己内酰胺类离子液体的热力学性质(英文)

A series of caprolactam ionic liquids(ILs) containing incorporated halide anions were synthesized.Their physical properties,such as melting points,heats of fusion and heat capacities,were measured by differential scanning calorimeter(DSC).The results indicate that these ionic liquids exhibit proper melting points,high value of heats of fusion,and satisfying heat capacities which are suitable for thermal energy storage applications.     

复合离子液体催化碳酸乙烯酯水解制备乙二醇(英文)

An ionic liquid system of [Bmim]X/[Bmim]OH (X Cl, BF4, and PF6,) was developed for the hydrolysis of ethylene carbonate to ethylene glycol. The important parameters, such as the variety of ionic liquids, molar ratio of [Bmim]X to [Bmim]OH, amount of ionic liquid, molar ratio of water to ethylene carbonate, reaction temperature, pressure and reaction time, were investigated systematically. Excellent yield (>93%) and high selectivity (99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions, the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.     

离子液体捕集二氧化碳的研究进展(英文)

Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.     

氯化胆碱·xZnCl_2离子液体在生物柴油制备中的应用(英文)

The inexpensive and moisture-stable Lewis-acidic ionic liquids were prepared and applied for transesterification of soybean oil to biodiesel.The influences of molar ratio of methanol to soybean oil,reaction temperature and amount of ionic liquids were investigated.The transesterification of soybean oil to biodiesel catalyzed by choline chloride·xZnCl2 ionic liquids showed many advantages such as mild conditions and lower cost.On the other hand,the non-ideal yield and complicated separation between biodiesel and soybean oil were also investigated and analyzed.The improvement on the systems of choline chloride·xZnCl2 was proposed for further investigation.     

具有羧酸官能团的功能性离子液体萃取分离钇的研究(英文)

A new kind of hydrophobic ionic liquids [1-alkyl-3-(1-carboxylpropyl)im][PF6] has been synthesized,and their extraction properties for Y(III) in the nitric acid medium was also investigated.The effects of extractant concentration,equilibrium pH of aqueous phase,salt concentration,temperature etc.were discussed.The results show that this kind of Task-Specific Ionic Liquid(TSIL) needs to be saponified before being used for the Y(III) ex-traction,and the extraction is acid dependent,and the extraction efficiency increases with the aqueous phase acidity decreasing.Furthermore,the loaded organic phase is easy to be stripped;more than 95% Y(III) could be stripped from the loaded organic phase when the stripping acidity is higher than 0.07 mol?L?1.The slope analysis technique is used to investigate the extraction mechanism,and a possible cation-exchange extraction mechanism is proposed in the present extraction system.     

1-丁基-3-甲基咪唑二氰胺盐离子液体的热稳定性和热分解动力学(英文)

Thermal stability and thermal decomposition kinetics of 1-butyl-3-methylimidazolium dicyanamide ([bmin+][N(CN) ]2-) were investigated using both isothermal and non-isothermal thermogravimetric analyses (TGA) under high pure nitrogen as carrier gas. The long-term thermogravimetric studies revealed that the highest temperature used should be 110 °C, at which [bmin+][N(CN)2-] lost less than 10% by mass in 10 hours. The non-isothermal activation energy values determined using Friedman and ASTM methods were (150±13) and (147±2) kJ·mol –1 , respectively. Multivariate non-linear-regression methods showed that expanded Fn and CnB models were the best fit models with highest correlation coefficient of 0.9994, and the apparent activation energies were consistent with iso-conversional methods.     

青霉素酰化酶基因工程菌 E.coli A_(56)(pPA22)水解青霉素 G 的动力学

用初速度法测定了青霉素酰化酶基因工程菌 E.coli A_(56)(pPA22)游离细胞和固定化细胞水解青霉素 G 的动力学常数,并进行了动力学模型的检验。该菌体酶活高,米氏常数小,固定化后米氏常数和苯乙酸抑制常数增大,底物抑制常数和6-APA 抑制常数没有变化。通过青霉素 G 裂解过程的考察,验证了青霉裂解动力学模型的适用性及动力学常数测定的可靠性。     

Ag/P(St-MMA)纳米复合高分子微球固定化青霉素酰化酶的研究

通过溶剂热法和无皂乳液聚合相结合,制备了P(St-MMA)高分子纳米微球.并以吸附沉积的方式在其表面沉积了Ag金属纳米粒子,最后将青霉素酰化酶共价连接在微球表面.初步研究了微球直径、银的质量分数等因素对固定化酶活力的影响.结果显示随着微球直径减小,固定化酶的偶联率和活力逐渐增加;银纳米粒子最多将固定化酶的偶联率和活力分别提高了42%和72%,固定化酶的最大表观活力(以干重记)达到了1 869 u/g,明显高于其它高分子载体固定化青霉素酰化酶的活力;实验证明银纳米粒子在青霉素水解过程中没有催化活力,但能大大提高青霉素酰化酶的催化活力.     

青霉素酰化酶固定化载体材料研究进展

就青霉素酰化酶固定化载体材料的研究和应用进行了论述。重点介绍了功能基化高分子聚合物、含环氧基高分子聚合物、离子型层状水滑石和介孔分子筛等新型载体的结构特性和对青霉素酰化酶的固定化作用,并对近年来固定化生物酶载体材料的发展动向和趋势加以评述和展望。     

以壳聚糖为载体固定化青霉素酰化酶的研究

介绍了以壳聚糖为载体固定化青霉素酰化酶需首先制备壳聚糖颗粒 ,使用戊二醛、甲醛、乙二醛 3种活化剂处理所得的壳聚糖颗粒 ,确定了以戊二醛为活化剂交联其上的氨基共价结合青霉素酰化酶的固定化方法。从戊二醛的浓度、pH值、固定化时间、固定化pH值、酶用量等条件摸索了最佳固定化条件 ,获得了酶活力为4 0 0 0 0U/ (g·h)、回收率为 5 0 %左右的固定化青霉素酰化酶。     

新型复合材料MnFe_2O_4@SiO_2-NH_2的制备及其固定青霉素G酰化酶

通过溶剂热法制备出高磁性的聚合物微球MnFe_2O_4,经正硅酸乙酯(TEOS)和3-氨基丙基三乙氧基硅烷(APTS)对微球表面进行改性修饰,制备出新型复合材料MnFe_2O_4@SiO_2-NH_2,并将其用于固定青霉素G酰化酶。在Si/Fe比为7 mmol/g、n(TEOS)∶n(APTS)=1∶1时,固定化酶PGA/MnFe_2O_4@SiO_2-NH_2在37℃下水解青霉素G钾合成6-氨基青霉烷酸,表观酶活为1 660 IU/g、载酶量为107.1 mg/g、比酶活为15.5 IU/mg、活性回收率为46.9%。经过6次重复使用,保留初始酶活的81.3%,在使用中固定化酶在磁场的作用下能够快速沉降与产物分离。     

Stabilization of native penicillin G acylase by ionic liquids

Five different ionic liquids, based on dialkylimidazolium cations associated with perfluorinated and bis{(trifluoromethyl)sulfonyl}imide anions, were used to investigate the scope and limitations of these new solvents as media for penicillin G acylase‐catalyzed reactions. Deactivation of the native enzyme in ionic liquids (ILs) and in organic solvents (toluene, dichloromethane and 2‐propanol) at low water content and 40 °C was investigated using the hydrolysis of penicillin G as activity test. Native penicillin G acylase shows greater stability in IL media than in organic solvents. For example, a half‐life time of 23 h was obtained in 1‐ethyl‐3‐methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [emim⁺][Tf₂N^?], which was about 2000‐fold higher than that in 2‐propanol. An enhancement of the PGA stability was observed by the presence of substrate in ionic liquids based on tetrafluoroborate and hexafluorophosphate anions, achieving the highest increase of the half‐life time in 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim⁺][PF₆^?]), which was about 9‐fold higher than the half‐life time in the absence of substrate. Copyright © 2007 Society of Chemical Industry     

青霉素酰化酶在高磁性无机复合材料上的固定化研究

利用共沉淀方法制备出饱和磁化强度为66.2emu/g的Fe3O4,通过溶胶-凝胶进行氨基功能化改性后饱和磁强度仍高达27.2e-mu/g,其剩磁和矫顽力均为0。对不同反应工艺制备的磁性复合载体进行固定化青霉素酰化酶（PGA）,当戊二醛的浓度为0.02%时,固定化酶的起始表观酶活为3198.38 IU/g,当戊二醛的浓度为0.1%时,进行持续间歇8次使用后,活性为起始活性的86.1%。     

Incorporating Lanthanum into Mesoporous Silica Foam Enhances Enzyme Immobilization and the Activity of Penicillin G Acylase Due to Lewis Acid-Base Interactions

Penicillin G acylase (PGA) has been immobilized on a lanthanum-incorporated mesostructured cellular foam (La-MCF) support by using the interaction between the strong Lewis acid sites on the surface of La-MCF and the free amino groups of lysine residues of PGA. The La-MCF support was successfully synthesized in situ through the addition of a citric acid (CA) complexant. The results of pyridine-IR spectroscopy show the presence of strong Lewis acid sites on the surface of the prepared La-MCF (with CA), attributed to the incorporation of lanthanum species into the framework of MCF. Through interaction with the strong Lewis acid sites, the enzymes can be firmly immobilized on the surface of the support. The results indicate that PGA/La-MCF (with CA) exhibits a high specific activity and greatly enhanced operational stability. For the hydrolysis of penicillin G potassium salt, the initial specific activity of PGA/La-MCF (with CA) reaches 10023 U/g. Even after being recycled 10 times, PGA/La-MCF (with CA) retains 89 % of its initial specific activity, much higher than the 77 % of PGA/Si-MCF.     

基于大分子拥挤原理的介孔二氧化硅中青霉素酰化酶的共价组装

To improve the covalent immobilization of penicillin acylase （PA）, macromolecular crowding theory was applied to its immobilization. Influence of mass ratio of enzyme to the silica, as well as, activation time with glutaraldehyde on the activity of assembled PA, was studied. In the mesopores, the effect of fl-cyclodextrin （β-CD） on the immobilization of the enzyme was also investigated. It was remarkable that the coupled yield and relative activity reached 99.5% and 92.3%, respectively, when penicillin acylase assembled covalently in the mesopores. The results here indicate that mimicked macromolecule crowding could significantly ameliorate the performance of covalently immobilized PA.     

磁性微粒对青霉素G酰化酶的固定化研究

将无机磁性粒子Fe3O4与有机材料海藻酸钠结合起来制成一种复合的磁性微粒,并将其进行表面修饰,通过化学共价法来固定青霉素G酰化酶。通过扫描电镜等对微粒进行形态学观察,并用傅立叶红外图谱表征微粒表面修饰基团。酶学性质研究表明,该微粒固定化的青霉素G酰化酶的最适pH值为7.5,最适温度为40℃。固定化酶与底物的亲和力有所降低,但是稳定性显著提高。重复催化研究结果表明,固定化酶具有比游离酶更广泛的温度及pH值适用范围,并且具有良好的热稳定性、可循环使用性和贮存稳定性。     

反胶束体系中青霉素酰化酶活性及稳定性研究

反胶束体系是一种新型的酶反应介质体系。构建合适的反应体系，使青霉素酰化在该体系中保持较高的酶活性，是实现反胶束体系中酶法合成头孢类抗生素的关键所在。本文分别考察了青霉素酰化酶在CTAB／正己醇和CTAB／异辛烷／正己醇两种反应胶束体系中不同水含量和pH值对酶活力的影响。结果表明：包埋于CTAB／异辛烷／正己醇反胶束体系中的青霉素酰化酶在W0为14，pH为7．2时表现出较高的酶活性。试验中还考察了不同温度对包埋于CTAB／异辛烷／正己醇反胶束体系中的青霉素酰化酶活力的影响，并与游离酶液进行了比较，该酶在所采用的反胶束体系中的最适水解反应温度为39℃，较游离酶液的最适水解温度升高了2℃。同时酶的热稳定性亦较游离酶液有所提高，表现在CTAB／异辛烷／正己醇反胶束体系中，经50℃保温240min，酶活保留率为76．0％，而在同样条件下游离酶液仅为36．5％。     

Hydrolysis of Penicillin G by Penicillin G Acylase Immobilized on Chitosan Microbeads in Different Reactor Systems

The kinetic parameters for penicillin G hydrolysis in systems with penicillin G acylase from Escherichia coli (free and immobilized on activated chitosan microbeads produced by electrostatic extrusion) were determined. The obtained kinetic results indicated that both systems (free and immobilized) are inhibited by high concentrations of the substrate (penicillin G) as well as by products of the reaction (6‐aminopenicillanic acid and phenylacetic acid). The microbeads appeared convenient for penicillin G acylase immobilization reducing negative inhibitory effects. The hydrolysis was also investigated in a packed bed reactor. The derived kinetic model predicted good hydrolysis rates in the reactor while the system with recirculation of the reaction mixture proved to be a potentially favorable solution providing operation at low shear stresses and possibly higher hydrolysis rates than in the packed bed reactor alone.