2-芳基丙硅烷的光化学反应机理

从理论及实验上研究了2-芳基丙硅烷(1)的光物理及光化学特性.结果表明,在极性溶液中观察到的强荧光带来源于分子内电荷转移(ICT);在非极性溶液中,化合物1的光化学反应产物为亚甲硅基并伴随着1,3-甲硅烷基的迁移;而在乙醇-己烷溶液中,光化学反应主要导致Si-Si键的裂解,通过研究光化学反应与温度的关系可确认,亚甲硅基与1,3-甲硅烷基的迁移来源于化合物1的不同电子激发态,非谐振双光子光化学反应(NRTP)结果表明,亚甲硅基迁移来源于化合物1的La电子态.     

硝酸与石蕊试液反应本质的质疑

硝酸与石蕊试液的反应曾经是高中化学教材中硝酸的性质实验之一,此内容也多次在高中生近年来的化学试题中出现,而硝酸与石蕊试液的作用情况比较复杂,其一是石蕊试液与稀硝酸和浓硝酸的反应现象不相同;其二是在不同温度下石蕊试液与浓硝酸反应的现象也不完全相同。室温下将紫色石蕊试液滴人稀硝酸中,溶液立即变为红色,微热之,无明显变化发生;而室温下将紫色石蕊试液滴人浓硝酸中,溶液的颜色会由红色变为橙色,最后变为黄绿色,并伴随有大量红棕色气体产生。对此实验现象,有的教师解释为浓硝酸具有强氧化性,石蕊试液与浓硝酸作用时发生了氧化还原反应,逸出的红棕色气体是浓硝酸的还原产物二氧化氮。而稀硝酸的氧化性弱于浓硝酸,在此仅表现出酸性,因而只能使紫色石蕊试液变红。浓硝酸与石蕊试液作用是否主要发生的是氧化还原反应？黄绿色产物是什么物质？针对上述疑问,我们进行了反复研究,大量实验事实说明,浓硝酸与石蕊试液在发生酸色反应后,主要发生的是硝化反应,同时伴随有硝酸的分解反应,二者发生氧化还原反应的可能性很小。     

探讨浓硝酸与铜反应的混合液呈绿色的本质原因

浓硝酸和铜反应的溶液为草绿色,说法较多,还存在疑问。通过大量的实验,认为主要是NO2和水反应生成的亚硝酸,再结合铜离子生成铜的亚硝酸化合物,使溶液呈绿色。     

The Chemistry of (U,Pu)O2 Dissolution in Nitric Acid

The focus of this paper is the chemistry of mixed uranium plutonium oxide (MOx,) in nitric acid. An overview of dissolution chemistry is discussed by comparing the differences in the dissolution characteristics of uranium and plutonium oxides. An overview of batch dissolution experiments, studying the dissolution chemistry of high surface area MOx powders and low surface area MOx pellets with reference to the effects of nitrous acid, nitric acid and temperature are described. The results are discussed in terms of the autocatalytic mechanism and mass transfer limited dissolution.     

A New Photochemical Reaction of Sulfonic Acid Esters

Abstract

In 1968 Zen and coworkers reported that thep-tolylsulfonyl group could be removed from carbohydrate systems by photochemical reaction (eq 1).¹ Since then other investigators have used this deprotection process in carbohydrate synthesis.^2-10 Mechanistic studies^11-16 have shown that tosylate photolysis is promoted by compounds (e.g., triethylamine) that donate an electron to an excitedp-toluenesulfonate to generate a radical anion (1). This intermediate then fragments to form the anion of the deprotected sugar (Scheme 1). Since generating a radical anion is the central element in this photochemical process, structural changes that impact radical anion formation should influence the reaction. Replacing the p - tolylsulfonyl group with the pentafluorophenylsulfonyl group generates a more stable radical anion (2) because the electronegative fluorine atoms can help stabilize the negative charge. Since we have a continuing interest in the photochemistry of sulfonic acid esters, we synthesized the pentafluorobenzenesulfonates (pentaflates) 3-6 and studied their photochemistry under electron transfer conditions.     

The Mechanism of Photochemical Release of Nitric Oxide from S-Nitrosoglutathione

Abstract— Laser flash photolysis of S-nitroso complexes of glutathione (GSNO) and bovine serum albumin (BSANO) via excitation at 355 nm has been used to investigate the photogeneration of nitric oxide (NO) and subsequent radical reactions. In the case of GSNO, liberation of NO was confirmed by its oxidation of oxyhemoglobin to met hemoglobin. Initial NO release is via homolytic cleavage of the S-N bond to produce the glutathione thiyl radical, GS, which can subsequently react with (a) ground-state GSNO (k= 1.7 × 10⁹M^?1/i> s^?1) to yield additional NO and oxidized glutathione, GSSG; and (b) oxygen (k= 3.0 × 10⁹M^?1 s^?1) to give the glutathione peroxy radical, GSOO, which subsequently reacts with ground-state GSNO (k= 3.8 × 10⁸M^?1 s^?1), also producing additional NO and GSSG. The relative concentrations of oxygen and GSNO in the system determine the major pathway for removal of G'. These secondary reactions occur at such high rates that they preclude radical recombination under low-intensity irradiation conditions. The quantum yield of overall loss of GSNO thus varies with both GSNO and oxygen concentrations; a value of 0.66 was determined for an aerated solution of GSNO (0.86 mM). In the case of GSNO, therefore, generation of NO is not due solely to homolysis of the S-N bond; secondary reactions of the radicals formed lead to further NO liberation. In rationalizing the known phototoxicity of GSNO, possible contributions from thiyl and thiyl-derived radicals should be considered. In contrast to GSNO, direct excitation of BSANO (containing one bound NO group per molecule) led to photodecomposition with a quantum yield of 0.09 but no evidence was obtained for liberation of NO into the bulk medium.     

Characterization of Nitro-Substituted Polybenzimidazole Synthesized by the Reaction with Nitric Acid

Abstract

Nitro-substituted poly[2,2′-(m-phenylene)-5,5′-bibenzimidazole]s (PBIs) were synthesized by the reaction of PBI with nitric acid in sulfuric acid under various conditions. The number of nitro groups substituted on the aromatic ring of PBI per polymeric unit varied from 1.44 to 3.55 according to the reaction conditions. An increase in reaction temperature and concentration of the nitric acid increased the degree of substitution. The inherent viscosity of the substituted polymer increased as the reaction temperature decreased. When the reaction temperature was 30°C, the inherent viscosity of the polymer increased as the concentration of nitric acid increased. The nitro-substituted PBI exhibited polyelectrolyte behavior in formic acid. The nitro groups substituted on PBI were dissociated when the polymer was heated to 450°C, displaying exothermic behavior, and the decomposition of polymer was proportional to its nitro group content. All nitro-substituted PBIs showed better solubilities in polar aprotic and acidic solvents, such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, formic acid, sulfuric acid, and trifluoromethanesulfonic acid.     

有毒有机污染物光化学降解及机理研究

水环境污染已成为全球性普遍关注的重要课题.Fenton氧化法和Fenton光化学氧化法由于它在处理废水中的有毒有机污染物方面呈现了其它处理方式不能取代的特点而具有广阔的应用前景.虽然Fenton氧化法是一种非常有效的废水处理方法,但是由于体系中大量的铁离子的存在,使得处理后的体系带有颜色,且沉降铁泥的处理大大增加了运行成本.此外,Fenton反应一般需要在pH小于3的酸性介质中进行及在反应过程中过氧化氢的利用率不高等不足都限制了该方法的广泛应用.在本文中,我们用铁络合物代替Fenton反应中的铁离子并首次把可见光引入到反应体系中氧化降解有机污染物,着重研究了铁络合物在可见光照射下在均相和异相反应体系中对有毒有机污染物的光催化降解动力学、光化学反应机理、微环境的影响、活性自由基的形成以及光降解产物等方面内容,并得出以下几个重要结论:     

Dissolution of Palladium Deposited onto a Fibrous Carbon Cathode in Nitric Acid Solution through Operation of a Short-Circuited Electrochemical System

Dissolution in 3.5 M NHO₃ of palladium deposited onto a fibrous carbon electrode from hydrochloric and nitric acid solutions was studied. The factors influencing the dissolution of palladium in contact with the electrode were revealed using a model of short-circuited electrochemical system.     

天然聚多糖的溶解机理及溶液性质

21世纪"绿色"化学已成为各国科学界和工业界研究与开发的方向.天然高分子中纤维素、甲壳素等聚多糖来源丰富,是重要的可再生资源,也是未来主要的化工原料之一.由于大量的分子内和分子间氢键,它们的溶解长期以来都是非常棘手的问题.另一方面,聚多糖的结构非常复杂,只有弄清楚其链构象和溶液性质,才可能进行合理的分子设计,实现其更好的应用.本文简要介绍了本课题组用碱/尿素水体系低温溶解纤维素和甲壳素等天然高分子的机理和溶液中分子链构象,以及活性多糖在水溶液中的链构象和溶液性质的研究进展.     

Mechanism of the Reaction of Xenon Tetraoxide with Hydrogen: A Photochemical Reaction

The dependence of the rate of a photochemical reaction of XeO₄with H₂on the concentrations of H₂and the diluent gases He and CO₂is studied at room temperature. The results are compared with the data for the dark reaction. A mechanism with the elementary energetic branched-chain reaction OH (v) + XeO₄OH + O + XeO₃is proposed to explain the results of the study.     

2-溴丙酸气相热消除反应的机理

用密度泛函（DFT）方法,在B3LYP/6-31G**水平上对2-溴丙酸气相消除反应机理进行了研究.计算表明,反应主要是通过半极化五元环结构过渡态进行的,羧基上的氢原子协助溴原子离去,羧基氧原子帮助稳定过渡态.在B3LYP/6-311＋＋G(3df,3pd)水平上对B3LYP/6-31G**优化的几何构型进行了单点能计算,计算所得反应的速度控制步骤的活化能为189.461 kJ•mol－1,偏离实验值((180.3±3.4) kJ•mol－1)5.08％.     

聚电解质复合物在表面活性剂水溶液中的溶解机理

聚电解质复合物 ( PEC)因其独特的物理化学性质而受到广泛关注 .对其研究主要集中在其结构及形成的影响因素 ,如聚电解质的分子量 [1,2 ] 、电荷密度、电荷强弱 [1,2 ] 及溶液离子强度 [3,4 ] ,而很少有关于聚电解质复合物溶解性的报道 [5,6 ] .一般认为组成 PEC的聚正离子 ( PC)和聚负离子 ( PA)之间 ,通过离子键形成网状交联结构而不溶于水及有机溶剂 .只有一种特殊的溶剂体系屏蔽溶剂可溶解此类复合物[7,8] .本文报道一类新的聚电解质复合物 :以二苯胺重氮树脂 DR为聚正离子 ,苯乙烯 -马来酸酐碱性水解物 ( PSMNa)为聚负离子的 P…     

探究铁和铝在浓硫酸和浓硝酸中的电化学行为

铁和铝在冷的浓硫酸和浓硝酸中都因被钝化而阻止其进一步被腐蚀,通过用Fe、Al做原电池的电极材料,考察其在浓硫酸、浓硝酸中的钝化情况：Fe、Al的钝化快慢、钝化后金属表面氧化膜的致密程度、酸液温度等对钝化的影响等均有所不同。     

Effect of Ethanedioic Acid Additives on the Dissolution of Manganese Oxides in Sulfuric Acid Solution

The effect of ethanedioic acid additives on the rate of manganese(IV) oxide dissolution in sulfuric acid solutions was studied by kinetic and electrochemical methods. Interaction modes were established, and some details of the studied process mechanism were elucidated. Interaction schemes corresponding to the observed kinetic dependences were proposed.     

Reaction of Octyl Ether with Nitric Acid and its Mixtures

Russian Journal of Organic Chemistry -     

正戊烷与SO2气相光化学反应自由基机理的ESR验证

烷烃与SO2的气相光化学作用为自由基反应[1].Penzhorn等[2]对C4以下的气相烷烃与SO2光化学反应产物的复杂性和多样性进行了推测,此后对该光化学反应机理的研究均以反应产物(特别是凝聚态产物)为基础进行的[3].为验证烷烃与SO2光化学反应体系中确实存在自由基,Makarov等[4]向正戊烷与SOz光化学反应体系中引入NO,通过对反应起始阶段的产物的光谱分析和反应动力学研究,论证了该反应的自由基过程.ESR技术是检测自由基的有效方法,Stokes等[5]利用自旋捕集-ESR技术成功地测得了气相羟基自由基的存在.     

纳米金催化没食子酸还原法制备纳米银及机理研究

通过在没食子酸与硝酸银的混合溶液中加入微量氯金酸，利用首先生成的纳米金对银离子还原的催化和成核作用，促进没食子酸与硝酸银反应制备了纳米银溶胶。研究了所得溶液的紫外可见吸收光谱特性，用HRTEM和EDX对纳米银颗粒的形貌和元素组成进行了表征和分析，并初步探讨了反应机理。实验结果表明，在优化的最佳条件下，用该法制备的纳米银最大吸收峰在420 nm左右，颗粒呈球形，粒度均匀，单分散性好。反应中微量氯金酸的加入是促进没食子酸与硝酸银反应生成纳米银的必要条件之一。该法操作简单，反应快速，无需特殊设备。     

铜与稀硝酸反应的实验

在锥形瓶口配一个带有分液漏斗、导管和一根铁丝的胶塞,铁丝下端弯成环状套一段蜡烛。