环糊精及其包结物的电化学研究及应用

本文概述了近年来环糊精及其包结物的电化学研究及应用，同时介绍了我们实验室开展的关于环糊精电化学研究的一些工作。     

三苄基氯化锡及其衍生物的合成

三苄基氯化锡最初用格氏法制得。Keiti等曾报道由锡和苄基氯直接制备,这时溶剂对反应的影响很大:用水作溶剂时得到三苄基锡;用甲苯作溶剂时得到二苄基二氯化锡;用正丁醇作溶剂时三苄基氯化锡的产率只有61％。在反应体系中加入KI、KBr或H_3PO_4等催化剂,三苄基氯化锡的产率也只有60％。本文用DMF作溶剂,AlCl_3-I_2作催化剂,并首次在反应体系中加入镁、锌、铝和钠等使副产物氯化亚锡还原成活性很高的金属锡,后者再与等基氯反应,可使三苄基氯化锡的产率提高到91.3％。文中还报导三种尚     

Investigation of the effects of Au-colloid modification on cobalt hexacyanoferrate film growth and mass transport by electrochemical quartz crystal microbalance

The growth of cobalt hexacyanoferrate (CoHCF) films on bare and Au-colloid-modified electrodes in nitrate or sulfate solutions was monitored by electrochemical quartz crystal microbalance. The average efficiency of CoHCF film growth for Au colloid modified electrodes is 23 and 12 ng cm(-2) s(-1) in KNO3 and K2SO4 solutions, respectively, while those values for the bare gold electrode are 15 and 9 ng cm(-2) s(-1), respectively. In K2SO4 solution, the apparent molar masses for the Au-colloid-modified electrode at lower and higher potential is 58.4 and 37.3 g mol(-1), respectively, which is larger than those for the bare gold electrode (51.7 and 26.3 g mol(-1), respectively). The respective results were also obtained in KNO3 solution. Furthermore, the difference of the apparent molar masses at lower and higher potential for Au-colloid-modified electrodes is smaller than that for bare gold electrodes in the same electrolyte. Additionally, the mechanism of charge propagation is dependent on different anions in electrolyte solutions at higher potentials where the second redox reaction of CoHCF occurs. Therefore, the existence of Au colloids can accelerate CoHCF film growth and weaken the effect of anions on mass transport.     

离子选择电极—流动注射分析法动力学测定葡萄糖存在下的果糖

本文将离子电极与流动注射分析相结合，利用３０℃下，在强碱性介质中，果糖和葡萄糖与２，４－二硝基酚钠反应速度明显差异，动力学测定了葡萄糖存在下果糖的含量。自制了２，４－二硝基酚电极作为动力学电位测定用的工作电极。本法测定果糖的范围为０．０２～１．００ｍｏｌ／Ｌ，其ＲＳＤ为４．０％～４．９％，ＲＥ为１．０～５．０％；当Ｃ葡／Ｃ果≤３倍时，葡萄糖的干扰不超过５％；本法也曾成功地用于果葡萄浆测定，其ＲＳＤ     

新显色剂二溴对甲基偶氮甲磺光度测定稀土的研究和应用

研究了新显色剂二溴对甲基偶氮甲磺光度测定铈组稀土总量的方法，在酸性介质中，试剂与以铈组稀土为代表稀土形成蓝色配合物，在６４４ｎｍ有最大吸收，铈含量在０～１５μｇ／２５ｍｌ范围内符合比耳定律，方法应用于钢铁中铈组稀土总量的直接测定，发现其准确性和重视性良好。     

Polymerization of styrene started by free radicals,generated by external force action-chemical potential gradient of the swelling agent — on the PVC/solvent optical phase boundary

Summary There were studied the process of styrene polymerization in PVC swollen surface layer initiated by free radicals generated under the action of chemical potential gradient as an external force. It was found that conversion of styrene into the block copolymer is an diffusion controlled process.

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Zusammenfassung Die Initiation des Prozesses der Polymerization von Styrol in den Oberflächenquellungsschichten von PVC wurde untersucht.Dabei wurde festgestellt, daß die freien Radikale, welche bei Zerreißung von spannungsbeanspruchten Bindungen, wie sie durch Einfluß von äußeren Kräften auf den Gradienten des chemischen Potentials des Quellungsmittels an Oberflächenquell bildungsmittel Polymer entstehen können, Polymerizationsprozesse des olefinischen Quellungsmittels initiieren können.

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Dedicated to ProfessorV. Kellö in celebration of his 60th birthday.     

新显色剂对溴苯酚偶氮若丹宁光度法测定Au（Ⅲ）的研究

提出了以显色剂对溴苯酚偶氮若丹宁[5-(5-溴-2-羟基苯偶氮)若丹宁]作为光度法测定Au(Ⅲ)试剂的新方法。在1.2mol·L~(-1)盐酸介质及阴离子表面活性剂十二烷基苯磺酸钠(SDBS)存在下,Au(Ⅲ)与试剂形成桔红色配合物,545nm处有最大吸收,摩尔吸光系数ε为7.75×10~4,Au(Ⅲ)浓度在0～44μg/25ml范围内服从比耳定律。方法灵敏度高,选择性好,配合物的稳定时间长,操作简便,已成功地应用于含金废水中Au(Ⅲ)的测定。     

高阻隔材料——偏氯乙烯悬浮共聚树脂

本文介绍偏氯乙烯悬浮共聚树脂的优异阻隔性能、合成配方与工艺。     

Band structure studies on crystalline C60, Ca3C60, and Ca5C60

The three-dimensional EHMO crystal orbital calculations for crystalline C₆₀, Ca₃C₆₀, and Ca₅C₆₀ are reported. The ground states of both undoped solid C₆₀ and partially doped Ca₃C₆₀ are found to be insulating with an indirect energy gap of 1.2 and 0.5 eV, respectively. In contrast, Ca₅C₆₀ forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level, which is found to be located close to a peak of the density of state. The character of crystal orbitals near the Fermi level for both Ca₃C₆₀ and Ca₅C₆₀ is completely carbonlike. In both cases, the Ca atoms are almost fully ionized and C₆₀ molecules form a stable negative charge state with six to 10 additional electrons. © 1995 John Wiley & Sons, Inc.     

铜(Ⅱ)-氨基酸水杨醛席夫碱-α-氨基酸三元配合物的稳定性研究

在25±0.1℃、I=0.1 mol·L^-1 KNO₃条件下，应用pH法测定了氨基酸水杨醛席夫碱(Sal∶A，A配体)-α-氨基酸(Aa,B配体)三元配合物的稳定常数，实验发现在三元配合物的稳定性与B配体的碱性之间存在良好的线性自由能关系。同时，以稳定性数据为探针，研究了三元配合物分子内存在的配体间疏水缔合作用。