半胱氨酸和谷胱甘肽氧化反应动力学的研究进展

本文对半胱氨酸和谷胱甘肽的氧化反应动力学的研究进展进行了综述。阐述了含硫氨基酸的生化性质、应用及其重要作用。分别对半胱氨酸、谷胱甘肽的氧化产物分析和动力学机理的研究成果进行了介绍。提出了巯基氨基酸及肽氧化反应动力学研究难点和可行的研究手段及方法。     

碳纳米管的氧化稳定性及反应动力学

碳纳米管自被发现以来 [1] ,已分别通过 HRTEM[1]、Raman[2 ,3]、ED[4 ]、STM和 STS[5]等对其结构、形态、层间距、直径分布、螺旋度、管壁及顶端的电子结构等物理性质进行了详细研究和表征。而碳纳米管在空气中的抗氧化性能的研究虽有文献报道 ,但关于纳米碳管氧化反应动力学的报道则相对较少[6～ 9] 。由于作为催化剂载体是碳纳米管在化学领域最具潜在的应用之一 ,因此 ,研究碳纳米管在空气中的抗氧化性及氧化反应动力学是一项很有意义的工作。本文利用 TG-DTA方法研究了碳纳米管在空气中的抗氧化性 ,同时与 C6 0 和石墨的实验结…     

醛类自氧化振荡反应动力学的研究

研究了醛类在乙酸和水混合溶剂中以Ｃｏ＾２＋和Ｂｒ＾－为催化剂的自氧化振荡反应。得知某些取代苯甲醛和脂肪醛在适当条件下能发生振荡，并研究了苯甲醛、正丁醛和乙醛的周期受动力学制约的影响，提出了相关的机理模型。依此模型以Ｇｅａｒ方法计算其振荡周期基本与实验结果相符。     

甲酸氧化反应动力学反应装置的改进

进行甲酸氧化反应动力学实验时,需要在反应前用去离子水清洗反应装置内壁。由于原反应装置（图1）存在缺陷,反应装置口使用橡皮塞,反应装置底部无活塞,每次换液时,需取出橡皮塞,倒出废液,洗净后再放回,操作不方便,而且容易损坏反应装置。在实验时,要将配制好的液体（水、溴、溴试剂、盐酸）加入到反应装置内,恒温并等待Br^-生成;但由于橡皮塞孔径较大,在加入甲酸之前,易有液体从橡皮塞孔径挥发,使液体浓度发生改变,影响实验结果。     

过氧乙酸催化氧化亚硫酸钙的反应动力学

利用间歇式反应装置, 研究了过氧乙酸催化氧化亚硫酸钠的本征反应动力学, 得到各反应物的分级数及表观活化能. 在此基础上, 利用鼓泡式反应装置, 通过改变pH、亚硫酸钙浓度、过氧乙酸浓度、空气流量及温度, 研究了过氧乙酸催化氧化亚硫酸钙的宏观反应动力学.     

加压氧化气氛下CaO固硫反应和动力学研究

在加压氧化气氛下研究CaO和SO2 的反应并对该过程进行动力学研究。结果表明 :低温时CaO和SO2 反应的直接产物是CaSO3 ;产物中的CaSO4 是CaSO3 氧化和歧化反应的双重结果。在更高温度 (6 5 0℃ )下发生的是CaO的直接硫酸化反应 ;压力相同时 ,升高温度反应速率和转化率增加 ,但存在一最佳的温度为 85 0℃左右。同一温度下 ,随压力的增加 ,CaO的转化率显著增加。包含可变有效扩散系数的未反应核模型 (EUSCModel)能较好地描述加压下CaO的固硫反应过程。在该模型中 ,用于决定反应速率控制步骤的Thiele模数定义为转化率的函数。Thiele模数和转化率的关系表明整个固硫反应过程是动力学和扩散的共同效应 ;计算得出动力学控制和扩散控制下的表观活化能分别为 43 87kJ·mol-1和 5 6 79kJ·mol-1。     

植物焦炭氧化中的平行反应及其动力学解析

通过建立多组分平行反应模型和开展非线性动力学解析, 理论上探索植物焦炭氧化中的平行反应以及其对焦炭氧化反应活性影响的机制. 运用高温管式炉并通入高纯氮气制备植物焦炭, 热处理温度分别设定为450、520和800 ℃. 运用同步热分析仪开展空气气氛中植物焦炭线性升温氧化实验, 并通过对热重和质量损失速率实验数据进行拟合以获取焦炭氧化动力学参数值. 解析结果证实, 对于低中热处理温度(450和520 ℃)制得的焦炭, 其质量损失速率及对应的热流率曲线的变化特征主要是由残留木质素、无定形碳及粗脂肪和粗蛋白等其它反应物质的平行氧化反应叠加而成; 当热处理温度达到800 ℃时, 焦炭中活性物质基本为无定形碳, 氧化则可简化为无定形碳的单步反应. 残留木质素氧化反应的活化能最低, 范围为86～147 kJ·mol^-1, 相应的温度作用区间为300～480 ℃; 无定形碳的活化能为174～208 kJ·mol^-1, 反应温度在370～520 ℃之间; 其它物质的反应活化能为214～225 kJ·mol^-1, 温度作用区间在420～510 ℃之间. 焦炭的氧化活性主要由残留木质素含量决定. 随着热处理温度升高, 残留木质素含量降低, 同时另两个反应组分的氧化活化能均有所增大, 导致焦炭的氧化反应活性下降.     

肾上腺素电氧化生成肾上腺素醌的反应动力学

使用以铂片为工作电极的长光程薄层电化学池,采用单电位阶跃计时吸收法测定了1．0mol·L^-1H2SO4和冰醋酸中,肾上腺素电氧化生成肾上腺素醌的动力学参数．实验结果表明：肾上腺素在1．0mol·L^-1H2SO4介质中比在冰醋酸中容易被氧化．     

N溴代丁二酰亚胺氧化醇反应的热动力学研究

氧化反应是有机化学中的一种重要反应类型,也是有机化学、化学工程和生物学家们研究的重点之一.但因其机理复杂,至今未见到用热动力学理论探索氧化反应体系的报道. N溴代丁二酰亚胺(NBS)是良好的溴化试剂,在不同反应条件下,它既可和不饱和键发生加成反应,也可在水溶液中作为次溴酸的来源,还可作为有效的氧化剂和脱氢剂.Reich和Reichstein首先报道了用N溴代乙酰亚胺将仲醇缓慢氧化为酮,Fieser等人报道了NBS的氧化作用.本文用RD-1型热导式自动量热计研究了35℃下NBS氧化异丙醇及环己醇2个反应体系,计算了反应速率常数,对反应的动力学及其机理提出了较合理的解释.     

甲醇在Pt-Sn/Pb电极上的氧化行为 Ⅱ.氧化反应动力学特征的研究

在甲醇燃料电池体系中,已确信甲醇会在铂电极上形成强吸附的中间物种:(1)这一吸附中间物种可与从水中得到的氧发生反应:(2)(3)为研究反应机理,采用过各种实验手段分析B_(ad(?))。本工作采用旋转园盘电极的电化学实验方法研究了甲醇氧化反应过程的中间物种,并求取反应过程的动力学参数以探讨氧化反应的机理,进而分析了双金属催化剂的作用机理。     

硫脲在10-甲基吩噻嗪修饰碳糊电极上的电催化氧化及电分析方法研究

研究了硫脲(Thiourea,Tu)在10-甲基吩噻嗪修饰碳糊电极(MPT/CPE)上的电催化氧化行为.结果表明,Tu在裸碳糊电极(CPE)上的直接电化学氧化过程十分迟缓,MPT/CPE对Tu的电化学氧化具有良好的催化作用.用计时电流法(CA)测定了Tu在MPT/CPE上的电极过程动力学参数,测得电荷传递系数α=0.61,电催化氧化反应的速率常数k=(1.96±0.10)×104(mol/L)-1·s-1.用方渡伏安法(SWV)测得催化氧化峰电流与Tu浓度在1.0×10-6～8.0×10-3mol/L范围内呈良好的线性关系,线性回归方程为,Ips(μA)=10.836c(10-3mol/L)+5.326,R=0.9984,检出限为2.2×10-7mol/L(S/N=3).方法可用于Tu的电化学法测定.     

典型醇类物质超临界水氧化反应途径研究

采用自主设计的连续流动气封壁超临界水氧化反应装置,研究了典型醇类物质甲醇、乙醇和异丙醇在超临界水中氧化的反应途径,并归纳了醇类物质超临界水氧化反应的规律及特点。研究结果表明,甲醇超临界水氧化反应的主要中间产物为甲醛,同样条件下转化率较乙醇和异丙醇低;乙醇和异丙醇超临界水氧化反应的主要中间产物为丙酮、乙酸、乙醛和甲醇等。三种醇超临界水氧化过程中均涉及到大量活性自由基的相互作用,表现为脱氢、裂解和聚合等反应形式;产物包括碳链增长、不变、降低三种类型。总体来看,醇类物质超临界水氧化反应的趋势是向碳链降低的方向进行,即通过一系列中间产物最后生成CO₂和水。     

The novel usage of thiourea nitrate in aryl nitration简

Thiourea nitrate （TN） was easily prepared from thiourea and nitric acid to explore its use as a new nitration reagent, Nitrations of various aromatic compounds utilizing TN in concentrated sulfuric acid were studied, TN could convert aromatic compounds to the corresponding nitrated derivatives with various abnormal yields under mild conditions. The results suggested that the reaction mechanism might be different from those of traditional nitration reagents.     

CO oxidation over the Pt-Rh system. 2. Reaction on an alloy

The oxidation of CO over thin films of a Pt-Rh alloy prepared by sequential vacuum evaporation of the metals on an inert support has been investigated at low pressures (P < 2'10^-5 mbar). The results are compared with the data on the individual surfaces of Pt and Rh. It is found that the activity of the alloy is intermediate between the activities of the individual metals. The effect of alloy formation on the catalytic activity in CO oxidation is discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

CO oxidation over a Pt-Rh system. 1. Reaction on individual metals

The reaction of CO oxidation over thin films of rhodium and platinum prepared by vacuum evaporation of the metals on an inert support has been investigated at low pressures (P < 2×10^-5 mbar). Rhodium has been found to be more active than platinum in this reaction. The reasons of the higher activity of Rh are discussed.     

Theoretical study on the oxidation mechanism of thiourea by hydrogen peroxide with water and hydroxyl assistance

This article presents a theoretical study on the oxidation reaction of thiourea by hydrogen peroxide in water or alkaline solutions using density functional and ab initio theories. This work also focuses on the analysis of the thermodynamic and kinetic properties of the predicted oxidation mechanism of thiourea using density functional and ab initio theories. The calculated results show that the activation energies, activation enthalpies, and activation Gibbs free energies of the reaction decreased and the releasable reaction energies, enthalpies and Gibbs free energies increased with the cooperation of water or hydroxyl anion. We conclude that the oxidation reaction of thiourea by hydrogen peroxide in water or alkaline solutions was easier and more completed than that in the gas state. The calculated results are consistent with the experiments.     

CO oxidation over the Pt-Rh system. 3. Reaction on a heterophase surface

The reaction of the CO oxidation over a Pt-Rh heterophase surface, which represents 10-20 nm platinum particles located on a rhodium film, which in turn is deposited on an inert support, has been investigated at low pressures (P < 2'10^-5 mbar). The results are compared with the data for the clean surfaces of Pt and Rh. In the high-temperature range, the rate of CO₂ formation on the heterophase surface is found to be higher than the sum of the rates on individual metals corrected by the surface area of the different metals. The nature of the synergistic effect in the CO oxidation is discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Study on dynamics characteristics of wet air oxidation of non-ionic surfactants

Wet air oxidation is an effective method to deal with highly concentrated nondegradable emulsification wastewater which contains non-ionic surfactants. This article illustrates our investigation on dynamic characteristics of wet air oxidation of typical non-ionic surfactants like polyether, phenol ether and widely used alcohol ether. The experimental results indicated that the oxidation rate of polyether, phenol ether and alcohol ether obviously ascended as the temperature rose. A good oxidation effect was available at 240℃. The TOC removal rate could reach 88.0%, 94% and 91.5%, after 125 min reaction. Alcohol ether was prone to an easier oxidation compared with polyether and phenol ether when the temperature was 220℃ or below. The oxidation rate of alcohol ether was higher than that of polyether at 160℃, while the oxidation rate of polyether was higher than that of phenol ether between 180℃ and 220℃. During the later period of the reaction at 240℃, the rate of phenol ether was higher than that of alcohol ether, which was still higher than that of polyether. Partitioned first order kinetics model analy-sis showed that the apparent activation energy of alcohol ether was lower than that of both polyether and phenol ether in the leading stage and lagging stage, and it was easy to acquire a higher oxidation rate for alcohol ether at low temperature. Three parameter general dynamics model analyses showed that the reason why the oxidation rate of polyether was lower than that of alcohol ether was that the oxidation of polyether was more apt to be converted to intermediate production than that of alcohol ether, whereas between 200℃ and 220℃, the direct oxidation rate of polyether and the oxidation rate of intermediate product were obviously lower than that of alcohol ether. The apparent activation energy of direct and indirect oxidation of polyether was 43.37 and 60.45 kJ?mol?1, respectively, while the corre-sponding apparent activation energy of alcohol was 38.74 and 58.09 kJ·mol?1, respectively.     

Reaction dynamics and statistical theory for the growth of hydrogen bonding clusters

The similarities between the formation of hydrogen bonds and polycondensation reactions are stated from the statistical viewpoint, and then taking the hydrogen bonding system of AaDd type as an example, the growing process of hydrogen bonding clusters is investigated in terms of the theory of reaction dynamics and statistical theory for polymeric reactions. The two methods lead to the same conclusions, stating that the statistical theory for polymerization is applicable to the hydrogen bonding systems. Based on this consideration, the explicit relationship between the conversions of proton-donors and proton-acceptors and the Gibbs free energy of the system under study is given. Furthermore, the sol-gel phase transition is predicted to take place in some hydrogen bonding systems, and the corresponding generalized scaling laws describing this kind of phase transition are obtained.     

Reaction mechanism of aerobic oxidation of alcohols conducted on activated-carbon-supported cobalt oxide catalysts

Catalytic performances and the reaction mechanism of Co(3)O(4)/AC (AC=activated carbon) for aerobic oxidation of alcohols carried out in the liquid phase were investigated. Co(3)O(4)/AC shows a high activity for aerobic oxidation of benzyl alcohol, comparable to noble metal catalysts (e.g., Au/AC) even in the absence of additives or promoters (e.g., NaOH). Changing preparation conditions, such as treatment temperature and/or time, can affect the catalytic performances of Co(3)O(4)/AC, due to decomposition of surface groups of the carbon support. Careful studies show that low alcohol conversions are obtained with either Co(3)O(4) or AC alone, which indicates that the high conversion observed over the Co(3)O(4)/AC is due to a synergistic effect between Co(3)O(4) and AC. Parallel experiments using a high-surface-area covalent triazine framework or oxygen-inert carbon nitride as support for the Co(3)O(4) catalyst also show lower conversions, which suggest that the ability of AC (in Co(3)O(4)/AC) to activate molecular oxygen is essential for the reaction. FTIR and XPS spectra taken from catalysts before and after the reaction confirm that oxygen activation proceeds mainly on the carbon support. As a result, it can be assumed that the alcohol dehydrogenation step proceeds on the metal oxide, whereas the oxygen activation step occurs mainly on the carbon support.