锰氧咔咯催化环己烷生成己二醛催化机理的理论研究

通过密度泛函理论计算,研究锰氧咔咯催化环己烷氧化成己二醛的反应,讨论该催化过程的多态反应活性.计算表明,该反应经历两步羟基化和一步C—C键断裂过程.两步羟基化都是由氢转移开始,形成碳自由基中间体,接着迅速发生的自由基反应形成二醇的中间体.C—C键断裂过程由氢转移开始,先形成氧自由基中间体,氧自由基单电子和邻近环C—C键存在强烈的相互作用,导致该C—C键活化断裂和第二个氢的协同转移.反应的速控步是第二步羟基化过程,因此碳自由基中间体的稳定性决定该反应的难易,这也解释了实验上观察到叔碳的活性大于仲碳的活性顺序.     

生物体系活性氧及反应中间体研究进展

生物体系活性氧及反应中间体是生物医学、分析化学领域重要研究对象 ,许多重要生命现象及重大疑难病症都与活性中间体有关。本文介绍了活性氧中间体、酶反应中间体、药物代谢中间体、化学振荡反应中间体近年来的重要进展 ,尤其是对中间体分析的困难及动力学分析法在解决这一问题中的优点作了中肯的评述。     

丙烯热反应生成甲基环戊烷的理论探讨

在UHF／3-21G水平上,应用从头算分子轨道法和能量梯度技术,并用Mller-Plesset二级微扰理论对能量进行了相关能校正,研究了丙烯在800K热反应形成甲基环戊烷的反应机理．求得该反应分三步进行：（1）两分子丙烯相互作用产生1,4-双自由基中间体;（2）1,4-双自由基中间体经氢迁移过程生成1,5-双自由基中间体;（3）1,5-双自由基中间体闭环形成甲基环戊烷．理论计算所得的机理与实验工作者推测一致．     

一种基于检测酶反应中间体而测定漆酶活性的动力学分析法

在反相胶束（AOT／n-octane）介质中，漆酶（laccase）－邻苯二胺（o-phenylenediamine,OPDA）本系的酶催化反应呈现“超级活性”，并且酶催化反应中间体与产物2，3－二氨基吩嗪（2，3－diaminophemazine,DAP）的吸收光谱能很好的剥离分开。通过理论，表明酶催化反应中间体生成的初始速率与漆酶活性存在定量关系，采用初始速率法测定中间体的浓度，建立了一种基于检测酶催化反应中间体而测定漆酶活性的动力学分析新方法。该方法由于在反相胶束介质中采用初始速率法进行测定，具有较高的灵敏度和选择性。测定漆酶活性的线性范围为0－2.5U；检出限为0.033U。     

氨基羧酸铁(III)配合物催化分解过氧化氢

用碘量法研究了[Fe（EDTA],[FeⅢ(DCTA)],[FeⅢ(EGTA)]催化分解H2O2反应，提出了反应动力学方程为-d[H2O2]/dt=k[FE(Ⅲ)][H2O2][H ]^-1，认为氨基羧酸铁（Ⅲ）配合物催化分解H2O2反应为键式自由基反应，反应中间体包括过氧铁（Ⅲ）配合物，氨基羧酸铁（Ⅱ）和HO-，HO2-自由基。     

直流放电制备CN自由基及其LIF探测

CN自由基是研究化学反应动力学的典型自由基，CN的动力学行为，如CN＋O2的反应已成为研究自由基－自由基反应的模型体系[1]，同时也在许多实际过程如燃烧过程，星际气体的形成过程中起着重要的作用[2，3]．利用含有CN的化合物进行光解、放电、与亚稳态原子分子进行传能反应是目     

对位取代苯磺酸钠在溶液及界面的光反应研究

用自旋捕捉－ＥＳＲ方法研究了对位取代苯磺酸在水溶液中光化学行为，结果表明ｐＨ的改变及半导体胶体的存在都能影响其光解过程，使产生的中间体发生变化，发生光解过程中产生的中间体之一是硫中心自由基ＳＯ＾－３，在一定的ｐＨ范围还有Ｃ中心自由基和氢自由基生成，在较低ｐＨ范围，初始反应速率与ｐＨ值呈指数关系。     

动力学分析法研究生物反应活性中间体及其相关反应

评述了动力学分析法研究生物反应活性中间体的意义，存在的困难，研究方法及近年来 一多学科交叉与渗透领域的研究进展。     

分子间自由基正离子反应研究进展

自由基正离子含有一个正电荷和一对未成对电子,是很多有机化学反应的重要的活性中间体。文章综述了近几年自由基正离子反应研究进展,主要包括化学氧化剂诱导的自由基正离子反应、可见光诱导的自由基正离子反应、电诱导的自由基正离子反应等方面的研究。     

气相自由基反应动力学的光电离质谱研究

气相自由基能与各种气体发生快速反应,在大气化学、燃烧化学和星际化学等重要的化学过程中起着关键性的催化作用。许多实验方法(例如荧光法和吸收法)已经用于研究气相自由基反应动力学过程,并取得许多重要的成果,但这些技术局限于探测小分子自由基反应。流动管反应器和闪光光解结合光电离质谱的实验技术以其通用性、多重探测性、选择性和灵敏性等多种优势,成为研究气相自由基反应的主要实验方法。本文介绍利用高通量、高分辨、连续可调的同步辐射光电离质谱开展多种自由基反应研究所取得的一些独创性的成果。另外,该技术具有独有的时间分辨、能量分辨和异构体分辨的能力,能够广泛用于大气化学、燃烧化学和星际化学中一些重要的气相自由基(如烷氧自由基、烃类自由基等)反应宏观动力学过程的研究。     

Hypervalent iodine-mediated aziridination of alkenes: mechanistic insights and requirements for catalysis

By detailed study of the possible side reactions in the previously reported aziridination of alkenes with N-aminoheterocycles mediated by hypervalent iodine reagents, the requirements to make this reaction catalytic in iodoarene have been determined. The reaction requires an oxidant that will oxidise iodoarenes but that does not oxidise alkenes, but it is possible that no such oxidant actually exists! A method in which the hypervalent iodine reagent can be recycled without the need for reisolation is possible. Further study into the mechanism of this reaction gives tentative evidence that the reaction proceeds through formation of an aminoiodane that reacts directly with the alkene, contrary to previous literature reports in which an acetoxyamine intermediate is suggested. The temperature effect of this reaction is remarkable.     

Studies related to alkylations of enolate anions of 1,4-benzodiazepinones

Treatment of 1,4-benzodiazepinone derivatives with a Wittig-Horner reagent, led to the desired carbon? carbon bond formation at the amide carbonyl carbon atom in reasonable yield. An examination of this reaction has shown that only secondary amides can be used, indicating that this process requires the amide proton. This observation would exclude the accepted mechanism for Wittig-Horner type reactions (four membered spiro ring intermediate), and an alternate mechanism, that involves cleavage of the anion prior to addition of the reagent to substrate is proposed.     

Improved method for the solid-phase synthesis of oligoribonucleotide 5'-triphosphates

We have developed an improved solid-phase method for the synthesis of 5'-triphosphates (5'-TPs) of oligoribonucleotides. The method is based on the use of salicyl phosphorochloridite as the phosphitylating reagent and the improvement is characterized by the use of the highly reactive pyrophosphorylating reagent tris(tetra-n-butylammonium) hydrogen pyrophosphate instead of the conventional tri-n-butylammonium salt for the nucleophilic substitution reaction to form the cyclic ester intermediate. The improved method can be used to generate oligoribonucleotide 5'-TPs efficiently and reproducibly.     

Development of novel reagent for Hantzsch reaction for the determination of formaldehyde by spectrophotometry and fluorometry.

A novel reagent, acetoacetanilide (AAA), was introduced to the determination of formaldehyde based on Hantzsch reaction. A simple and highly sensitive fluorometric method was achieved by using AAA. The main advantages in the use of this reagent are: the reaction is carried out at room temperature without any heating system, the cyclization product based on Hantzsch reaction is soluble in water, and the product can be detected by spectrophotometry and fluorometry. The maximum absorption wavelength of the product occurs at 368 nm, and the maximum excitation and emission wavelengths are found at 370 and 470 nm, respectively. Several important experimental variables of the procedures were examined; particularly, the reaction temperature, reaction time, concentrations of reagents, and pH of the reagent solution were optimized for improving the detecting sensitivity. The calibration graph was linear in the range of 1 x 10(-7) - 1 x 10(-6) M or much higher concentrations. The limit of detection (LOD), based on three times of the standard deviation of the reagent blank, was 2.0 x 10(-8) M. The proposed method was applied to the determination of formaldehyde in environmental water samples. Many foreign species commonly existing in water samples did not interfere with the determination of formaldehyde in the proposed method.     

Water-soluble phosphinothiols for traceless staudinger ligation and integration with expressed protein ligation

The traceless Staudinger ligation is an effective means to synthesize an amide bond between two groups of otherwise orthogonal reactivity: a phosphinothioester and an azide. An important application of the Staudinger ligation is in the ligation of peptides at a variety of residues. Here, we demonstrate that the traceless Staudinger ligation can be achieved in water with a water-soluble reagent. Those reagents that provide a high yield of amide product discourage protonation of the nitrogen in the key iminophosphorane intermediate. The most efficacious reagent, bis(p-dimethylaminoethyl)phosphinomethanethiol, mediates the rapid ligation of equimolar substrates in water. This reagent is also able to perform a transthioesterification reaction with the thioester intermediate formed during intein-mediated protein splicing. Hence, the traceless Staudinger ligation can be integrated with expressed protein ligation, extending the reach of modern protein chemistry.     

A practical approach to the synthesis of 2,4-disubstituted oxazoles from amino acids

[reaction: see text] A new sequence for the synthesis of various 2,4-disubstituted oxazoles from alpha-amino acids is reported. The method is shown to be general and incorporates the reagent combination, triphenylphosphine/hexachloroethane, for cyclodehydration of intermediate alpha-acylamino aldehydes. Implementation of this reagent system for the conversion of alpha-acylamino ketones to oxazoles is briefly investigated.     

Development of Dipolar Proton Transfer Reaction Mass Spectrometer for Real-time Monitoring of Volatile Organic Compounds in Ambient Air

Volatile organic compounds (VOCs) in ambient air can participate in photochemical reactions, which lead to the generation of secondary pollutants such as ozone and aerosol. So real-time and accurate monitoring of atmospheric VOCs plays an important role in the study of the causes of air pollution. On the basis of proton transfer reaction mass spectrometry (PTR-MS) research, a novel dipolar proton transfer reaction mass spectrometer (DP-PTR-MS) for real-time and on-line monitoring of atmospheric VOCs was developed. Compared with conventional PTR-MS with one kind of reagent ion H₃O⁺, DP-PTR-MS had three kinds of reagent ions H₃O⁺, OH^?, (CH₃)₂COH⁺, which could be switched according to the actual detection need. So DP-PTR-MS can improve the qualitative ability and expand the detection range effectively. The reagent ion H₃O⁺ can be used for detecting VOCs whose proton affinities are greater than that of H₂O. The reagent ion OH^? can be used to identify VOCs cooperating with the reagent ion H₃O⁺, and can also be used for detecting some inorganic substances such as CO₂. The reagent ion (CH₃)₂COH⁺ can be used for accurately detecting NH₃ under interference elimination circumstances. The limit of detection (LOD) and sensitivity of DP-PTR-MS were measured by using six kinds of standard gases. The results showed that the LOD for detecting toluene was 7 × 10^?12 (V/V) and the sensitivity for detecting ammonia reached 126 cps/10^?9 (V/V). The ambient air in Hefei city was on-line and real-time monitored for continuous 78 h with DP-PTR-MS. The results showed that the newly developed DP-PTR-MS could be used for long-term and real-time monitoring atmospheric VOCs at the concentration of 10^?12 (V/V) level. DP-PTR-MS is an important tool to the study of the causes of atmospheric pollution and the monitoring of trace VOCs emissions.     

Transmetalation of palladium enolate and its application in palladium-catalyzed homocoupling of alkynes: a room-temperature, highly efficient route to make diynes

A novel pathway for the homocoupling reaction has been achieved using a similar protocol as the cross-coupling reaction. Ethyl bromoacetate is chosen to initiate the coupling reaction through oxidative addition to a Pd(0) species, and an PdBr(enolate) intermediate is formed. This intermediate can undergo double transmetalation with an alkynyl copper reagent, and reductive elimination produces a variety of diynes in high yields.     

Influence of low-frequency vibrations on the chemical reaction rate in the liquid phase for reagent association

A bistable state of a reaction system was theoretically shown to be possible for a multistage chemical reaction in the case of reagent association. The conditions for the bistability origin with a possible substantial change in the rate of reaction product formation were determined. The conditions for the appearance of oscillations of intermediate concentrations and the possibility for the origination of the corresponding acoustic frequencies were studied. The action of external vibrations with the frequency coinciding with that of intrinsic intermediate concentration oscillations can increase the reaction rate of reaction product formation.     

Evidence for the intermediacy of π-allylic metal complexes in the reaction of allylic halides with grignard reagent in the presence of transition metal halides

The reactions of allyl bromide and crotyl chloride with Grignard reagent catalyzed by π-allyl and crotyl metal complexes of nickel, cobalt, and iron, and the stoichiometric reaction of the complexes with the Grignard reagent have been examined. The similarity in catalytic behaviour of the complex and the corresponding metallic halide affords further evidence in support of the previous proposal that the π-allylic metal intermediate plays an important role in the catalytic reaction. The stoichiometric reaction suggests that the dependence of distribution of product in the catalytic process on the type of both allylic halide and metal is attributable to the facility of ligand exchange between the π-allylic complex and Grignard reagent.