Potentiometric studies on the complexation equilibria between some trivalent lanthanide metal ions and biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS)

Summary The chelation behaviour of some trivalent lanthanide and yttrium metal ion with biologically active 2-hydroxy-1-naphthaldehyde thiosemicarbazone (HNATS) has been investigated by potentiomotric measurements at 20±0.5°C in 75% (v/v) dioxane-water medium at various ionic strengths of sodium perchlorate. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of (average number of ligand bound per metal ion) andpL (free ligand exponent). The formation constants of metal chelates have been computed on a PC-XT computer, using a program patterned after that of Sullivan et al. to give _n values using weighted least squares method. TheS _min values (S _min =²) have been calculated. The order of formation constants of chelates was found to be: La³⁺3+3+3+3+3+3+3+3+3+. The formation constants of the chelates formed have been correlated to size and ionization potentials of the metal ions.

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Potentiometrische Untersuchungen der Komplexierungsgleichgewichte zwischen einigen trivalenten Metallionen und biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS)

Zusammenfassung Es wurde das Chelierungsverhalten einiger trivalenter Lanthanidenionen mit biologisch aktivem 2-Hydroxy-1-naphthaldehyd-thiosemicarbazon (HNATS) mittels potentiometrischer Messungen bei 20±0.5°C in 75% (v/v) Dioxan-Wasser bei verschiedener Ionenstärke an Natriumperchlorat untersucht. Die Methode nach Bjerrum und Calvin in der Modifikation nach Irving und Rossotti wurde zur Ermittlung der Werte (mittlere Anzahl an Liganden pro Metallion) undpL (Exponent an freiem Liganden) verwendet. Die Komplexbildungskonstanten wurden in Anlehnung an Sullivan et al. an einem PC-XT Computer errechnet. DieS _min-Werte (S _min=²) wurden ebenfalls bestimmt. Die Reihung der Chelatbildungskonstanten war: La³⁺3+3+3+3+3+3+3+3+3+. Die Bildungskonstanten sind mit der Größe und dem Ionisierungspotential der Metallionen zu korrelieren.

     

Surface properties of finite classical Coulomb systems: Debye-Hückel approximation and computer simulations

We report analytical and numerical studies of surface correlations in finite, homogeneously polarizable, classical Coulomb systems placed in an insulating or conducting environment. Their purpose is to understand the phenomenological, shape-dependent laws of electrostatics, from the point of view of statistical mechanics; we focus on the knowledge of the dielectric susceptibility of the system, a quantity proportional to the equilibrium fluctuation of the system's instantaneous polarization per unit volume. This goal has been achieved for a system in a conducting state. The picture is that the shape-dependent part of the susceptibilities results from the action of unbounded observables (the second moments of the instantaneous polarization of the system) on long-range surface correlations and that the relations of electrostatics are verified by means of shape-dependent thermodynamic limits. This picture is supported (i) by exact solutions and asymptotic analysis of the Debye-Hückel approximation of multicomponent plasmas in disks and spheres with insulating and conducting environment and also in ellipses in a vacuum, and (ii) by computer simulations of a one-component plasma in a disk with different environments, notably a conducting environment with permeable and impermeable wall. These observations have revealed for the first time the reason why the susceptibility of a conducting disk in a conductor with impermeable walls diverges linearly with the radius of the disk: this is due to the occurrence of long-range radial correlations in the conductor. These findings are quantitatively interpreted in terms of a novel canonical Debye-Huckel approximation as contrasted to the ordinary grand canonical version. Lastly a fresh look at the problem of the surface correlations of a conductor in a vacuum, which places the observer close to the surface of the conductor but in the vacuum, is presented and applied to the disk, the ellipse, the cylinder, the sphere, and the wedge.     

钛合金（TC-6）二阶和三阶弹性常数

 用脉冲回波重叠法测量了钛合金（TC-6）的二阶、三阶弹性常数。实验中发现dμ/dp<0（p<0.17 GPa）,dμ/dp>0（p>0.17 GPa）。     

CaTiO3纳米粉体溶胶-凝胶法合成、表征及介电特性

采用无机盐溶胶-凝胶法制备了CaTiO₃纳米粉体，采用TG-DTA、XRD、TEM等技术进行了表征，并探讨了CaTiO₃纳米粉体烧结特性及介电效应。结果表明，干凝胶800 ℃低温煅烧可获得粒径分布较窄、平均粒径为60～70 nm的单相CaTiO₃纳米粉。纳米CaTiO₃粉具有较大的比表面积，使作为粉体烧结驱动力的表面能剧增，促使CaTiO₃在1 200 ℃实现致密烧结，比固相法制备的微米粉烧结降低100～200 ℃，且具有较宽的烧结温区。与微米级粉体烧结体介电特性相比，纳米粉具有更高的Q_f值。纳米CaTiO₃粉制备的陶瓷在1 250 ℃烧结2 h，获得优良的介电性能：ε_r=172，Q_f=4 239 GHz，τ_f=+7.68 × 10^-4 ℃^-1。     

Influence of hydrogen bonding on the properties of water molecules adsorbed in zeolite frameworks

Three hydrated aluminosilicate frameworks—LiABW, NaNAT, and BaEDI—are partly optimized with the periodic Hartree–Fock CRYSTAL95 code. In particular, we optimized the positions of the adsorbed water molecules including the positions of the framework cations (ABW, NAT) or part of the framework atomic positions (ABW). This allowed us to compare cation–water clusters in the gas and adsorbed states and discuss the influence of hydrogen bonding to the framework oxygen atoms or to the neighbor water molecules on the atomic properties (quadrupole coupling constant, anisotropy of electric field gradient) of the adsorbed water molecules. The LiBIK structure obtained from X‐ray diffraction is also considered to illustrate the hydrogen bonds occurring between adsorbed water molecules. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

An Oscillation Condition for an Electrode－separated Piezoelectric Sensor in Non－electrolyte Liquid

ＡｎＯｓｃｉｌｌａｔｉｏｎＣｏｎｄｉｔｉｏｎｆｏｒａｎＥｌｅｃｔｒｏｄｅ－ｓｅｐａｒａｔｅｄＰｉｅｚｏｅｌｅｃｔｒｉｃＳｅｎｓｏｒｉｎＮｏｎ－ｅｌｅｃｔｒｏｌｙｔｅＬｉｑｕｉｄＳＨＥＮＤａ－ｚｈｏｎｇ，ＨＵＡＮＧＭｉｎｇ－ｓｈａｎ，ＬＩＮＳｏｎｇ，Ｎ...     

SYNTHESIS OF LIQUID CRYSTALLINE POLYACRYLATES WITH THIOESTER AS BRIDGE-BOND

A new series of acrylates with the same mesogens containing thioester as bridge-bondwere synthesized, and the acrylates were characterized by H~1 NMR, IR and MS. Thepolymers were obtained by radical polymerization using AIBN as initiator. The monomersand polymers exhibit thermotropic-enantiotropic liquid crystalline behavior.     

Dimerization of some substituted benzoic acids in aqueous solution from conductance measurements

Precision molar conductances of benzoic, o-toluic, 2,6-dimethylbenzoic, 2,3,6-trimethylbenzoic, and, o-fluorobenzoic acids have been determined in aqueous solution as a function of temperature and of concentration up to near saturation (<0.035 M). At the higher concentrations molar conductances are found to be less than anticipated for the simple dissociation of a 1-1 electrolyte. Although the deviations are only 1% or less they have been interpreted to show that these acids are dimerized in solution. The interpretation includes an assumption that the dimer ionizes to produce a triple ion. Increasing numbers of methyl groups lead to increasing dimerization. For those acids with two ortho groups the dimerization increases with increasing temperature while the other three show decreasing dimerization with increasing temperature. Temperature functions have been determined for the dimerization constants and from these functions standard changes in enthalpy, entropy, and heat capacity have been determined. Comparisons are made with dimerization studies in non-aqueous solvents. From these as well as the behavior of benzene in water it is concluded that a major factor driving the dimerization is hydrophobic interaction. To provide a limiting conductance of the triple ion needed in the dimerization calculations a conductance study was also made for o-Phenylbenzoic acid on the assumption that its anion provides an approximate model of the triple ion.     

植物胞外钙调素与拮抗剂W7-Agarose结合作用的荧光光谱法研究

W 7-agarose是常用的细胞外CaM功能的拮抗剂,本实验采用荧光光谱法研究了水溶液中钙调素拮抗剂W 7-agarose与植物胞外钙调素的相互结合反应。W 7-agarose是一种将W 7-共价连接到颗粒型agarose(琼脂糖)的粒子。W 7-agarose颗粒较大且容易沉淀,静置5m in后,溶液中的荧光强度完全由游离的CaM产生。在溶液中加入W 7-agarose后,溶液中一部分CaM与其结合后沉降至荧光比色皿底部,导致溶液中CaM的荧光强度下降。由此可以确定溶液中游离CaM的浓度。根据公式lg{[Q]t(F0-F)/F0}=nlg{[Q]tF/F0} lgnK[B]t,从而计算出配位体系的结合常数和配比。研究表明:二者以摩尔比1∶1结合,其平衡常数为4.9×105。由此进一步计算了W 7-agarose对胞外钙调素的拮抗率,在拮抗剂W 7-agarose浓度达到15~20μmol/L时,拮抗率可达到90%以上,与文献报道的生物学体内实验结果一致,从分子水平上解释了W 7-agarose与CaM的结合作用。     

高聚物固体电解质聚氧化乙烯－溴化铜复阻抗谱及介电常数的静水压效应

采用分子量５００万的聚氧化乙烯和无水溴化铜，通过混溶蒸发法制备成高聚物固体电解质Ｐ（ＥＯ）ｎ－ＣｕＢｒ２薄膜，并在０．１～３００ＭＰａ范围不同的流体静水压下详细测量其复平面阻抗谱，分别得到在不同压力下离子电导率和介电常数与测量频率的关系．进一步解谱准确地求出Ｐ（ＥＯ）ｎ－ＣｕＢｒ２（ｎ＝１２、１６）薄膜离子电导率和介电常数的静水压效应，并结合Ｘ－光物相分析，根据离子迁移通道的物理图象和高聚物的极化机构进行了初步的讨论．添加２０％的增塑剂碳酸丙烯酯，较大改进了压力下的导电性．１２０～３００ＭＰａ的离子电导率提高一个数量级