稀土与含硫有机配体配合物的研究: I. 二乙氨基荒酸稀土配合 物Et~2NH~2 [RE9S~2CNEt~2)~4]的合成、表征与结构

在干燥氮气氛中,以乙醇为溶剂制备出稀土与二乙氨基荒酸二乙铵形成的十五个配合物,测定了它们的红外及紫外光谱、热谱和电导,确定该类配合物组成为Et~2NH~2[RE9S~2CNEt~2)~4](RE=La-Lu,Y;Pm除外)。镧配合物的X射线结构分析表明,在该配合物中四个二乙氨基荒酸根各通过两个硫原子与镧离子成键,从而形成八配位的十二面体阴离子,并与二乙铵阳离子形成离子缔合型的配合物分子。     

氯化镧与甘氨酸配位反应的热化学研究

The reaction enthalpy of coordination reaction of lanthanum chloride with Glycine is determined by solution calorimetry in an isoperibel reaction calorimeter. The calormetric solvent is the solution of hydrochloric acid (2 mol·L- 1), a new thermochemical cycle is designed. According to the results, the following date:()(298.2 K)=- 4.310 kJ·mol- 1()(La(Gly)3Cl3· 5H2O, s, 298.2 K)=- 4222.93 kJ·mol- 1 were obtained.     

二(对氯苄基)锡双吗啉氨荒酸酯和二(对氯苄基)氯化锡N,N-二乙基氨荒酸酯的合成、表征及晶体结构

利用二(对氯苄基)二氯化锡和吗啉氨荒酸钠、N,N-二乙基氨荒酸钠反应,合成了二(对氯苄基)锡双吗啉氨荒酸酯C24H28Cl2N2O2S4Sn (Mr = 694.31) 1和二(对氯苄基)氯化锡N,N-二乙基氨荒酸酯C19H22Cl3NS2Sn (Mr = 553.54) 2。用X-射线单晶衍射测定了这2个化合物的晶体结构,测试结果表明:化合物1的晶体为单斜晶系,空间群C2/c, a = 21.998(9), b = 6.469(3), c = 20.204(8) ,β= 94.444(6)o , Z = 4, V = 2866.3(19) 3, Dc = 1.609 g/cm3, μ(MoKα) = 1.394 mm-1, F(000) = 1400,S = 0.955, (?)max = 0.000,R = 0.0389, wR = 0.0817。化合物2的晶体为单斜晶系,空间群P21/c, a = 13.088(10), b = 9.304(7), c = 19.593(14) ,β = 107.158(10)o, Z = 4, V = 2280(3) 3, Dc = 1.613 g/cm3,μ(MoKα) = 1.660 mm-1, F(000) = 1104,S = 1.010, (?)max = 0.001,R = 0.0290, wR = 0.0651。在化合物1中,锡原子呈六配位畸变八面体构型, 化合物2的锡原子则是五配位畸变三角双锥构型。     

二(对氯苄基)锡双吗啉氨荒酸酯和二(对氯苄基)氯化锡N,N-二乙基氨荒酸酯的合成、表征及晶体结构

利用二(对氯苄基)二氯化锡和吗啉氨荒酸钠、N, N-二乙基氨荒酸钠反应, 合成了二(对氯苄基)锡双吗啉氨荒酸酯C24H28Cl2N2O2S4Sn (Mr = 694.31) 1和二(对氯苄基)氯化锡N, N-二乙基氨荒酸酯C19H22Cl3N2S4Sn (Mr = 553.54) 2。用X-射线单晶衍射测定了这2个化合物的晶体结构, 测试结果表明:化合物1的晶体为单斜晶系, 空间群C2/c, a = 21.998(9), b = 6.469(3), c = 20.204(8) ,β= 94.444(6)o, Z = 4, V = 2866.3(19) 3, Dc = 1.609 g/cm3, m(MoKa) = 1.394 mm-1, F(000) = 1400, S = 0.955, (D/s)max = 0.000, R = 0.0389, wR = 0.0817。化合物2的晶体为单斜晶系, 空间群P21/c, a = 13.088(10), b = 9.304(7), c = 19.593(14) ,β=107.158(10)o, Z = 4, V = 2280(3) 3, Dc = 1.613 g/cm3, m(MoKa) = 1.660 mm-1, F(000) = 1104, S = 1.010, (D/s)max = 0.001, R = 0.0290, wR = 0.0651。在化合物1中, 锡原子呈六配位畸变八面体构型, 化合物2的锡原子则是五配位畸变三角双锥构型。     

稀土与含硫有机配体配合物的研究: I. 二乙氨基荒酸稀土配合 物Et~2NH~2 [RE9S~2CNEt~2)~4]的合成、表征与结构

在干燥氮气氛中,以乙醇为溶剂制备出稀土与二乙氨基荒酸二乙铵形成的十五个配合物,测定了它们的红外及紫外光谱、热谱和电导,确定该类配合物组成为Et~2NH~2[RE9S~2CNEt~2)~4](RE=La-Lu,Y;Pm除外)。镧配合物的X射线结构分析表明,在该配合物中四个二乙氨基荒酸根各通过两个硫原子与镧离子成键,从而形成八配位的十二面体阴离子,并与二乙铵阳离子形成离子缔合型的配合物分子。     

氯·氨荒酸基·二苯基锗配合物的合成

以二苯基二氯化锡和氨荒酸盐为原料,合成了13种氯．氨荒酸基．二苯基锗配合物,利用元素分析,IR和1HNMR表征了这些配合物的结构,生物活性测试结果表明,该类化合物对KB和Bel癌细胞具有较好的抑制活性。     

二苄基一氯化锡氨荒酸酯的合成与表征

合成了13个新的二苄基氯化锡氨荒酸酯化合物(PhCH_2)_2Sn(Cl)S_2CNRR＇。利用元素分析、UV.IR.H NMR谱和TG-DTA表征了它们的结构 初步生物活性研究表明,有些化合物表现出体外抑制白细胞P_(388)生长的活性。     

Et2NH2[Nd(S2CNEt2)4]的晶体结构和生成反应焓变

在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化钕与二乙氨基荒酸二乙铵(D-DDC)配合物,确定其组成为Et2NH2[Nd(S2CNEt2)4].单晶结构分析表明,配合物中4个二乙氨基荒酸根各通过2个硫原子与钕离子成键形成八配位十二面体阴离子,并与二乙铵阳离子形成缔合型分子.晶体属单斜晶系,空间群P21/n,a=1.37517(14)nm,b=2.1146(2)nm,c=1.44641(15)nm,β=102.028(2)°,Z=4.用微量热法测定了298.15K下水合氯化钕和D-DDC在无水乙醇中的溶解焓及二乙氨基荒酸钕液相生成反应焓变分别为(-17.89±0.096),(50.280±0.151)和(-10.116±0.065)kJ/mol,求得固相生成反应焓变.     

具有Cl…Cl作用的一维链状有机锡配合物——二(对氯苄基)氯化锡吡咯烷氨荒酸酯的合成、表征及晶体结构

A novel complex, chlorodi(p-chlorbenzyl)tin dithiotetrahydropyrrolocarbamate, has been synthesized. The crystal structure has been determined by X-ray single crystal diffraction. The crystal of the complex belongs to monoclinic with space group C2/c, a=3.070 0(19) nm, b=0.787 9(5) nm, c=2.374 9(15) nm, β=119.63(9) °, Z=8, V=4.993(5) nm³, D_c=1.515 g·cm^-3, μ=1.521 mm^-1, R₁=0.047 4, wR₂=0.097 2. The structure of the complex consists of discrete molecule containing five-coordinate tin atom in a seriously distorted trigonal bipyramidal configuration. The molecules are packed in the unit cell in one-dimensional chain polymer through a weak interaction between the chlorine atoms of the adjacent molecules. CCDC: 220743.     

Thermochemistry on Coordination Behavior of Praseodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of praseodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) has been synthesized conveniently in absolute alcohol and dry N2 atmosphere. The title complex was identified as Et2NH2[Pr(S2CNEt2)4] by chemical and elemental analyses, the bonding characteristics of which were characterized by IR spectrum.The enthalpy of solution for praseodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K, and the enthalpy changes of liquid-phase reaction of formation for Et2NH2 [ Pr(S2CNEt2)4] at different temperatures were determined by miccocalorimetry. On the basis of experimental and calculated resuits, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy),the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.     

Thermochemical Study of Coordination of Holmium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of holmium chloride hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized via mixing their solutions in absolute alcohol under a dry N2 atmosphere. The elemental and chemical analyses show that the complex has the general formula Et2NH2[Ho(S2CNEt2)4]. It was also characterized by IR spectroscopy. The enthalpies of the dissolution of holmium chloride hydrate and D-DDC in absolute alcohol at 298.15 K o and the enthalpy changes of liquid-phase reactions of the formation of Et2NH2[Ho(S2CNEt2)4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of the liquid-phase reaction of the complex formation were obtained, The enthalpy change of the solid-phase complex formation reaction at 298.15 K was calculated by means of a thermochemical cycle.     

Coordination behavior of erbium chloride hydrate with diethylammonium diethyldithiocarbamate

The complex of erbium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) has been synthesized conveniently in absolute alcohol and dry N₂ atmosphere. The title complex was identified as Et₂NH₂[Er(S₂CNEt₂)₄] by chemical and elemental analyses, the bonding characteristics of which was characterized by IR. The enthalpies of solution of erbium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et₂NH₂[Er(S₂CNEt₂)₄] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase Chemistry and Thermochemstry on Coordination Behavior of Zinc Chloride with Leucine

The solubility property of the ZnCl2-Leu-H2O(Leu=L-a-leucine) system at 298.15K in the whole concentration range was investigatey by the semimicro-phase equilibrium method.The corresponding solubility diagram and refractive index diagram were constructed.The results indicated that there was one complex formed in this system.namely,Zn(Leu)Cl2.The complex is congruently soluble in water.Based on Phase equilibrium data,the complex was prepared.Its composition and properties were characterized by chemical analysis,elemental analysis,IR spectra,and TG-DTG.The thermochemical properties of coordination reaction of zinc chloride with L-a-leucine were investigated by a microcalorimeter.The enthalpies of solution of L-a-leucine in water and its zinc complex at infinite dilution and the enthalpy change of solid-liquid reaction wrer determined at 298.15K.The enthalpy change of soild phase reaction and the standard enthalpy of formation of zinc complex were claculated.On the basis of experimental and calculated results,three thermodynamic parameters(the activation enthalpy,the activation entropy and the activation free energy),the rate constant and three kinetic parameters(the activation energy,the preexponential constant and the reaction order) of the reaction,and the standard enthalpy of formation of Zn(Leu)^2 (aq) were obtained.The results showed that the title reaction took place easily at studied temperature.     

氯化镧拮抗内毒素作用的初步研究

用定量鲎基质显色法测定LaCl3结合内毒素（LPS）的能力。通过ELISA，荧光宣RT－PCR方法观察LaCl3对LPS诱导的小鼠腹腔巨噬细胞（Mψ）肿瘤坏死因子－α（TNF－α）分泌及TNF－αmRNA表达的影响。通过小鼠死亡观察LaCl3和LPS毒性的影响。结果显示LaCl3具有结合LPS，抑制TNF－α分泌及TNF－αmRNA表达，降低LPS毒性的作用。     

The Effect of Magnesium Chloride Hydrate on the Fire Retardation of Cellulosic Fibers

Thermal analysis was used to investigate the effect of the addition of magnesium chloride hexahydrate as a fire retardant to cellulosic fibers. The kinetics of the decomposition of the cellulosic material were first studied. The decomposition of the dry salt was also investigated and three steps disclosed. Then, the fabrics were impregnated into salt solutions of different concentrations and the loss in mass was followed by thermal analysis. The percent loss in mass was compared to that of pure cellulosic fabric at different temperatures. It was found that there is an appreciable improvement in fire retardation at a minimum percent add-on of the salt of 35%. This revised version was published online in August 2006 with corrections to the Cover Date.     

氯化镧对水稻幼根质膜标准氧化还原系统的影响

稀土对农作物有促进生长、增加产量的作用。研究表明稀土元素不能进入植物细胞内而只停留在细胞膜外[1] ,因此细胞膜可能是稀土元素发生作用的原初位点。植物细胞质膜上存在的氧化还原系统 ,可以催化一系列氧化还原反应 ,能够促进矿质元素的吸收、控制植物的生长、参与溶质的转运等[2 ] 。关于稀土对质膜标准氧化还原系统的影响及对铁元素吸收的影响尚未见报道 ,本实验用两相法分离纯化水稻幼苗根质膜 ,观察ＬａＣｌ3 对质膜氧化还原系统活性的影响及对水稻吸收铁元素的影响。1　 材料和方法1.1　 实验材料　　水稻 (Ｏｒｙｚａｓａｔｉｖａ…     

L-亮氨酸与醋酸铜固相配位反应的热化学研究

L-亮氨酸与醋酸铜固相配位反应的热化学研究     

水介质中硼酸盐-氯化镧的摩擦磨损性能研究

采用四球摩擦磨损试验机考察了硼酸钠、硼酸钾和氯化镧在水介质中的极压、抗磨和减摩性能,采用扫描电镜（SEM）、X射线能谱（EDX）、X射线光电子能谱（XPS）分析了磨斑表面形貌、主要元素的分布特征和化学状态。结果表明,硼酸钠、硼酸钾和氯化镧可一定程度地提高水的极压、抗磨和减摩性能,硼酸钾性能最优,硼酸盐与氯化镧复合后性能进一步改善。硼酸盐与氯化镧复合前摩擦表面擦伤严重,复合后擦伤明显减小,表面形成的La2O3,B2O3,Fe3O4和Fe2O3起到了良好的极压、抗磨和减摩作用。