绝热量热和热分析研究8－羟基喹啉的热力学性质

采用绝热量热和热分析技术研究了8-羟基喹啉的热力学性质。用精密绝热量热仪测定了8-羟基喹啉在78 K ~370 K 温区的低温热容。根据实验测定的热容数据计算出了热容拟合方程及热力学函数,得到该物质的熔点、摩尔熔化焓和摩尔熔化熵分别是(345.74±0.15) K、(13.93±0.11) kJ· mol-1 和 (40.26±0.33) J·K-1·mol-1。 根据热力学函数关系式计算了其在78 K ~370 K 温区每隔5 K 的热力学函数 和 。通过部分熔化实验计算出该样品及其绝对纯物质的熔化温度分别是 345.601 K和345.761 K。根据Van’t Hoff方程计算出该样品纯度的摩尔分数为 0.9978。用DSC技术进一步考察了该物质的热稳定性。     

对氨基苯甲酸的合成研究进展

综述了以对硝基苯甲酸为原料合成对氨基苯甲酸的近期研究进展。并从技术和经济角度讨论了各种合成方法的优点与不足。     

无水苯甲酸锂的合成、结构表征及热化学研究

用分析纯苯甲酸和一水氢氧化锂作为反应物, 采用水热合成法制得苯甲酸锂. 利用X射线粉末衍射、FTIR、元素分析及化学分析等方法对样品进行组成和结构表征. 采用精密自动绝热热量计测量了其在80~400 K范围内的摩尔热容, 利用最小二乘法将此温区热容实验值对折合温度进行拟合, 得到热容随温度变化的多项式方程. 通过设计合理的热化学循环, 选用0.1 mol/L HCl溶液作为量热溶剂, 利用等温环境溶解-反应热量计分别测定合成反应的反应物和产物在所选溶剂中的溶解焓, 得到反应焓Δ_rH_m⁰=-(9.75±0.27) kJ/mol. 利用Hess定律计算出苯甲酸锂的标准摩尔生成焓Δ_fH_m⁰(C₆H₅COOLi, s)=-(307.82±0.57) kJ/mol.     

溶解量热法测三氧化钼标准生成焓

用溶解量热法,以KIO_4和KOH组成的弱碱性溶液为量热溶剂,设计3个不同的热化学循环,用RD-1型热导式自动量热计测定了MoO_3的标准生成焓,并推荐其值为ΔH_(t(moO_3))~0(298.15K)=-765.0±6.8kJ·mol~(-1)。     

二水醋酸镉与邻氨基苯甲酸的分步固相反应的热化学研究

用溶解量热法,以一定比例的盐酸(0.2mol·L     

苏糖酸钾的低温热溶及标准摩尔生成焓测定

以苏糖酸与碳酸氢钾反应制得苏糖酸钾K(C₄H₇O₅)·H₂O，通过红外光谱、热重、化学分析及元素分析等对其进行了表征。用精密自动绝热热量计测量了该化合物在78K-395K温区的摩尔热容。实验结果表明，该化合物存在明显的脱水转变，其脱水浓度、摩尔脱水焓以及摩尔脱水熵分别为：(380.524 ± 0.093) K，(19.655 ± 0.012) kJ/mol 和 (51.618 ± 0.051) J/（K·mol）。将78K-362K和382K-395K两个温区的实验热容值用最小二乘法拟合，得到了两个表示热容随温度变化的多项式方程。以RBC-II型恒容转动弹热量计测定目标化合物的恒容燃烧能为(-1749.71 ± 0.91) kJ/mol，计算得到其标准摩尔生成焓为(-1292.56 ± 1.06) kJ/mol。     

量热法对醋酸铜与缬氨酸固相反应的热化学研究

用具有恒温环境的反应热量计，分别测定L－Val(s)、Cu(OAc)2H2O(s）和trans-Cu(L-Val)2(s)、HOAc(1)、H2O(1)在4mol/L HCl溶液中的溶解焓，根据设计的一个热化学循环，可计算出该固相配位反应的反应焓△tHm^φ（298.15K)=20.601kJ/mol，并计算出配合物trans-Cu(L-Val)2(s)的标准生成焓，推荐其值为：△fHm^φ（298.15K)=－1151.31kJ/mol。     

毛细管电泳在拮抗药物对氨基苯甲酸、对羟基苯甲酸和磺胺分析测定中的应用

本文报道了一种用毛细管区带电泳法(CZE)分离与测定对氨基苯甲酸、对羟基苯甲酸及磺胺类药物的新方法.电泳条件为:用 20mmol/L硼砂-20mmol/L H_3PO_4-20 mmol/Lβ-环糊精-4％乙醇(pH 7.0)作电泳液,L-抗坏血酸为内标,280nm为检测波长,样品由电进样方式(10kV/10s)引入毛细管(51.2 cm×50μm i.d.,有效分离长度为 38.5 cm).在24.5°C下,6 min内三者可达基线分离(电泳电压 25kV),且在一定范围内可进行定量分析,保留时间(Tr)及A_(样品)/A_(内标)的RSD值分别小于1.0％和5.0％.本法的建立为研究这三者共存于高等动物及微生物体内时的生理作用提供了一种可共选择的新方法.     

稀土-对氨基苯甲酸配合物的合成及结构研究

对氨基苯甲酸与稀土离子在水热条件下反应得到组成为[Ln(p-Ab)3(H2O)]n(p-Ab=对氨基苯甲酸根阴离子,Ln=Sm(1)、Gd(2)、Er(3))的配位聚合物,而Gd(Ⅲ)离子与对氨基苯甲酸在常规溶液条件下反应得到组成为{[Gd(p-Ab)3(H2O)2].H2O}2(4)的双核配合物。配合物(1)-(3)晶体属单斜晶系,P2(1)/n空间群;中心离子配位数为8。配合物为二维层状结构。配合物(4)为双核结构,配体氨基未参与配位。其晶体属三斜晶系,Pī空间群。配位多面体为8配位的双帽三角棱柱体。     

5-氨基间苯二甲酸钠和5-羟基间苯二甲酸钠的热力学性质

在水溶液中合成了5-氨基间苯二甲酸钠(1)和5-羟基间苯二甲酸钠(2)固态样品,元素分析和TG-DTG确定其组成符合C8H5O4NNa2·H2O(1)和C8H4O5Na2·H2O(2).用精密自动绝热热量计测定了它们在78～400K温区的低温热容,将实验值用最小二乘法拟合,得到热容随温度变化的多项式方程,用此方程进行数值积分,得到该温区内每隔5K的舒平热容值和各种热力学函数值.用RD496-2000型微热量计测定了样品在298.15K时的标准摩尔溶解焓分别为ΔsolHmθ(1,s)=-44.552±0.164kJmol-1和θΔsolHm(2,s)=-36.055±0.154kJmol-1,计算了其水合阴离子标准摩尔生成焓分别为θΔfHm(C8H5O4N2-,aq)=-684.56±1.67kJmol-1和ΔfHmθ(C8H4O52-,aq)=-1263.43±2.13kJmol-1.用RBC-II型精密转动弹热量计测定了样品的恒容燃烧热分别为ΔcU(1,s)=-13382.14±5.28Jg-1和ΔcU(2,s)=-10339.15±4.15Jg-1,计算了它们的标准摩尔燃烧焓和标准摩尔生成焓分别为ΔcHmθ(1,s)=-3252.90±1.28kJmol-1和θΔcHm(2,s)=-2522.64±1.01kJmol-1,ΔfHmθ(1,s)=-1406.46±1.66kJmol-1,θΔfHm(2,s)=-1993.79±1.46kJmol-1.     

Crystal Structures of Urokinase-type Plasminogen Activator in Complex with 4-（Aminomethyl） Benzoic Acid and 4-（Aminomethyl-phenyl）-methanol

Urokinase-type plasminogen activator （uPA） is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors of uPA have been shown to prevent the spread of metastasis and tumor growth, and accordingly uPA is widely recognized as a target for the treatment of cancer. In this work, we report the crystal structures of the complexes of uPA with its inhibitors： 4- （aminomethyl）-benzoic acid （AMBA） and 4-（aminomethyl-phenyl）-methanol （AMPM）, both at a resolution of 2.35 А. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that AMBA is a better inhibitor for uPA （Ki = 2.68 mM） than AMPM （Ki = 13.99 mM）. The structural study shows that the binding mode of inhibitor AMBA on uPA is similar to that of AMPM on uPA, both docked into the active site S1 pocket of uPA. Structural details of these complexes are provided to explain the difference of inhibitory constants.     

4-硝基苯甲醇的低温热容和标准摩尔生成焓

用精密自动绝热量热计测定了4-硝基苯甲醇（4-NBA）在78 ~ 396 K温区的摩尔热容。其熔化温度、摩尔熔化焓及摩尔熔化熵分别为:(336.426 ± 0.088) K, (20.97 ± 0.13) kJ×mol-1 和 (57.24 ± 0.36) J×K-1×mol-1.根据热力学函数关系式,从热容值计算出了该物质在80 ~ 400 K温区的热力学函数值 [HT - H298.15 K] 和[ST - S298.15 K]. 用精密氧弹燃烧量热计测定了该物质在T＝298.15 K的恒容燃烧能和标准摩尔燃烧焓分别为 (C7H7NO3, s)＝- ( 3549.11 ± 1.47 ) kJ×mol-1 和 (C7H7NO3, s)＝- ( 3548.49 ± 1.47 ) kJ×mol-1. 利用标准摩尔燃烧焓和其他辅助热力学数据通过盖斯热化学循环, 计算出了该物质标准摩尔生成焓 (C7H7NO3, s)＝- (206.49 ± 2.52) kJ×mol-1 .     

含胆固醇和 4-(反式-正烷基环己基)苯甲酸结构单元的双液晶基元液晶化合物的合成及其性质

本文合成了一系列含有胆固醇和4-（反式-正烷基环己基）苯甲酸结构单元的新型双液晶基元液晶化合物。这些化合物中两个介晶基元是利用不同长度的氧烷酰基连接在一起。利用FT-IR、MS、1H NMR、POM、DSC 表证了所得化合物的结构和介晶性,并选择几种双液晶基元液晶测定了它们的机械黏度和在主体液晶中的螺旋扭曲力（HTP)。结果表明,绝大多数化合物显示较低相变温度的胆甾相（N*）,并且被选择的化合物的平均机械黏度和螺旋扭曲力类似于或优于胆甾醇任酸酯。     

烟酸的低温热容和标准摩尔生成焓

利用精密自动绝热热量计测量了分析纯烟酸在78～400 K温区的低温热容. 用最小二乘法将实验摩尔热容对温度进行拟合, 得到了热容随温度变化的多项式方程. 用此方程进行数值积分, 得到在此温区每隔5 K的舒平热容值和相对于298.15 K时的热力学函数值. 利用精密静止氧弹燃烧热量计测定了烟酸在298.15 K时的恒体积燃烧能为 Δ_cU＝ －(24528.3±16.1) J•g^－1. 依据物质燃烧焓定义计算出烟酸的标准摩尔燃烧焓为: Δ_cH_m^o＝－(3019.05±1.98) kJ•mol^－1. 最后, 依据Hess定律计算出烟酸的标准摩尔生成焓为: Δ_fH_m^o＝－(56.76±2.13) kJ•mol^－1.     

Low‐Temperature Heat Capacities and Standard Molar Enthalpy of Formation of Gramine (C11H14N2)

Low‐temperature heat capacities of gramine (C₁₁H₁₄N₂) were measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 401 K. A polynomial equation of heat capacities as a function of temperature was fitted by least squares method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at 5 K intervals. The constant‐volume energy of combustion of the compound at T=298.15 K was measured by a precision oxygen‐bomb combustion calorimeter as Δ_cU=−(35336.7±13.9) J·g⁻¹. The standard molar enthalpy of combustion of the compound was determined to be Δ_cH_m⁰=−(6163.2±2.4) kJ·mol⁻¹, according to the definition of combustion enthalpy. Finally, the standard molar enthalpy of formation of the compound was calculated to be Δ;_cH_m⁰=−(166.2±2.8) kJ·mol⁻¹ in accordance with Hess law.     

Syntheses and Characterization of Two Coordination Polymers Constructed by the Ligand 3,5‐Bis(pyridin‐4‐ylmethoxy)benzoic Acid

Two coordination polymers, namely [Zn(L1)(OAc)]·H₂O ( 1 ) and [Cd(L1)₂] ( 2 ), where L1 = 3,5‐bis(pyridin‐4‐ylmethoxy)benzoic acid, have been synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analysis. Complex 1 has a 2D layer structure in which the hydrogen bonds between lattice water molecules and uncoordinated carboxylate oxygen atoms of the ligand L1 in the adjacent layers extend the 2D layer into a 3D supramolecular architecture. The structure of 2 is a 2D (3,5)‐connected net with (3·5²)(3²·5³·6⁴·7) topology. In addition, the luminescent properties of complexes 1 and 2 have been studied in the solid state at room temperature.     

Syntheses and Crystal Structures of Copper(II) and Silver Complexes with 5‐Methyl‐1‐(4‐Methylphenyl)‐1,2,3‐Triazol‐4‐Carboxylic Acid

Two novel complexes [Cu L ₂(MeOH)] ( 1 )and [Ag₂ L (H L )₂(MeOH)] ( 2 ) ( L = 5‐methyl‐1‐(4‐methylphenyl)‐1,2,3‐triazol‐4‐carboxylic acid) were synthesized and characterized by elemental analysis, IR and X‐ray diffraction. Complex 1 is a mononuclear structure; the molecules were assembled into an infinite 2–D supramolecular by the C–H···O weak interactions. Complex 2 is a centrosymmetric dinuclear structure with bis(unidentate) carboxylato co‐ordination mode, and the molecules were assembled into 2–D layers by C–H···O and O–H···O weak interactions.     

1，1－二氨基2，2－二硝基乙烯（DADE）的热化学性质、热行为和热分解机理

The constant-volume combustion energy, △cU （DADE, s, 298.15 K）, the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene （DADE） have been investigated by a precise rotating bomb calorimeter, TG-DTG, DSC, rapid-scan fourier transform infrared （RSFT-IR） spectroscopy and T-jump/FTIR, respectively. The value of △cHm （DADE, s, 298.15 K） was determined as （-8518.09±4.59） j·g^-1. Its standard enthalpy of combustion, △cU （DADE, s, 298.15 K）, and standard enthalpy of formation, △fHm （DADE, s, 298.15 K） were calculated to be （-1254.00±0.68） and （- 103.98±0.73） kJ·mol^-1, respectively The kinetic parameters （the apparent activation energy Ea and pre-exponential factor A） of the first exothermic decomposition reaction in a temperature-programmed mode obtained by Kissinger＇s method and Ozawa＇s method, were Ek=344.35 kJ·mol^-1, AR= 1034.50 S^-1 and Eo=335.32 kJ·mol^-1, respectively. The critical temperatures of thermal explosion of DADE were 206.98 and 207.08 ℃ by different methods. Information was obtained on its thermolysis detected by RSFT-IR and T-jump/FTIR.