模式识别—人工神经网络在化学中的若干新应用

本文通过我们应用模式识别－人工神经网络方法预报新化合物、熔盐相图以及复杂化学反应体系的研究，展示应用模式识别－人工神经网络方法与物理化学理论相结合，研究化学现象的可能性和应用价值。     

Stability of Copper(II), Nickel(II) and Zinc(II) Binary and Ternary Complexes of Histidine,Histamine and Glycine in Aqueous Solution

The binary and mixed-ligand complexes formed between ligands (histidine (His), histamine (Him) and glycine (Gly)) and some transition metals (Cu(II), Ni(II) and Zn(II)) were studied potentiometrically in aqueous solution at (25.0 ± 0.1) C and I = 0.10 M KCl in order to determine the protonation constants of the free ligands and stability constants of binary and ternary complexes. The complexation model for each system has been established by the software program BEST from the potentiometric data. The most probable binding mode for each binary species of histidine and for all mixed species was also discussed based upon derived equilibrium constants and stability constants related to the binary species. The ambidentate nature of the histidine ligand, i.e. the ability to coordinate histamine-like, imidazolepropionic acid-like and glycine-like modes was indicated from the results obtained. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters, log K, log X and ₁₁₁₀. The concentration distributions of various species formed in solution were also evaluated. In terms of the nature of metal ion, the complex stability follows the trend Cu(II) > Ni(II) > Zn(II), which is in agreement with the Irving-Williams order of metal ions. Thus, the results obtained were compared and evaluated with those in the literature.     

Thermodynamics of molecular interactions in ethyl iodide+toluene mixtures

The excess Gibb's free energy of mixing, G^E, for ethyl iodide+toluene at 25°C have been obtained from the measured vapor pressuure data. The H^E and G^E values for ethyl iodide+toluene are positive throughout the ethyl iodide concentration range and G^E>H^E. The results have been analyzed in terms of Flory and ideal associated model theory of nonelectrolyte solutions. It has been observed that the ideal associated model approach which assumes the presence of AN and A₂B molecular species describes well (within±10 J-mol^–1 in the worst case) the general dependence of H^E on X_A (mole fraction of ethyl iodide) over the whole composition range for ethyl iodide+toluene mixtures. The equilibrium constants for A+A AB and 2A+BA₂B reactions along with the enthalpies of formation of AB and A₂B molecular species have been calculated.     

A study of preferential solvation of N-alkyl pyridinium iodides in mixed solvents containing acetonitrile

The charge transfer (CT) band maximum of N-alkyl pyridinium iodide (NAPI) has been studied as a function of the composition of binary mixed dipolar aprotic solvents. The deviation from linearity of the energy maximum (E₁₂) and the mole fraction (of a component solvent) plot is explained as due to a preferential solvation by the more polar cosolvent in the binary mixture. The extent of preferential solvation has been observed to vary with the composition, the maximum being towards the less-polar end. The role of hydrogen bond donating ability of a solvent in preferential solvation is discussed.     

以短链季铵盐/脂肪酸盐为模板合成超微孔二氧化硅

超微孔材料具有1~2 nm的孔径,在分离、催化应用中有望展现出择形催化的能力。 寻找经济、简便的合成超微孔材料的表面活性剂体系是一项有意义的工作。 本研究以短链季铵盐(十烷基三甲基溴化铵,记为C₁₀TAB)和不同链长脂肪酸酸盐混合胶束为模板剂,硅酸钠为硅源,成功制备出高度有序超微孔SiO₂。 通过小角X射线衍射、N₂吸附-脱附、傅里叶变换红外光谱、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术手段对产品的结构和性能进行了表征。 结果表明,合成体系中脂肪酸盐碳链长、加入量、晶化温度等对产物孔道有序性有很大影响。 当选择正辛酸钠(SO)为助表面活性剂,当n(C₁₀TAB):n(Na₂SiO₃):n(SO):n(H₂O)=1:1.5:0.3:800,晶化温度为80 ℃时,可以得到高度有序超微孔SiO₂。 煅烧后样品比表面积为1300 m²/g,孔体积0.49 cm³/g,孔径分布在1.90 nm。     

Linear silver clusters in aqueous solution (clusterites): radiation-induced chemical synthesis and properties

The formation and properties of the products of the radiation-induced chemical reduction of silver ions in aqueous solutions containing sodium polyacrylate were investigated. The absorption spectra of these species exhibit a band at 290 mn and a band in the visible region. The latter shifts from 470 nm to -800 nm with time or after the addition of silver ions. The species obtained (clusterites) arc linear silver clusters bound to the carboxyl groups of the ion exchanger. The red shift of the visible band is due to the increase in their size. The mechanism of the formation and the structure of the clusterites are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1429–1435, June, 1996.     

稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究

合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr₂(L-α-Glu)₂(ClO₄)(H₂O)₇](ClO₄)₃•4H₂O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78～370 K温区, 用精密绝热量热仪测量其低温热容, 在285～306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度T_tr、相变焓Δ_trH_m和相变熵Δ_trS_m分别为(297.158±0.280) K, (12.338±0.016) kJ•mol^－1和(41.520±0.156) J•K^－1•mol^－1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm^－3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: Δ_fH_m⁰＝－(7223.1±2.4) kJ•mol^－1.     

用亚硝基R盐螯合树脂分离富集催化极谱法测定矿石中的铱

本文研究了利用亚硝基Ｒ盐螯合形成的树脂，分离富集试液中痕量贵金属元素铱的实验条件。并利用ＪＰ－１型示波极谱仪，在１．５０ｍｏｌ／Ｌ盐酸＋５．０×１０＾－５ｍｏｌ／Ｌ硫脲＋０．２ｍｏｌ／Ｌ盐酸＋５．０×１０＾－５ｍｏｌ／Ｌ硫脲＋０．２ｍｏｌ／Ｌ碘化钾＋碲（ρ（Ｂ）＝０．４ｍｇ／Ｌ）的混合底液中，对铱进行极谱催化波测定。在示波极谱仪上峰电位约－０．５５Ｖ（银汞齐为参比电极），可测定试液中５．０×１．０     

3-Diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolat(II) — Synthese und Struktur

3-Diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II) — Synthesis and Structure Bis-(N′, N′-diethyl-N-benzoylselenoureato)nickel(II) reacts with diphosgene in benzene to 3-diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II). Its structure is confirmed by RKSA and ESCA. The compound consists of cations, which are planar fivemembered rings and of tetrahedral tetrachloroniccolate(II) anions. The complex is isomorphic with 3-diethylamino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolate(II).