微波辐射-酶耦合催化(MIECC)反应

将微波辐射用于非水相酶催化可以获得很多有别于常规加热下的反应结果.本文讨论了微波的非热效应在酶促反应中的表现,探讨了微波辐射对酶的结构、构象、活性及酶催化反应动力学的影响,以及微波辐射-酶耦合催化对反应的对映选择性、底物专一性、前手性选择性和区域选择性的影响.在大多数场合,适当的微波辐射不会损伤酶活而且可以提高反应速率,而对酶特异性的影响则不一而论.     

微波辐射-酶耦合催化(MIECC)反应

将微波辐射用于非水相酶催化可以获得很多有别于常规加热下的反应结果.本文讨论了微波的非热效应在酶促反应中的表现,探讨了微波辐射对酶的结构、构象、活性及酶催化反应动力学的影响,以及微波辐射-酶耦合催化对反应的对映选择性、底物专一性、前手性选择性和区域选择性的影响.在大多数场合,适当的微波辐射不会损伤酶活而且可以提高反应速率,而对酶特异性的影响则不一而论.     

微波技术应用于非水相酶学催化的研究进展

综述了近年来微波辐射在非水相酶学催化方面的应用,重点介绍了微波辐射对非水相酶催化反应动力学、反应产率、选择性及酶学性质的影响。参考文献43篇。     

大孔树脂对红霉素的吸附动力学研究

利用大孔吸附树脂Amberlite XAD16及HZ816对红霉素的吸附动力学实验,研究了温度、初始浓度、溶液pH值及搅拌速度等因素对吸附过程的影响.结果表明,Amberlite XAD16及HZ816对红霉素的吸附速率符合一级吸附动力学方程及颗粒内扩散方程,过程受液膜扩散阻力及颗粒内扩散阻力共同影响.同时,表观吸附速率常数与颗粒内扩散速率常数均随着温度的升高而增大,随着初始浓度的增大而增大,随着溶液pH值增大而增大,随着搅拌速度加快而增大.     

微波辐射-酶耦合催化(MIECC)反应

将微波辐射用于非水相酶催化可以获得很多有别于常规加热下的反应结果。本文讨论了微波的非热效应在酶促反应中的表现,探讨了微波辐射对酶的结构、构象、活性及酶催化反应动力学的影响,以及微波辐射-酶耦合催化对反应的对映选择性、底物专一性、前手性选择性和区域选择性的影响。在大多数场合,适当的微波辐射不会损伤酶活而且可以提高反应速率,而对酶特异性的影响则不一而论。     

微波法煅烧高岭土及合成洗涤助剂4A沸石

本文用微波法煅烧高岭土并合成4A沸石.与传统高温热处理法相比,微波法煅烧的高岭土其活化深度好,增白程度高,粒度细,能耗大为降低,显示了明显的优越性.本文还采用煅烧后的活性高岭土为原料,在微波辐射下进行4A沸石的合成,并用XRD、DTA、SEM、白度计、钙离子交换度等进行表征.与传统水热处理法相比,微波法所得样品在结晶度、白度和钙离子交换能力方面均显优势,且大大地加快了沸石晶化反应速率.经动力学处理,发现微波法合成4A沸石的晶核形成及晶体成长的表观活化能均有所下降,说明微波辐射能促进新相的形成,加快整个晶化反应速率.     

粒度对纳米氧化镍与硫酸氢钠水溶液反应动力学的影响

以纳米氧化镍与硫酸氢钠水溶液为反应体系,研究了不同粒度反应物反应的动力学参数,并讨论了粒度对动力学参数的影响.结果表明,反应物粒度对该反应的速率常数、指前因子和表观活化能均有显著的影响;随着反应物粒径的减小,速率常数增大,指前因子和表观活化能减小,且指前因子的对数和表观活化能分别与反应物粒径的倒数呈线性关系.     

微波辐射对淀粉结构及性质的影响

简单地介绍了微波对淀粉的辐射作用,并综述了微波辐射对淀粉形态结构和结晶结构以及淀粉凝胶化性质、热性质等影响的国内外研究进展,如微波辐射可改变淀粉颗粒形状、结晶结构及其结晶度.微波辐射时间及辐射能等技术参数能够改变淀粉的凝胶化性质,而淀粉的含水量也是重要的影响因素.淀粉的溶解性、润胀性和吸水性都会因微波辐射而较原淀粉下降.     

微波助离子液体中Y掺杂TiO_2光催化剂制备及微波强化光催化活性

在微波助离子液体介质中制备稀土元素Y掺杂改性TiO_2光催化剂,以提高催化剂的光催化降解活性,用XRD、SEM和BET等测试手段对催化剂结构进行表征;以甲基橙溶液和苯酚溶液为模拟污染物,分别在紫外光照(UV)和微波辐射-紫外光照(MW-UV)条件下考察TiO_2-Y催化剂的光催化活性;以对苯二甲酸作为荧光探针利用荧光技术检测TiO_2-Y催化剂表面所产生的羟基自由基,并对光催化降解反应进行动力学分析,探索了光催化降解反应机理.实验结果表明,通过优化反应条件后制得的TiO_2-Y催化剂具有较高光催化活性和热稳定性,在UV和UV-MW条件下降解甲基橙和苯酚溶液1.5h后,甲基橙降解率分别为98.3%和99.5%,苯酚降解率分别为97.5%和98.2%.荧光光谱分析表明,TiO_2-Y在MW-UV条件下产生的羟基自由基比UV条件下要多,因而微波辐照具有强化TiO_2-Y降解模拟污染物的作用;反应动力学数据分析表明,TiO_2-Y光催化降解甲基橙溶液反应呈现一级反应动力学规律,其表观速率常数K最大值为0.051 9min-1.     

微波加热对以槲皮素为甙元的黄酮甙的稳定性的影响

以乙醇为溶剂．分别采取微波和回流加热萃取法从番石榴叶中萃取槲皮素．高效液相色谱法测定槲皮素的萃取收率。对回流萃取液进行微波加热．槲皮素收率随微波加热温度的增加而显著增加。分别测定了温度为100、110、120℃的微波萃取动力学曲线以及60、70和78℃的回流加热萃取动力学曲线,计算结果显示,微波萃取和回流加热萃取均符合一级动力学方程,微波萃取槲皮素的活化能是回流加热萃取活化能的2倍多．平均表观速率常数是回流加热萃取的125倍。计算得到的活化能数据和实验结果均显示微波加热产生的高温可导致以槲皮素为甙元的黄酮甙发生分解。     

Kinetic modeling of vinyl acetate telomerization catalyzed by metal transition complexes under thermal and microwave heating

A kinetic model for the redox-initiated radical telomerization of vinyl acetate activated by microwave irradiation is presented. Four approaches based on the “microwave” or “thermal” effects were used to study the cases under microwave irradiation. One of the models assumes microwave-induced generation of radicals from monomer. The second model considers higher reaction temperatures than those reported in the experiments. The third model assumes that microwave radiation affects specifically catalyst-involved reactions. The fourth model is a combination of the second and third ones. The kinetic model captures well the effect of initiator, catalyst and solvent contents, as well as absence or presence of microwave irradiation, on polymerization rate and molecular weight development. Limiting monomer conversions and fairly constant values of number average molecular weight and molar mass dispersity were predicted by the model, which agrees with experimental observations.     

磁处理对乙酸乙酯皂化反应速率的影响

磁处理对乙酸乙酯皂化反应速率的影响邹立壮王晓玲张丕俭王风阁（烟台师范学院化学系烟台２６４０２５）周保学（山东师范大学化学系济南２５００１４）关键词磁处理乙酸乙酯皂化速率常数中图分类号Ｏ６４３．１本文对典型的水溶液中进行的二级反应——乙酸乙酯皂化反应进...     

微波-炭还原法处理一氧化氮的研究

报道了一种不需要催化剂而直接采用微波-炭还原技术处理-氧化氮(NO)的新方法.讨论了气体流量、反应温度、微波功率和施加微波时间对活性炭与一氧化氮发生还原反应的影响.比较了连续施加微波和间歇式施加微波方式下一氧化氮与活性炭发生化学反应转化为无公害的氮气(N₂)和二氧化碳(CO₂)的效率.研究结果表明,微波功率和反应器的类型及升温速率对一氧化氮与活性炭反应效率的影响较大.在连续施加微波时,一氧化氮与活性炭反应率可达98％以上.此外,还对一氧化氮与活性炭反应后的产物进行了表征.     

O(3P)原子与丁酮反应速率常数的测定

The measurement of the kinetic rate constant of the reaction of O(~3P) atoms with n-butanone at 288K is carried out. O(~3P) atoms were generated by a microwave discharge flow system and the residual concentration was detected by NO_2* chemiluminescence. The specific rate constant obtained is κ=(6.2±1.2)×10~(-15)cm~3 molecule~(-1) s~(-1) (T=288 K).A correlation diagram of molecular orbitals for the reaction is discussed.     

离子分子反应装置的建立及应用

本文报导离子分子反应装置的建成并测量了O~++N_2反应的速率常数k.O~+离子由微波放电和电极电离产生,经快速流动,用四极质谱仪检测到.中性分子N_2经支管进入流动管,并与O~+离子反应,在温度为298 K 时,测得该反应速率常数为k=(2.50±0.52)×10~(-12)cm~3·molec~(-1)·s~(-1)(T=298 K)     

Nonthermal Effect of Microwave Irradiation in Nonaqueous Enzymatic Esterification

Microwave has nonthermal effects on enzymatic reactions, mainly caused by the polarities of the solvents and substrates. In this experiment, a model reaction with caprylic acid and butanol that was catalyzed by lipase from Mucor miehei in alkanes or arenes was employed to investigate the nonthermal effect in nonaqueous enzymatic esterification. With the comparison of the esterification carried by conventional heating and consecutive microwave irradiation, the positive nonthermal effect on the initial reaction rates was found substrate concentration-dependent and could be vanished ostensibly when the substrate concentration was over 2.0 mol L⁻¹. The polar parameter log P well correlates the solvent polarity with the microwave effect, comparing to dielectric constant and assayed solvatochromic solvent polarity parameters. The log P rule presented in conventional heating-enzymatic esterification still fits in the microwaved enzymatic esterification. Alkanes or arenes with higher log P provided positive nonthermal effect in the range of 2 ≤ log P ≤ 4, but yielded a dramatic decrement after log P = 4. Isomers of same log P with higher dielectric constant received stronger positive nonthermal effect. With lower substrate concentration, the total log P of the reaction mixture has no obvious functional relation with the microwave effect.     

Influence of microwave irradiation on enzyme kinetics

The in vitro effect of 2.45 GHz microwave irradiation on porcine pepsin activity under controlled temperature and absorbed microwave power via kinetic parameters was evaluated. Kinetic study with respect of time of irradiation demonstrated the existence of an inactivation effect of microwaves at pH 2 on pepsin molecule. Bovine serum albumin (BSA)-bromphenol blue (BPB) complex was used as substrate for the assay of pepsin by kinetic method. Depending on absorbed microwave dose, the degree of caused inactivation varies from 39.11 to 45.91% for 5 and 20 min of pepsin MW irradiation, respectively. The V _maxapp and K _mapp were calculated for low (5 min of MW irradiation) and higher specific absorbed dose (20 min of MW irradiation), as well as for untreated enzyme, from double reciprocal Lineweaver-Burk plot. The effect of microwaves on substrate (BSA-BPB complex) was also investigated. For reaction performed with MW irradiated substrate for 5 min the reaction rate was decreased for 15.15%, while for 20 min of substrate irradiation reaction rate was decreased for 25.52% compared to the control reaction. The article is published in the original.     

Non-thermal effects of microwaves on protease-catalyzed esterification and transesterification

The non-thermal effects of microwave irradiation on enzyme-catalyzed reactions have been evaluated by keeping the reaction temperature constant during irradiation. Subtilisin-catalyzed transesterification and α-chymotrypsin-catalyzed esterification have been carried out in six solvents of differing polarities and at three different temperatures. In all cases, microwave irradiation was found to increase the initial reaction rates by 2.1-4.7 times at all hydration levels. It is also shown that microwave irradiation can be used in conjunction with other strategies (like pH tuning and salt activation) for enhancing initial reaction rates.     

微波作用下的多肽固相缩合反应及动力学研究

分别在微波作用以及传统加热两种方式下, 研究了Fmoc-Val-OH与NH₂-Tyr(t-Bu)-Wang树脂的固相缩合反应及其动力学. 测定了温度变化对反应速率的影响, 并获得了两种方式下的缩合反应的宏观动力学参数: 300 W微波作用下表观缩合反应级数为2.3, 活化能为104.7 kJ/mol; 传统方法中表观反应级数为2.9, 活化能为142.4 kJ/mol. 微波作用将常规条件下的连接率由68%提高到95%, 而所需时间降为常规条件的1/14.