BIPHASIC PHOTOCHEMISTRY: THE FIRST ACTINOMETRIC REACTION ON A SOLID SUPPORT

Abstract Measurements were performed to determine the action spectrum and dose dependence for photoreactivation of E. coli B_s-1 cells after γ-irradiation. The similarities between photoreactivation after UV- and after γ-irradiation in action spectra, kinetics, and other characteristics indicate that the increased survival of γ-irradiated cells after illumination with photoreactivating light is the result of true photoenzymatic repair.     

连续一级反应的热动力学研究

本文把时间比法引入热动力学研究,建立了连续一级反应的热动力学研究法,并用来研究了一个连续反应体系的热动力学,验证了该方法的正确性.     

高分子线性柔性链在超滤过程中第一类突变现象的观察

利用一种双层结构的膜屏蔽了每个微孔所产生的流场之间的相互作用,从而首次观测到理论上预计的高分子线性柔性链在超滤过程中的第一类突变现象,即仅当宏观流速高于一宏观阈值时,高分子长链方可通过尺寸远小于链无扰半径的微孔,且该宏观阈值与高分子链的长短无关.另外,实验中的过滤膜含有多个微孔,实验结果显示,当一给定的宏观流速低于宏观阈值时,部分微孔会被无法通过的较长的高分子链堵塞,造成未堵塞微孔中的微观流速大于微观阈值.因此,较短的高分子链可从未堵塞的微孔通过滤膜.     

THE DIRECT OBSERVATION OF A PSORALEN-THYMINE UVA INDUCED SOLID-STATE CYCLOADDITION REACTION PRODUCT BY SINGLE-CRYSTAL x-RAY DIFFRACTOMETRY

Single-crystal x-ray diffraction methods have been used to directly observe and simultaneously determine the molecular structure of the UVA induced cis-syn photocycloaddition product in a partially photolyzed single crystal of a psoralen(pyrone ring side)-DNA(thymine) interaction model compound, 1'-(8-oxypsoralen)-8'(thym-1"yl)3',6'-dioxaoctane.     

MICELLAR CATALYSIS OF COMPOSITE REACTIONS I MICELLAR EFFECT ON THE CONSECUTIVE FIRST ORDER REACTION

The micellar catalytic model (or the consecutive first order reaction has been proposed in this paper. It was applied to the alkaline hydrolysis of dimethyl phthalate in micellar solutions of surfactants (CTAB, SDS and Triton X-100), and the alkaline hydrolysis of bis (2,4-dinitrophenyl) posphate in CTAB micellar solution. Rate constants obtained in micellar phase indicate that the two steps of alkaline hydrolysis of dimethyl phthalate are both inhibited by all of the surfactants investigated. CTAB micelle exhibits a greater catalytic effect on the alkaline hydrolysis of bis (2, 4-dinitrophenyl) phosphate. this may be arised from the local concentration effect of hydroxide ion in CTAB micellar phase. Nevertheless. the second order rate constant of bis-(2, 4-dinitrophenyl) phosphate in the micellar phase is smaller than that in the bulk phase.     

CHARACTERISTICS OF THE PRIMARY REACTION OF HYPOCRELLIN A PHOTOSENSITIZATION

The primary reaction of photosensitization of Hypocrellin A (HA) has been studied byusing techniques of ESR, spin-trapping and spin-counteraction. The experiments show thatHA is able to generate not only ~1O_2,but also O_2~-·OH and HA~- which are observed for thefirst time. The conversion of generating active oxygen into generating nonoxygen free rad-ical is confirmed as well. Based on the characteristics of the primary reaction which gene-rates these active substances (transient products), it is proposed that the photosensitized dam-age for the biological system by HA is probably related to not only ~1O_2 itself, but also amultiple effect from ~1O_2 as well as O_2~-,·OH and HA~+ free radical.     

一类Narcissistic反应过渡态的优化

我们对一类narcissistic 反应XCH_2-CH_2Y→[过渡态TS]→YCH_2—CH_2X (1)进行了研究,结果表明其过渡态能在对称性限制下由能量极小化方法较容易地给出. 采用IMSPAK分子轨道从头算程序,在IBM VM/370计算机系统上用STO—3G极小基组以平衡几何构型的能量梯度优化方法,在对称性限制下对反应(1)的几种反应体系的过渡态构型进行了优化,其结果列于表1.     

新型偶氮化合物光致变色的研究

具有光致变色现象的有机化合物近年来一直为世人所关注.这是因为此类化合物在光信息存储材料方面具有潜在的应用价值.偶氮化合物作为一类重要的染料,已广泛地被人们从温度、溶剂、及光照波长等许多方面进行过研究^[1-3].     

STUDY ON A NOVEL KIND OF CHEMILUMINESCENCE REACTION

Acidic hydrogen peroxide solution,in the presence of a certain metalcation,can react with alkaline solution and produce chemiluminescence lightemission.The present paper firstly reports this novel kind ofchemiluminescence reaction.The effect of some factors and metal ions on thechemiluminescence reaction has been tested and studied.     

THERMIC REACTION OF THIOPYRIDONES

Abstract

Some reactions of phosphazenylcyclophosphazenes are reported. Their NMR spectra are discussed and related to conformation. X-ray crystallographic data are presented.     

蒽镁的某些化学反应

本文报道了蒽镁与O_2,H_2,C_2H_2,CO,CO_2,(CH_3)_2CO,C_2H_5Br的反应。其中,蒽镁与(CH_3)_2CO和C_2H_5Br的反应可以分别作为合成(9,10-二氢-9-蒽基)二甲基甲醇和9,10-二乙基-9,10-二氢蒽的简易方法。     

一种用于研究金属氢化反应的量热系统

将RD-1型量热计的样品管改装成能测量金属氢化反应热效应的量热系统,量热计常数经电能标定,峰高法和面积法所测结果的相对精度为0.5-1％。     

A STUDY OF THE SAFRANINE-ASCORBIC ACID PHOTOCHEMICAL REDOX REACTION

Abstract— Flash-photolysis of safranine in deoxygenated 5 per cent aqueous pyridine produces a transient bleaching, which disappears by a second order process. Very probably this transient species consists of a pair of radicals or radical ions and not of the safranine in the triplet state. These radicals are also produced in chlorophyll sensitized reactions. Present results combined with previous work by us[I] indicate that the chlorophyll sensitization of safranine bleaching involves the formation of these radicals.
The direct photochemical reduction of safranine to its leuco form occurs through the intermediate formation of the radicals. The appearance and disappearance of these radicals is fast compared to the role of photochemical formation and thermal disappearance of leuco safranine. Ascorbic acid influences but is not essential to the photo-bleaching of safranine in 5 per cent aqueous pyridine. An increase in ascorbic acid concentration increases the steady-state yield of the radicals but decreases the steady-state yield of the leuco safranine. In the absence of ascorbic acid or other added substance, safranine photobleaches irreversibly in deoxygenated 5 per cent aqueous pyridine. A plausible mechanism is proposed in explanation of the direct photochemical reduction of safranine.     

不同硫醚化合物和单线态氧反应能力的研究

本工作采用Young提出的方法,利用二苯基苯并呋喃及硫醚类化合物对单线态氧的竞争反应,通过荧光强度的比较,测定了一系列烷基和芳基硫醚化合物和单线态氧反应的速度常数。对所得结果,联系立体效应和电子诱导效应进行了讨论。     

A NEW TYPE OF PHOTOCHEMICAL ADDITION REACTION OF ELEMENTAL SULFUR TO OLEFINS

Abstract

Photochemical reactions of elemental sulfur with several olefins were studied. Irradiation of a mixture of elemental sulfur and norbornylene with 3500 Å light afforded 3,4,5-trithiatricyclo[5.2.1.0]decane (1) and 2,3-epithionorbornane (2). Similarly, several thiane derivatives (4–6) were found to be formed by the photolysis of a mixture of cyclohexene and sulfur.     

INVERSION OF A NONLINEAR DYNAMICAL MODEL FROM THE OBSERVATION

A technique for inversion of a nonlinear dynamical model from the observations has been developed, and examined by using the Lorenz system. The results show that the Lorenz system can be accurately inversed by using the observation data set. This technique will be broadly used in establishing the nonlinear dynamical model from an actual data set.     

DARZENS REACTION OF 2-CHLOROMETHYLBENZOXALINE

2-chloromethylbenzoxaline reacted with aromatic aldehydes in alkaline solution,giv-ing Darzens condensation product:2-aryl-3-benzoxalinyloxiranes.     

光电化学方法研究嵌入反应

自从七十年代Steele和Armand等提出用嵌入材料作为电池的活性物质以来,新型的高能锂电池有了很大的发展.这类电池反应的特点是伴随电子转移的同时还有锂离子进入阴极主体晶格中,故称为嵌入反应.然而,从研究嵌入反应的方法来看,除了电位扫描等经典的电化学技术以外,用的是X射线衍射、X射线光电子能谱等非现场的表面测试技术,分析放电后阴极中有锂存在,证明这类反应机理是锂离子的嵌入反应.迄今为止,尚未见到在放电过程中现场检测锂离子嵌入的方法的报导.鉴于嵌入反应电池的阴极材料大多数是金