Synthesis and Spectral Properties of Mixed-Ligand Complexes of Lanthanide Perchlorate with Bis-(phenylsulfinyl)ethane and Organic Lewis Bases

Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spectral (IR, UV Visible) data. The complexes were Ln(bphse) 2(bipy)(ClO 4) 3· n H 2O and Ln 2(bphse) 3(phen) 2(ClO 4) 6·H 2O(where Ln=Nd, Eu and Gd; n =0～2). IR spectral data confirmed that the lanthanide ions were coordinated by oxygen atoms from bphse and nitrogen atoms from phen or bipy. Exitation and emission spectra of Eu complexes were measured and discussed.

Synthesis and Crystal Structure of a Cadmium Coordination Polymer with Dicyanamide and 1,2-Bis(1,2,4-triazol-1-yl)ethane

The new cadmium（N） coordination polymer [Cd（bte）2（dca）2]n 1 （bte = 1,2-bis（1,2,4- triazol-1-yl）ethane, dca = dicyanamide） was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 8.7148（15）, b = 8.6142（17）, c = 15.204（3） A, fl= 92.100（10）°, V= 1140.6（4） A3, Z= 2, Mr = 572.87, Dc= 1.668 g/cm3, F（000） = 572, /t = 1.004 mm-l, the final R = 0.0654 and wR = 0.1429 for 1737 observed reflections （I 〉 2σ（I））. The cadmium atom is coordinated equatorially by four nitrogen atoms from four bte ligands and axially by two nitrogen atoms from two dca anions to adopt a distorted octahedral geometry. Each bte molecule bridges two cadmium（II） atoms. Two strands of bte molecules are wrapped around each other, and held together by cadmium（H） atoms. 1 Forms a double chain structure containing eighteen-membered Cd2（bte）2 rings.

Two Cobalt(II) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine:Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL_2]X·H_2O (X = ClO_4^-, N

The reactions of Co（C1O4）2·6H2O and Co（NO3）2.6H2O with the di-Schiff base ligand N,N＇-bis-（1-benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine （LA） in ethanol have been investigated. The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2]（ClO4）E·H2O 1 and [CoL2]（NO3）E·H2O 2 as isolatable products （L= N-（1- benzimidazo-2-yl-ethylidene）-ethane-1,2-diamine）, where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA. Both complexes were characterized by X-ray crystallography. Crystal data for complex 1： monoclinic, space group P21/c, a = 11.9214（10）, b = 23.5828（17）, c = 14.0387（12）A, β = 135.219（4）°, C22H30Cl2CoN8O9, Mr = 680.37, V = 2780.1（4） A^3 ,Z = 4, Dc = 1.625 g/cm^3,μ（MoKa） = 0.876 mm^-1, F（000） = 1404, the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections （I 〉 2σ（I））. Crystal data for complex 2： monoclinic, space group P21/c, a = 18.2162（16）, b = 10.0610（6）, c = 18.593（2）A, β = 130.099（3）°, C22H30CoN10O7, Mr = 605.49, V = 2606.5（4） A3 Z = 4, Dc = 1.543 g/cm^3,μ（MoKa） = 0.722 mm^-1, F（000） = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections （I 〉 2σ（I））. X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere. In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4^- （or NO3^-） groups to form a 3D framework. In complex 2, the strong π-π interactions increase the stability of the structure.

Studies of Disulfoxide Complexes of Lanthanide Ⅴ.Lanthanide Perchlorate Complexes with Meso-bis(phenylsulfinyl)ethane

Lanthanide perchlorate complexes with meso-bis（phenylsulfinyl）ethane（meso-BPhSE）of type[LnL3-ClO4]（ClO4）2,where Ln=La～Nd,Sin,Gd～Ho,Tm～Lu,have been prepared and characterized by elementalanalysis,electrical conductance,infrared and electronic spectra,magnetic moment measurement and thermalanalysis.Meso-BPhSE acts as a neutral ligand which combines with lanthanide ion through oxygen atom ofdisulfoxide moieties.In all complexes,except that of Ho,meso-BPhSE does not behave as a complete bidentatechelate but does coordinate,at least partially,as a monodentate ligand.For the Ha complex all meso-BPhSEacts as bidentate ones.

Studies on the extraction of uranium (VI) by bis (hexylsulfinyl) ethane

The extraction of uranium (Ⅵ) by bis(hexylsulfinyl)ethane(BHxSE) in nitric acid aqueous solution hasbeen investigated. The extracted species appeared to be UO2(NO3)2@2BHxSE. Influences of nitric acid concentration,NaNO3 concentration, Na2C2O4 concentration and temperature on the extraction equilibrium were investigated andthe thermodynamic functions of the extraction reaction were obtained.

Kinetics on Thermal Decomposition of Iron(III) Complexes of 1,2-Bis(Imino-4’-Antipyrinyl)Ethane with Varying Counter Anions

A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.

Ruthenium Bisphosphine Catalyst on Functionalized Silica: Novel Efficient Catalyst for Carbon Dioxide Hydrogenation to Formic Acid

A novel efficient catalyst for the hydrogenation of carbon dioxide to formic acid ruthenium bisphosphine on functionalized silica was in situ synthesized, affording turnover frequency （TOF） of 1190 h^-1 at 100% selectivity under 80℃ with total pressure of 16.0 MPa. The catalyst can be separated from the reaction mixture easily and reused with moderate loss of activity.

Syntheses,Structures and Luminescent Properties of Cd(Ⅱ)/Zn(Ⅱ) Coordination Polymers Based on the Flexible 4-Substituted Bis(1,2,4-triazole) Ligand

Two new cadmium（II） and zinc（II） coordination polymers, {[Cd（btre）0.5- （mip）（H2O）2]·H2O}n （1） and [Zn（btre）（mip）]n （2）, were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions （btre = 1,2-bis（1,2,4-triazol-4-yl）ethane, H2mip = 5-methyl-1,3-benzenedicarboxylic acid）. Complex 1 belongs to the triclinic system, P space group, with a = 8.9830（6）, b = 10.0579（6）, c = 10.2479（9） , α = 98.837（6）, β = 115.975（8）, γ = 106.370（6）°, V = 756.30（11） 3 and Z = 2; complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.0332（3）, b = 14.9947（7）, c = 15.9689（7） ？, β = 97.1170（10）°, V = 1671.12（13） ？3 and Z = 4. Compounds 1 and 2 based on the same N/O-donor ligands show different structures. The one-dimensional chains of 1 are further linked by hydrogen bonding and π-π interactions to yield a three-dimensional supramolecular structure. The two-dimensional （6,3） networks of 2 are further extended into a 3D framework via π-π interactions. Thermal stabilities and luminescence of 1 and 2 were investigated.

Synthesis,Spectra,X-ray Diffraction and Thermal Studies of New Zn(Ⅱ) Compounds Based on Dibenzoylmethane

Two new zinc（Ⅱ） compounds with dibenzoylmethane and N-donor ancillary ligands,[Zn（μ-pyz）（dbm）_2]_n（1） and [Zn（dbm）_2（μ-bpe）Zn（dbm）_2]（2）（Hdbm = dibenzoylmethane,pyz = pyrazine and bpe = 1,2-bis（4-pyridyl）ethane）,have been prepared and characterized using elemental analysis,IR,~1H NMR and 13 C NMR spectroscopy,and studied by thermal gravimetric analysis as well as single-crystal X-ray diffraction. The crystal and molecular structures of 1 and 2 have been solved by X-ray diffraction and they turned out to be a one-dimensional coordination polymer with linear dispositions of metal atoms and binuclear compound,respectively. These one-dimensional polymers are further connected to form a 3D supramolecular network by C–H···O（only in 2） and π-π interactions.

Synthesis, Reactions and Characterization of 1,1’-(1,4-Phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(ethan-1-one)

Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.

抑制IP3R-Ca^(2+)途径对对乙酰氨基酚所致肝损伤及其线粒体内质网结构偶联的影响

目的探讨抑制肌醇-1,4,5-三磷酸受体(IP3R)-Ca^(2+)途径对对乙酰氨基酚(APAP)所致肝损伤及其线粒体内质网结构偶联(MAMs)的影响。方法40只SPF级雄性C57BL/6小鼠随机分为正常对照组、模型组、IP3R抑制剂(2-APB)组、钙离子螯合剂(BAPTA-AM)组,每组10只。模型组、2-APB组、BAPTA-AM组单次腹腔注射APAP(300 mg/kg)。注射APAP前30 min,2-APB组腹腔注射2-APB(20 mg/kg),BAPTA-AM组腹腔注射BAPTA-AM(2.5 mg/kg)。腹腔注射APAP 24 h后处死各组小鼠。测定血清丙氨酸氨基转移酶(ALT)、天门冬氨酸氨基转移酶(AST)水平;HE染色观察肝脏病理变化;透射电镜观察肝细胞中线粒体、内质网结构及MAMs变化;测定肝组织匀浆中的Ca^(2+)水平;Western blot测定肝组织中线粒体融合蛋白1(MFN1)、线粒体融合蛋白2(MFN2)、1,4,5-三磷酸肌醇受体1(IP3R1)、葡萄糖调节蛋白75(GRP75)蛋白表达水平。结果与正常对照组相比,模型组小鼠血清ALT及AST水平有所升高(P<0.01),肝脏组织病理学可见肝细胞排列紊乱,并出现肝细胞变性、小叶中心性坏死;透射电镜示线粒体嵴断裂、消失,内质网肿胀断裂,MAMs数量增加;肝组织匀浆中Ca^(2+)含量增加(P<0.01);MFN1、MFN2蛋白表达降低(P<0.01),IP3R1及GRP75蛋白表达增加(P<0.01)。与模型组相比,2-APB组和BAPTA-AM组小鼠血清ALT、AST水平下降(P<0.01),肝脏病理变化明显改善,MAMs减少,肝组织匀浆中Ca^(2+)含量减少(P<0.01),MFN1、MFN2的蛋白表达水平上调(P<0.01),IP3R1及GRP75蛋白表达降低(P<0.01)。结论抑制IP3R-Ca^(2+)途径可以保护APAP所致的肝损伤,其机制与降低肝脏Ca^(2+)水平、减少MAMs数量、调节MAMs相关蛋白的表达有关。

KSCN-双(正-辛基亚磺酰)乙烷-乙酸丁酯体系萃取钯的研究

研究了KSCN存在条件下双 (正 辛基亚磺酰 )乙烷 (简称BOSE) 乙酸丁酯体系对钯的萃取。当盐酸浓度高于 1mol/L时 ,KSCN BOSE/乙酸丁酯体系对钯的萃取率高于 99% ,说明以SCN-作为无机离子配体 ,BOSE作萃取剂时对Pd(Ⅱ )有强萃取作用。斜率法测定萃合物的化学式组成为Pd∶BOSE∶SCN-=1∶2∶2。测定萃取前后水相和有机相的电子吸收光谱 ,特征吸收峰的移动表明生成了新的萃合物。分别测定KSCN、BOSE和萃合物的红外光谱 ,表明SCN-和BOSE均是由硫原子与钯配位。

铽(Ⅲ)的双亚砜配合物的荧光性质

测量了双（苯基亚砜）乙烷（ｂｐｈｓｅ），双（苯基亚砜）丙烷（ｂｐｈｓｐ），双（苯基亚砜）丁烷（ｂｐｈｓｂ）和铽（Ⅲ）的配合物的吸收光谱和荧光光谱及其寿命．讨论了配体性质、阴离子及镧系离子对铽（Ⅲ）配合物荧光性能的影响．

内燃机用阻燃型空气过滤纸的研制

实验探讨了以十溴二苯乙烷为主体的溴-锑协同阻燃体系中溴-锑元素质量比对空气过滤纸阻燃效果的影响,结果表明,二者最适质量比为3∶1。在此比例下,进一步研究了阻燃剂用量对空气过滤纸阻燃性能、力学性能以及透气性的影响,结果显示,阻燃剂留着率为25%时,阻燃性能达到GB/T14656—1993要求,此时挺度提高了约20%,但耐破度和透气度分别下降了约11%和10%。

不锈钢表面功能性硅氧烷膜的制备与性能研究

采用双功能性1,2-二(甲氧基二乙氧基硅基)乙烷为原料,在奥氏体304不锈钢表面制备了有机-无机杂化硅氧烷膜(BMBSE),并通过FTRA-IR、SEM、EIS、动电位极化曲线及接触角测量仪对薄膜的性能进行测试和表征。结果表明,致密完整无缺陷的双功能性BMBSE硅氧烷通过形成Si—O—Fe化学键与不锈钢基体结合;硅烷膜与水的接触角为94.2°,具有一定的疏水性;在55%的溴化锂溶液中的动电位极化曲线和EIS测试表明,双功能性硅氧烷BMBSE膜极大的改善了不锈钢的耐腐蚀能力。同时,给出了不锈钢表面双功能性硅氧烷BMBSE膜的阻抗模型以及相关拟合参数。

双(十二烷基亚磺酰)乙烷溶剂萃取钯及其机理的研究

本文研究用双(十二烷基亚磺酰)乙烷(BDSE)萃取钯的性能,在KI存在下从9mol/L盐酸介质中用含有BDSE的氯仿能定量萃取钯。有机相的钯可被硫脲或氨溶液反萃继之用TMK-Triton X-100光度法测定。研究了萃取的最佳条件及干扰情况。斜率法测得萃合物组成为Pd:I:BDSE=1:2:1,红外光谱证实萃合物中BDSE的二个亚砜以硫原子与钯配位。萃合物为异配位体络合物。提出了选择性萃取分离钯的新方法。

1，2─双（二乙基膦基）乙烷的合成

以二乙基氯化膦为原料，经乙炔化及加氢两步合成了１，２－双（二乙基膦基）乙烷，产率超过文献值。用红外光谱和核磁共振波谱分别测定了结构。

离子液体催化邻二甲苯与二氯乙烷的烷基化反应性能

报道了无水AlCl3 与季铵盐形成的离子液体催化邻二甲苯与 1,2 -二氯乙烷烷基化反应 ,反应产物为1,2 -双 (3,4 -二甲基苯基 )乙烷。短碳链季铵盐氯代乙基吡啶或氯代丁基吡啶与无水AlCl3 形成的离子液体具有与产物易于分离的优点 ,1,2 -双 (3,4 -二甲基苯基 )乙烷的分离产率为 4 0 %～ 6 0 %。催化剂重复使用 4次 ,目标产物的产率和纯度没有明显的变化。长链季铵盐溴代十六烷吡啶和十六烷基三甲基溴化铵与无水AlCl3 形成的离子液体溶解在反应物和产物中 ,使得产物与催化剂较难分离 。

双(正辛基亚磺酰)乙烷萃取铂的性能和机理

用正辛基硫醇与１，２－二溴乙烷合成双（正辛基硫代）乙烷，继而制得双（正辛基亚磺酰）乙烷（ＢＯＳＥ）．研究题示试剂用于溶剂萃取铂的性能和机理．实验表明，在ＫＩ存在下２～６ｍｏｌ／Ｌ盐酸介质，ＢＯＳＥ—乙酸丁酯能定量萃取铂（Ⅳ）．研究萃取与反萃取的最佳条件，ＩＣＰ—ＡＥＳ分析表明常见贱金属离子不被萃取，一定量的贵金属离子不干扰（除钯外）．斜率法测得萃合物的组成为ＰｔＩ２（ＢＯＳＥ），红外光谱指出ＢＯＳＥ的亚砜硫原子与Ｐｔ（Ⅱ）配位，萃合物为一混型配位络合物．

新萃取剂双(正-辛基亚磺酰)乙烷溶剂萃取钯的性能和机理

研究在KI存在下用双(正-辛基亚磺酰)乙烷(简写BOSE)的乙酸丁酯溶液对钯(Ⅱ)的萃取性能.实验结果表明,从pH3至6mol/L盐酸介质中能定量萃取钯(Ⅱ),详细研究最佳萃取与反萃取条件和干扰情况.斜率法测得萃合物摩尔比为Pd:I:BOSE=1:2:1,分子式为PdI_2(BOSE).红外光谱证实萃合物中BOSE的两个亚砜基的硫原子与钯配位,萃合物为异配位体络合物.该法选择性高,可用于某些样品中钯的分离与测定.