L-丙氨酸和L-组氨酸与铜离子混配合物的热化学

合成了一种新的氨基酸与铜 (Ⅱ )混配型配合物 ,并用具有恒定温度环境反应热量计 ,测定了配合物和反应物在 2 98 2K时 2mol·L-1HCl溶液中的溶解焓 ,由设计的热化学循环得出了配合反应焓变ΔrHm =1 45 92kJ·mol-1,根据热力学原理计算出该配合物的标准摩尔生成焓ΔfHm ,[Cu(Ala·His) ]·4H2 O =-2 0 0 6 5 8kJ·mol-1,为进一步研究这类物质提供了热化学基础参数。     

七水氯化铈与甘氨酸丙氨酸三元固态配合物的热化学

合成了Ce3+与甘氨酸丙氨酸混配体配合物, 通过红外光谱分析、元素分析、热重分析和化学分析, 确定了配合物的组成为Ce(Gly)2(Ala)3Cl3*2H2O, 并用溶解量热法分别测定了CeCl3*7H2O(s), 2Gly(s)+3Ala(s)和Ce(Gly)2(Ala)3Cl3*2H2O(s)在2 mol*L-1 HCl中的溶解焓; 再根据盖斯定律设计了一个热化学循环, 计算得到了七水氯化铈与甘氨酸丙氨酸反应的反应焓ΔrHmθ (298.15 K)=29.075 kJ*mol-1, 并求出了Ce(Gly)2(Ala)3Cl3*2H2O(s)标准生成焓△fHmθ [Ce(Gly)2(Ala)3Cl3*2H2O, s, 298.15 K]=-4468.0 kJ*mol-1.     

三氯醋酸钕与8-羟基喹啉配合物的热化学研究

用溶解量热法 ,在自行研制的具有恒定温度环境的新型反应量热计中 ,测定了NdCl3·6H2 O(s)、CCl3COOH(s)和Nd(TCA) 3·3H2 O(s)在1mol/LHCl中的溶解焓。再根据盖斯定律设计了一个热化学循环 ,计算得到了六水合氯化钕与三氯醋酸反应的反应焓ΔrHmθ(2 98.15K) =2 0 1.688kJ/mol,并求出了Nd(TCA) 3·3H2 O(s)的标准生成焓ΔfHmθ[Nd(TCA) 3·3H2 O ,s ,2 98.15K ] =-3 0 5 3 .3kJ/mol。同时测定了Nd(TCA) 3·3H2 O(s) ,C9H7NO(s) ,Nd(TCA) (C9H6 NO) 2 (s)和CCl3COOH(s)在 4mol/LHCl、二甲亚砜和无水乙醇混合溶剂中的溶解焓 ,再根据盖斯定律设计了一个热化学循环 ,计算得到了三氯醋酸钕与 8 羟基喹啉反应的反应焓ΔrHmθ(2 98.15K) =-3 .2 2 6kJ/mol,并求出了Nd(TCA) (C9H6 NO) 2 (s)的标准生成焓ΔfHmθ[Nd(TCA) (C9H6 NO) 2 ,s ,2 98.15K] =-13 5 5 .6kJ/mol。     

配合物Zn(Phe)(NO3)2·H2O(s)的低温热容和标准摩尔生成焓

利用精密自动绝热热量计直接测定了配合物Zn(Phe)(NO3)2·H2O(s) (Phe:苯丙氨酸)在78-370 K温区的摩尔热容. 通过热容曲线的解析得到该配合物的起始脱水温度为, T0=(324.27±0.37) K. 将该温区的摩尔热容实验值用最小二乘法拟合得到摩尔热容(Cp, m)对温度(T)的多项式方程, 并且在此基础上计算出了它的舒平热容值和各种热力学函数值. 依据Hess定律, 通过设计热化学循环, 选择体积为100 mL浓度为2 mol·L-1 的盐酸作为量热溶剂, 利用等温环境溶解-反应热量计分别测定混合物{ZnSO4·7H2O(s)+2NaNO3(s)+L-Phe(s)}和{Zn(Phe)(NO3)2·H2O(s)+Na2SO4(s)}的溶解焓为, ⊿dH0m,1 =(69.42±0.05) kJ·mol-1, ⊿dH0 m,2 =(48.14±0.04) kJ·mol-1, 进而计算出该配合物的标准摩尔生成焓为, ⊿fH0m =-(1363.10±3.52) kJ·mol-1. 另外, 利用紫外-可见(UV-Vis)光谱和折光指数(refractiveindex)的测量结果检验了所设计的热化学循环的可靠性.     

Tb甘氨酸配合物的热化学研究

本文合成了配合物Tb(Gly)2Cl3·3H2O,用高精度全自动绝热量热仪在81～378 K温区测定了热容,发现在186.054 K和 244.063 K分别存在固-固相变。对配合物进行TG-DTG分析,推测了可能的热分解机理。通过设计适当的Hess热化学循环,利用溶解反应量热计测定了该配合物在298.15 K的标准摩尔生成焓为 -3109.5±3.1 kJ×mol-1。     

锌与组氨酸配合物在水中的溶解焓

在 2 98 .1 5 K下对 L- α苯丙氨酸及其锌配合物 Zn( Phe) Cl2 · 12 H2 O,Zn( Phe) 2 Cl2 ·H2 O,Zn( Phe) ( NO3) 2 ·H2 O,Zn( Phe) 3( NO3) 2 · H2 O和 Zn( Phe) SO4· H2 O在水中的溶解焓进行了测定。计算了 Phe( aq)的标准生成焓。讨论了阴离子不同和锌与苯丙氨酸摩尔比不同对溶解焓的影响。     

硝酸镝与丙氨酸配位反应的热化学研究

采用新型的具有恒温环境的反应热量计 ,以 2mol L的HCl作溶剂 ,分别测定了 [Dy(NO3) 3·6H2 O +4Ala]和Dy(Ala) 4(NO3) 3·H2 O在 2 5℃时的溶解焓。通过设计的热化学循环得到六水硝酸镝与丙氨酸配位反应的反应焓ΔrHmθ=30 .638kJ mol,并计算出配合物Dy(Ala) 4(NO3) 3·H2 O在 2 98.1 5K时的标准生成焓ΔfHmθ=-3833.8kJ mo     

L-半胱氨酸合锌(Ⅱ)钠的热化学

氨基酸与金属微量元素形成的配合物广泛存在于动植物体中并参与许多生命过程。我们在前文[1 ,2 ] 基础上制备了Na2 [Zn(Cys) 2 ]·5H2 O ,通在2 98 2K用具有恒定温度环境的反应热量计[3] 测定了反应物和生成物在4mol·L- 1 HCl溶液中的溶解焓,过热化学循环计算出配合物的标准生成焓△fH　m(Na[Zn(Cys) 2 ]·5H2 O ,s) =- 2 82 8 32 3kJ·mol 1 。1　实验部分1 .1　试剂与仪器L 半胱氨酸(L cys)为生化试剂,纯度>99 0 % ,ZnSO4·7H2 O、C2 H5OH、Na2 SO4、NaOH为分析纯试剂,实验用水均为二次蒸馏水。UV 2 5 0型紫外可见光谱仪(…     

La(NCS)_3·4.5H_2O与18C6在乙醇中的配合行为及热化学研究

采用半微量相平衡方法研究了三元体系La(NCS)3·4.5H2O-18C6-C2H5OH在298.15K的溶解度,测定了各饱和溶液的折光率。该体系形成两种化学计量的配合物,其组成分别为:犤La(NCS)318C6犦·4.5H2O?和犤La2(NCS)6(18C6)3犦·9H2O?,?为溶解一致化合物,?为溶解不一致化合物。依据相平衡结果,制备了两种固态配合物,用IR,DTG,TG,DSC及电导对配合物进行了表征。测量了298.15K时18C6,配合物?在无水乙醇中的热效应,依据本文所设计的热化学循环,求得了溶解一致化合物?的标准生成焓,ΔfHm(犤La(NCS)318C6犦·4.5H2O,s)为-3196.7kJ·mol-1。     

β—三氯化锡基丙烯酸甲酯与Schiff碱配合物分解反应及产物结构表征

将酯基锡 Me O2 CCH2 CH2 Sn Cl3( 1 )与 Schiff碱 ( 2 -HOC6 H4CH NC6 H5) ( 2 )反应合成配合物Me O2 CCH2 CH2 Sn Cl3· ( 2 -HOC6 H4CH NC6 H5) ( 3) ,在其反应混合液放置过程中发生分解生成酯基锡与无机氯离子形成的配合物 Me O2 CCH2 CH2 Sn Cl4- · H+ ( 4)和酯基锡与 Schiff碱的酚氧负离子取代生成的配合物Me O2 CCH2 CH2 Sn Cl2 · ( 2 -OC6 H4CH NC6 H5) ( 5 ) .用元素分析、IR及 NMR对配合物 3,4 ,5进行了表征 ,并对配合物 4的晶体结构进行了解析 .配合物 4为正交晶系 ,空间群 P2 cn,a=0 .785 2 ( 2 ) nm ,b=1 .2 2 36( 1 0 ) nm,c=1 .695 2 ( 4) nm,α=β=γ=90°,V=1 .62 87nm3,Z=4 ,Dc=1 .79g/ cm3,F ( 0 0 0 ) =860 ,μ=2 2 .2 cm- 1 ( Mo) ,R=0 .0 4 49,ωR=0 .0 382 .配合物 4的空间构型为畸变的八面体构型 ,中心锡原子的配位数为 6.配合物 5为 Schiff碱中的酚氧负离子取代配合物 1中的一个氯离子形成的配合物 ,锡原子的配位数为 5     

Sizes of atoms and ions and covalency of bonding in molecules and crystals

A new system of atomic radii for the elements up to barium inclusive is constructed. Values of the radii are chosen so as the dependence between the dissociation energy of diatomic homonuclear molecules and a depth of atom overlapping is monotonous, and the scatter of data is minimal. The depth of overlapping is calculated as a difference between the sum of atomic radii and an experimental interatomic distance. Conclusions are made that: the radii of free atoms and ions are determined by the value of the electron density equal to 0.01 au; they considerably change in molecules and crystals only as a result of the charge transfer from cation to anion; covalent bonding is well described by the overlapping of free atoms (ions), confined by the surface of the given radius, and its energy depends upon the depth of overlapping of valence electron densities of atoms. A method of overlapping atoms is proposed for the approximate estimation of ionic sizes and charges in bound systems.     

Thermodynamics of ionization of water over wide ranges of temperature and pressure

We have summarized results of many experimental investigations of the thermodynamics of ionization of H₂O(liq.) from 0–300°C and from 1.0 atm to nearly 8000 atm. Results of these investigations (equilibrium constants, enthalpies of ionization, heat capacities, partial molal volumes, and compressibilities) have been used for a number of thermodynamic calculations. It is particularly noteworthy that it is possible to use thermal data from 0–145°C with an equilibrium constant for 25°C in calculating reasonably accurate equilibrium constants for temperatures as high as 300°C. Similarly, it is possible to use volumetric data that refer to 1.0 atm in calculating useful equilibrium constants that apply for pressures as high as 2000 atm.Much of the work reported here was done while the author was on leave at the University of Lethbridge.     

Thermochemical study of aliphatic and phenyl-substituted geminal diacetates

The standard enthalpies of combustion _c H ^o of aliphatic diacetates1 and aromatic diacetates2 were measured calorimetrically. The enthalpies of vaporization _vap H ^o or sublimation _sub H ^o of1 and2 were obtained from the temperature function of the vapor pressure measured in a flow system. From _f H ^o(g) of1 and2 new values of group increments for the estimation of standard enthalpies of formation of these classes of compounds were derived. The geminal interaction energy between the geminal acyloxy groups shows no anomeric stabilization.Geminal Substituent Effects, Part 12, for part 11 see Ref. 7.     

Molecular Modelling of Thermodynamic and Related Properties of Mixtures

The results of recent developments on modelling of supramolecular ordering and physicochemical properties of molecular mixtures have been reviewed. The main attention is paid to the unified approach based on a generalized quasichemical model for a set of thermodynamic, dielectric and optical properties of mixtures, self-organized by specific bonding. Interrelations between thermodynamic, as well as dielectric, and optical properties of liquid mixtures, reflecting different molecular parameters, and the characteristics of quasichemical processes are presented. Applications for thermodynamic functions of mixing, permittivity, coefficients Rayleigh light scattering in molecular mixtures are considered. Data on thermodynamics of aggregation in mixtures have been obtained. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermochemistry of heteroatomic compounds 22. Enthalpies of combustion and formation of alkyl(aryl)arsines and arsenites in the condensed and gaseous phases

The enthalpies of combustion (ΔH _comb) of five primary, secondary, and tertiary alkyl(aryl)arsines in the condensed state were calculated using the equation ΔH _comb = −385.8–110.3N, where N is the number of bond-forming electrons. The dependence presented is used for the calculation of the enthalpies of combustion of full esters and amidoesters of arsinous acid of noncyclic and cyclic structures. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1042–1043, May, 2007.     

汞和镍对人血淋巴细胞转化及DNA合成的效应

通过测定＾３Ｈ－ＴｄＲ渗入细胞ＤＮＡ的方法研究了氯化汞和氯化镍对人血淋巴细胞转化和ＤＮＡ合成的效应，结果表明，氯化汞和氯化镍对人外周血淋巴细胞的转化和ＤＮＡ合成的效应是双相性的：在极低浓度下汞、镍化合物均可促进淋巴细胞转化和ＤＮＡ合成，而在高浓度下则抑制淋巴细胞转化和ＤＮＡ合成。汞、镍化合物对淋巴细胞的这种刺激效应比细胞有丝分裂素－植物血凝素的刺激效应要弱，汞对细胞转化和ＤＮＡ合成的刺激效应比镍强     

等物质的量定律及其应用

本文指出了滴定计算中等物质的量规则的缺陷,并提出了等物质的量定律,将这个反映化学反应客观规律的定律定义为:在氧化还原反应体系中氧化剂与还原剂得与失电子的物质的量相等;在酸碱反应体系中酸与碱得与失质子的物质的量相等;在沉淀反应中阳离子与阴离子所具有电荷的物质的量相等;在络合滴定中金属离子与氨羧络合剂的物质的量相等。等物质的量定律可用下式表达:(i=k)∑(i=1)△n(1/z_Ai)Ai=(i=P)∑(i=1)△n(1/z_Bi)Bi。这个定律及其表达式能使复杂的滴定分析计算简单化、规范化。     

Information content of data and variables and types of weighting in least-squares regression methods

Algorithms are given for evaluating the relative amount of useful information related to a particular parameter which is carried by individual data points and intervals of the variables. The algorithms provide an efficient means of using the information contained in a set of data. Applications to the optimization of weighting in regression methods are described. Several informational and combined informational-statistical types of weighting are studied as a means of improving the accuracy and precision of the parameters obtained by non-linear regression.     

微量元素与防病治病

介绍了微量元素在防治疾病中的作用及对健康长寿的意义，涉及人体必需微量元素，有害元素，有机锗，微量元素是健康长寿的重要手段以及微量元素与现代文明病。     

Synthesis and Interferon-Inducing Activity of Azo-Derivatives of Gossypol and Its Imines

New azo-derivatives of gossypol and its imines were described. Their physicochemical properties and data on their interferon-inducing activity were presented.