过硼酸钠对于有机物的氧化作用的研究——Ⅰ.过硼酸钠对于芳胺和芳硫醚的氧化作用

在有机合成中,过硼酸钠用作氧化剂的实例虽为数不多,但其优点已很明显,例如反应条件温和、选择性强、毒性低、价廉,且过硼酸钠还原后生成无毒的硼酸钠,易于处理或排放。因而过硼酸钠是一种很值得研究的新型氧化剂。水文报道了过硼酸钠对于芳胺(邻-和对-硝基苯胺)及含有吸电子基的芳硫醚的氧化作用:     

Asymmetric synthesis of actinoidic acid derivatives

Synthesis of fully protected actinoidic acid derivative 3 and selectively protected biaryl bisamino acid 4, intermediates for vancomycin total synthesis, are reported.     

The radical cation of syn-tricyclooctadiene and its rearrangement products

The syn dimer of cyclobutadiene (tricyclo[4.2.0.0(2.5)]octa-3,7-diene, TOD) is subjected to ionization under different conditions and the resulting species are probed by optical and ESR spectroscopy. By means of quantum chemical modelling of the potential energy surfaces and the optical spectra, it is possible to assign the different products that arise spontaneously after ionization or after subsequent warming or illumination of the samples. Based on these findings, we propose a mechanistic scheme which involves a partitioning of the incipient radical cation of TOD between two electronic states. These two states engage in (near) activation-less decay to the more stable valence isomers, cyclooctatetraene (COT*+) and a bis-cyclobutenylium radical cation BCB*+. The latter product undergoes further rearrangement, first to tetracyclo[4.2.0.0(2,4).0(3,5]oct-7-ene (TCO*+) and eventually to bicyclo[4.2.0]octa-2,4,7-triene (BOT*+) which can also be generated photochemically from BCB*+ or TCO*+. The surprising departure of syn-TOD*+ from the least-motion reaction path leading to BOT*+ can be traced to strong vibronic interactions (second-order Jahn-Teller effects) which prevail in both possible ground states of syn-TOD*+. Such effects seem to be more important in determining the intramolecular reactivity of radical cations than orbital or state symmetry rules.     

高分子气体分离膜材料的化学结构与气体透过性能之间的关系

本文以硅橡胶和聚酰亚胺为基础,从高分子的化学组成、分子链段的运动能力、侧基的大小及其作用等几个方面,讨论了聚合物的化学结构对其均质膜的气体选择透过性能的影响,以溶解扩散过程对气体分离膜材料的透气行为进行了剖析,井简述高分子化学结构对其成膜时结晶情况的影响及对气体透过的作用;还概述了气体分离膜科学发展的历史以及基本原理.     

O(~1D)+Si(CH_3)_3Cl反应生成振动激发的OH(υ≤5)

实验光谱学和理论计算都发现,“重原子”能隔离分子中的某些振动能景,如SiH_4中Si—H振动泛频的“局域模”.Roger 等在研究F 原子与M(CH_2CH=CH_2)_4(M=Sn,Ge)的反应中,发现了Sn,Ge 对过剩能量转移到其它部分有强烈的阻碍作用(在中间态的寿命时间内).最近,在研究O(~1D)+M(CH_3)_4生成OH(v)反应中,观测到类似的现象.M=C 时,Lutz 用激光诱导荧光方法检测OH 的振动分布,振动是冷的,v=1与v=0的布居比为0.05,     

稀土萘乙酸邻菲绕啉三元配合物的合成和表征

合成了6种稀土(RE)-萘乙酸(NAA)-邻菲绕啉(Phen)固体配合物,其通式为RE(NAA)_3·Phen(RE=Y,La,Nd,Sm,Eu,Er)。通过元素分析,摩尔电导,IR,UV-Vis,H-NMR,XPS和TG-DTA分析,研究了配合物组成、性质及稀土离子与配体间的成键特性。     

导电复合材料葡萄糖氧化酶传感器的研究

报导了用乙基纤维素和乙炔黑获得的导电复合材料构成的葡萄糖氧化酶生物传感器的制备方法.讨论了多种因素对该生物传感器响应电流的影响.测得此电极酶催化反应的活化能为40.3 kJ•mol－1. AFM实验表明，用环己烷洗去石蜡的导电复合材料 葡萄糖氧化酶生物传感器具有粒状结构，这有利于酶催化反应的进行.     

Asymmetric Arrangement of Monolayer in the Multilayer Films of 2-Hydroxy-4,4''''-dihexyloxy-azobenzene

IntroductionConstructionoffunctionalmolecularunitsintostruc turallywell definedsupramolecularassemblieshasattract edgreatattentionduetotheirpotentialapplicationsincomplexelectronicstructuresandmoleculardevices .1 5Amongthevariousfunctionalorganicmolecules ,azoben zenederivativeshavebeenwidelystudiedbecauseoftheirinterestingphotoresponsivebehavior .6 11Extensivestudieshaveshownthatsuitablydesignedazobenzenederivativescanformlongrangeorderedarrangementoftwo orthree dimensionalmolecularlatticeat…     

HY沸石上2,6-二叔丁基萘的择形合成

 研究了脱铝HY沸石（n（Si）／n（Al）＝3．8）上萘（naph）的\r\n选择性叔丁基化反应．结果表明，八面沸石对该反应过程有较好的择形\r\n催化作用，两种异构化产物（2，6－二叔丁基萘和2，7－二叔丁基萘）\r\n之间存在着热力学平衡，即两种异构化产物可在酸性中心位上相互转化\r\n．在以叔丁醇为烷基化试剂，WHSV＝2h－1，n（t－BuOH）／n（naph）\r\n＝3，反应温度为120℃的反应条件下，萘的转化率可达98．43％，β－\r\n位选择性可高达100％，二叔丁基萘收率可达74．34％，2，6－二叔丁\r\n基萘／2，7－二叔丁基萘质量比为6．24．     

CRYSTAL AND MOLECULAR STRUCTURE OF THE COMPLEX OF METHOXYCARBONYLETHYLTIN TRICHLORIDE WITH SALICYLIDENE－M－TOLUIDINE

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