为6·6的情况下,通过分添加底物可有效提高产物(S)-CHBE浓度至75·1g/L.     

Crystal Structure of the Coordination Polymer of Sodium with Hydrazone Derivant of Acetoacetanilide

One new polymer, [Na(NPHSNPAB)(CH_3OH)]_n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ~1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex: C_(17)H_(17)N_4NaO_9S, M_r = 476.39, triclinic system, space group P1, a = 8.8741(18), b = 10.942(2), c = 12.039(2) ?, α = 65.74(3), β = 77.49(3), γ = 84.30(3)o, V = 1040.3(4) ?~3, Z = 2, D_c = 1.521 g/cm~3, λ = 0.71073 ?, F(000) = 492, S = 1.106, R = 0.0614 and w R = 0.1423 for 2945 observed reflections with I 2(I). X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C–H···O, N–H···O, O–H···O, and O–H···S hydrogen bonds. Moreover, sodium(I) center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π···π stacking interaction in the polymer. The average bond distance of the two dicyclic units(3.768 ?) indicated strong π···π stacking interaction. The complex displays greenyellow emission at room temperature.     

二维介孔超薄Cd_(0.5)Zn_(0.5)S纳米片:形成机制及光催化分解水制氢性能（英文）

太阳光驱动的光催化分解水产氢是一种绿色制氢技术,并以氢为载体可实现太阳能向化学能的转化.目前开发高效、稳定的可见光催化剂仍是本领域的研究热点.在各类光催化材料中,Cd_(0.5)Zn_(0.5)S固溶体比Ti O_2及g-C_3N_4具有更优异的光催化产氢活性,但它一般为团聚了的纳米颗粒或纳米微球,表面积小,比表面反应迟缓,从而限制了其实际应用.通常,超薄多孔二维结构光催化剂具有高比表面积,能够为反应物分子与催化剂之间提供大量接触界面并促进传质,此外,特定晶面暴露赋予了其大量不饱和配位表面原子,使反应物分子更容易在催化剂表面吸附活化,提升表面催化反应动力学.本文首先采用乙二胺与水的混合溶液制备了无机有机杂化的硫化锌-乙二胺(记为:Zn S(en)_(0.5)).随后,分别以Zn S(en)_(0.5)为硬模板、以乙二醇为反应介质、氯化镉为镉源,通过溶剂热阳离子交换得到了无机有机杂化的Cd_(0.5)Zn_(0.5)S(en)_x中间产物.最后,将Cd_(0.5)Zn_(0.5)S(en)_x在纯水中进行水热反应脱除晶格内乙二胺分子得到了2D介孔超薄Cd_(0.5)Zn_(0.5)S纳米片.TEM测试发现,纳米片表面存在大量孔洞,其主要源于Cd_(0.5)Zn_(0.5)S(en)_x的相变过程及其晶格内乙二胺分子的逃逸导致的晶格畸变.AFM观察结果表明,最终产物Cd_(0.5)Zn_(0.5)S纳米片厚度约为1.5 nm;其比表面积可达63.5 m~2/g,几乎是相应纳米颗粒的两倍.以三乙醇胺(TEOA)为牺牲剂时,Cd_(0.5)Zn_(0.5)S纳米片的产氢速率达到19.1 mmol·h~(-1)·g~(-1),是相应纳米颗粒的两倍多.即使在纯水中,Cd_(0.5)Zn_(0.5)S纳米片产氢速率仍可达到1395μmol·h~(-1)·g~(-1),超过了目前所报道的未加修饰的光催化剂的活性.其优异的活性源于其独特的结构优势,包括载流子迁移距离的缩短、表面不饱合原子及比表面积的增大.但在纯水中其严重的光腐蚀仍然亟待克服.此外,为进一步增强其活性,通过机械复合的方法得到了Ni Co_2S_4/Cd_(0.5)Zn_(0.5)S二元复合光催化剂,其在TEOA为牺牲剂时制氢速率可达62.2 mmol·h~(-1)·g~(-1),在纯水制氢速率达到2436μmol·h~(-1)·g~(-1).电化学、UPS及EPR分析表明,Ni Co_2S_4与Cd_(0.5)Zn_(0.5)S纳米片间形成了肖特基接触,进一步促进了载流子分离能力,提高了复合物的产氢活性.以本工作为基础,还可制备其他高活性的CdZnS-基功能光催化材料用于太阳能转化或其他领域.     

Synthesis,Crystal Structure and Bioactivity of N-（phenethylcarbamothioyl）cyclopent-1-enecarboxamide

The compound N-(phenethylcarbamothioyl)cyclopent-1-enecarboxamide was synthesized by the reaction of cyclopent-1-enecarbonyl isothiocyanate with phenethylamine in acetone, and its structure was characterized by IR, 1H NMR and X-ray crystal structure determination. The crystal of the title compound belongs to triclinic, space group P1 with a = 6.9500(7), b = 9.4618(9), c = 11.3256(11), α = 71.522(9), β = 81.830(8), γ = 89.237(8)o, Z = 2, V = 698.80(12)3, Dc = 1.304 g/cm3, μ = 0.225 mm-1, F(000) = 292, R = 0.0413 and wR = 0.1073 for 1996 observed reflections with I 2σ(I). Intramolecular N(2)–H(2)···O(1) interactions as well as intermolecular N(2)–H(2)···O(1), N(1)–H(1)···S(1) and C(12)–H(12)···S(1) hydrogen bonds help to stabilize the crystal structure. X-ray diffraction analysis reveals that the structure of the new compound exhibits a one-dimensional infinite chain-like structure. The cytotoxicity of the compound was investigated by MTT assay. The results show that the compound is toxic to A549 tumor cell.     

Synthesis,Crystal Structure and Biological Activity of 2-(1-(3-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl)piperidin-4-yl)-N-isopropyl-1,3-thiazole-4-carboxamide

The title compound 2-(1-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl)piperidin-4-yl)-N-isopropylthiazole-4-carboxamide(C21H22Br Cl N6O2 S,Mr = 536.04) has been synthesized,and its structure was characterized by IR spectra,1H-NMR,13C-NMR,EA,and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic system,space group P/c with a = 15.146(3),b = 11.573(2),c = 26.937(5) ?,β = 103.64(3)°,V = 1839.0(6) ?3,Z = 4,Dc = 1.557 g/cm3,μ(Mo Ka) = 0.71073 mm-1,F(000) = 2192,R = 0.0601 and w R = 0.1392.There exist one intramolecular hydrogen bond at N–H···N and four intermolecular weak interactions at O(2)···H(1),Cl(1)···H(12),O(1)···Cl(1) and S(1)···O(2).Bioassay results indicated that the title compound had good fungicidal and antiviral activities against tobacco mosaic virus.     

Syntheses,Crystal Structures,SHG Response and Purple Luminescent Property of Tetra(isothiocyanate) Mn(Ⅱ) and Substituted Benzyl Triphenylphosphonium Cations

Researches on multifunctional molecular materials with both nonlinear optical activity and fluorescence properties have received much interest in molecular chemistry since they have wide application prospects. Here a novel ionic compound 2(BPP)~+·[Mn(NCS)_4]~(2-)(1) was synthesized via the assembly of benzyltriphenylphosphorus chloride, isothiocyanate and manganese chloride, which displays both strong SHG response and purple luminescence. Compound 1 belongs to monoclinic system and crystallizes in Cc space group. X-ray single-crystal diffraction analysis shows that Mn~(2+) ions are tetra-coordinated with N atoms of four NCS-ions through forming a distorted tetrahedral configuration. The anion Mn(NCS)_4~(2-) forms a 1D chain structure through strong S···S interaction. At the same time, there are abundant C–H···S and π···π interactions, which further accumulate into a three-dimensional supramolecular structure. Solid-state fluorescence studies show that the complex 1 has strong purple fluorescence with emission wavelength of 396 nm under excitation wavelength 248 nm. In particular, the second harmonic generation(SHG) measurements show that compound 1 has nonlinear optical activity and its SHG response is 2.25 times that of standard potassium dihydrogen phosphate(KDP). This multifunctional molecular material with SHG response and purple fluorescence is of great significance for the development of new metal organic complexes with potential application prospects.     

Analysis of Intra-and Intermolecular Hydrogen Bonds and Quantum Chemical Calculations on 1-(3-Fluorobenzoyl)-3-(4-trifluoromethylphenyl) thiourea

1-(3-Fluorobenzoyl)-3-(4-trifluoromethylphenyl)thiourea, C_(15)H_(10)F_4N_2OS, has been synthesized firstly and determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system, space group C2/c with a = 31.87(3), b = 7.705(9), c = 12.591(14) ?, b = 106.06(2)°, V = 2971(6) ?~3, Z = 8, D_c=1.530 g·cm~(–1), F(000) = 1392, m = 0.266 mm~(–1), S = 1.06, the final R = 0.070 and w R(I 2s(I)) = 0.249. The crystal structure revealed that the carbonyl thiourea unit in the determined compound was mostly planar due in part to the formation of intramolecular N–H···O=C and C–H···S=C hydrogen bonds that form two S(6) rings. The intermolecular contacts of the crystal structure have been preformed based on the Hirshfeld surface and their associated 2D fingerprint plots. In the packing diagram of the synthesized compound, the C=S group formed two types of intermolecular hydrogen bonds by the H–N(C=O) group and the H–C of the phenyl ring, respectively, and they formed R2 2(8) and R_2~2(14) ring motifs, respectively. The crystal packing form was also stabilized by the intermolecular hydrogen bonds C–H···O(1–x, y, 0.5–z) with the R_2~2(10) ring motifs. In addition, supramolecular layers sustained by π-π stacking interactions(between the C(2)~C(7) rings with the C(10)~C(15) rings) are formed in the crystal structure of the title compound. The electronic and reactivity were assessed by the natural bond orbital(NBO) analysis in this study.     

Synthesis,Crystal Structure and Antibacterial Activity of Dibenzyl Dithiocarbamate Bismuth Complex

A new complex, {Bi(Ⅲ)[S2CN(CH2C6H5)2]3}2·2CH3CN, was synthesized and characterized by elemental analysis, IR, TG, 1H NMR and X-ray single-crystal diffraction. The complex crystallizes in the triclinic system, space group P1, with a = 12.705(6), b = 13.430(6), c = 15.489(12) , α = 102.135(12), β = 99.649(12), γ = 111.521(9)°, Z = 1, V = 2315(2) A3, Dc = 1.531 g·cm-3, F(000) = 1068, μ = 4.116 mm-1, the final R = 0.0559, w R = 0.1069 and S =1.056. The coordinated geometry of Bi(Ⅲ) with six sulfur atoms from three ligands is a distorted pentagonal pyramidal configuration, and the structural system is formed by weak interactions of Bi···S between two molecules. The complex was valued for its antibacterial activity by agar-streak method. It was found that the complex is weakly active against three of the five tested bacterial organisms.     

A New Zn(Ⅱ) Coordination Polymer Constructed by 1,4-Benzenedithiolate Dianion: [Zn(SC_6H_4S)(1,3-DPA)]_n

A new one-dimensional polymer, [Zn(SC6H4S)(1,3-DPA)]n(1, SC6H4 S = 1,4-benzenedithiolate and 1,3-DPA = 1,3-diaminepropane), has been synthesized and characterized by elemental analysis, PXRD, IR spectra, and single-crystal X-ray diffraction. The complex crystallizes in triclinic system, space group P1, with a = 6.7119(1), b = 9.0230(2), c = 10.4943(2) ?, α = 69.288(1), β = 75.848(1), γ = 81.513(1)o, V = 575.123(19) ?3, Dc = 1.615 g/cm3, Z = 2, F(000) = 288; the final S = 1.070, R = 0.0234, and w R = 0.0551. The compound consists of an infinite zigzag chain formed by [Zn(1,3-DPA)]2+ units joined by SC6H4 S ligands. Each chain interacts with neighboring chains via weak N–H···S hydrogen bonds to form an extended three-dimensional(3D) supramolecular network. The thermal and photoluminescent properties of 1 have also been investigated.     

一种新的反应路径实现高体积能量密度的锂硒电池

作为硫(S)的同族元素,硒(Se)在化学和电化学性质上与硫类似。应用于二次锂金属电池时,Se作为正极活性物质,通过Se+2Li?Li2Se的电化学转化进行可逆地锂化和脱锂,具有较高的理论比容量(675 mAh·g^?1)。虽然其理论比容量低于S(1672 mAh·g^?1),但是Se的密度较大,从而其理论体积比容量(3253 mAh·cm^?3)与S(3467 mAh·cm^?3)相当1。另外,Se具有远高于S的电导率(Se:≈10?5 S cm^?1;S:≈10?30 S·cm^?1),以及与商用碳酸酯电解液更好的兼容性2–4,这些特性使得锂硒(Li-Se)电池体系有望兼具高功率和体积能量密度。