离子液体修饰超顺磁性纳米颗粒用于青霉素G酰化酶固定化(英文)

Functionalized ionic liquids containing ethyoxyl groups were synthesized and immobilized on magnetic silica nanoparticles(MSNP) prepared by two steps,i.e.,Fe3O4 synthesis and silica shell growth on the surface.This magnetic nanoparticle supported ionic liquid(MNP-IL) were applied in the immobilization of penicillin G acylase(PGA).The MSNPs and MNP-ILs were characterized by the means of Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),transmission electron microscopy(TEM),and vibrating sample magnetometer(VSM).The results showed that the average size of magnetic Fe3O4 nanoparticles and MSNPs were ~10 and ~90 nm,respectively.The saturation magnetizations of magnetic Fe3O4 nanoparticles and MNP-ILs were 63.7 and 26.9 A?m2?kg?1,respectively.The MNP-IL was successfully applied in the immobilization of PGA.The maximum amount of loaded enzyme was about 209 mg?g?1(based on carrier),and the highest enzyme activity of immobilized PGA(based on ImPGA) was 261 U?g?1.Both the amount of loaded enzyme and the activity of ImPGA are at the same level of or higher than that in previous reports.After 10 consecutive operations,ImPGA still main-tained 62% of its initial activity,indicating the good recovery property of ImPGA activity.The ionic liquid modified magnetic particles integrate the magnetic properties of Fe3O4 and the structure-tunable properties of ionic liquids,and have extensive potential uses in protein immobilization and magnetic bioseparation.This work may open up a novel strategy to immobilize proteins by ionic liquids.     

New Alkylation Route of Benzene with Ethylene Catalyzed by [bmim]Cl/FeCl_3 Ionic Liquid

Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR     

Prediction and verification of heat capacities for pure ionic liquids

The heat capacity of ionic liquids is an important physical property,and experimental measuring is usually used as a common method to obtain them.Owing to the huge number of ionic liquids that can be potentially synthesized,it is desirable to acquire theoretical predictions.In this work,the Conductor-like Screening Model for Real Solvents(COSMO-RS) was used to predict the heat capacity of pure ionic liquids,and an intensive literature survey was conducted for providing a database to verify the prediction of COSMO-RS.The survey shows that the heat capacity is available for 117 ionic liquids at temperatures ranging 77.66-520 K since 2004,and the 4025 data points in total with the values from 76.37 to 1484 J·mol~(-1)·K~(-1) have been reported.The prediction of heat capacity with COSMO-RS can only be conducted at two temperatures(298 and 323 K).The comparison with the experimental data proves the prediction reliability of COSMO-RS,and the average relative deviation(ARD) is 8.54%.Based on the predictions at two temperatures,a linear equation was obtained for each ionic liquid,and the heat capacities at other temperatures were then estimated via interpolation and extrapolation.The acquired heat capacities at other temperatures were then compared with the experimental data,and the ARD is only 9.50%.This evidences that the heat capacity of a pure ionic liquid follows a linear equation within the temperature range of study,and COSMO-RS can be used to predict the heat capacity of ionic liquids reliably.     

Statistical mechanics and artificial intelligence to model the thermodynamic properties of pure and mixture of ionic liquids

In this paper, the volumetric properties of pure and mixture of ionic liquids are predicted using the developed statistical mechanical equation of state in different temperatures, pressures and mole fractions. The temperature dependent parameters of the equation of state have been calculated using corresponding state correlation based on only the density at 298.15 K as scaling constants. The obtained mean of deviations of modified equation of state for density of al pure ionic liquids for 1662 data points was 0.25%. In addition, the performance of the arti-ficial neural network (ANN) with principle component analysis (PCA) based on back propagation training with 28 neurons in hidden layer for predicting of behavior of binary mixtures of ionic liquids was investigated. The AADs of a col ection of 568 data points for al binary systems using the EOS and the ANN at various temperatures and mole fractions are 1.03%and 0.68%, respectively. Moreover, the excess molar volume of all binary mixtures is predicted using obtained densities of EOS and ANN, and the results show that these properties have good agree-ment with literature.     

Effects of additive NaI on electrodeposition of Al coatings in AlCl3-NaCl-KCl molten salts

Effects of NaI as an additive on electrodeposition of Al coatings in AlCl₃-NaCl-KCl(80-10-10 wt-%)molten salts electrolyte at 150°C were investigated by means of cyclic voltammetry,chronopotentiometry,scanning electron microscopy and X-ray diffraction(XRD).Results reveal that addition of NaI in the electrolyte intensifies cathodic polarization,inhibits growth of Al deposits and increases number density of charged particles.The electrodeposition of Al coatings in the AlCl₃-NaCl-KCl molten salts electrolyte proceeds via three-dimensional instantaneous nucleation which however exhibits irrelevance with NaI.Galvanostatic deposition results indicate that NaI could facilitate the formation of uniform Al deposits.A compact coating consisting of Al deposits with an average particle size of 3μm was obtained at a current density of 50 mA?cm^?2 in AlCl₃-NaCl-KCl molten salts electrolyte with 10 wt-%NaI.XRD analysis confirmed that NaI could contribute to the formation of Al coating with a preferred crystallographic orientation along(220)plane.     

Removal of mercaptans from light oils using ionic liquid–NaOH aqueous solution as extractants

The application of ionic liquids as alternatives to conventional organic solvents in the extraction process has been investigated. In the present study, fourteen species of imidazolium-based ionic liquids were added into the Na OH(aq) to remove the mercaptans. The influences of anion species and cation alkyl chain length of the imidazolium-based ionic liquids on the performance of mercaptan removal from light oils have been discussed.The efficiency of extraction for mercaptans exhibited the order of [Ac]~-N [OH]~-≈ [Br]~-N [BF4]~-. The longer alkyl chain imidazolium-based ionic liquids contributed to enhance desulfurization rate of 1-butyl mercaptan.100% desulfurization rate of 1-butyl mercaptan was achieved by the anion of Ac-ionic liquids and Na OH(aq)at a volume ratio of 40:1(V(oil):V(ionic liquid)) and a short equilibrium time within 10 min.     

[bmin]Cl/[FeCl3]离子液体催化的苯与1-十八烯烷基化反应

Abstract The study on the catalysis of ionic liquids for alkylation of benzene with 1-octadecene to synthesize LAB （linear alkylbenzenes） was performed. The results showed that the most important factor that governed the conversion of olefin and selectivity of LAB was reaction temperature. Moreover, the effects of different ionic liquids and molar ratio of benzene to 1-octadecene on the conversion and selectivity were obviously in different degrees. The reaction temperature, molar ratio of benzene to 1-octadecene and the amount of catalyst were lower, compared with the traditional reaction technologies. The experimental results demonstrated that the ionic liquid had higher activity at 30℃, with over 98% selectivity of monoalkylbenzene and 100% conversion of the olefin at the molar ratio 0.08 of FeCl3 in ionic liquid to 1-octadecene and 10 for benzene to 1-octadecene.     

Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22 zeolite

The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process.Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation.To regulate the isobutane/1-butene adsorption ratio,four types of ionic liquid (i.e.,IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite.The as-synthesized IL-immobilized MCM-22 (i.e.,MCM-22-IL) was characterized by FTIR,TGA,BET,XPS and XRD,and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume.But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly improved by the immobilization of ionic liquids.The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs.Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O,the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio.The results illustrated that immobilizing ionic liquids is an effective way to modify the textural,chemical and morphological properties of MCM-22.Accordingly,the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.     

Measurement of thermal conductivity,viscosity and density of ionic liquid [EMIM][DEP]-based nanofluids☆

This article studied experimentally the effect of multi-wall carbon nanotubes(MWCNTs)on the thermo physical properties of ionic liquid-based nanofluids.The nanofluids were composed of ionic liquid,1-ethyl-3-methylimidazolium diethylphosphate [EMIM][DEP],or its aqueous solution[EMIM][DEP](1)+ H_2O(2)and MWCNTs without any surfactants.The thermal conductivity,viscosity and density of the nanofluids were measured experimentally.The effects of the mass fraction of MWCNTs,temperature and the mole fraction of water on the thermo physical properties of nanofluids were studied.Results show that the thermal conductivity of nanofluids increases within the range of 1.3%–9.7% compared to their base liquids,and have a well linear dependence on temperature.The viscosity and density of the nanofluids exhibit a remarkable increase compared with those of the base liquids.Finally,the correlation of the effective thermal conductivity and viscosity of the nanofluids was made using the models in the literatures.     

N-烷基-N-甲基咪唑系列离子液体中ZSM-5分子筛催化环已烷氧化反应

Heterogeneous oxidation of cyclohexane by tert-butyl hydroperoxide (TBHP) was carried out over ZSM-5 catalysts with different Si/Al ratios in ionic liquids and organic molecular solvents. Higher yield and selectivity of the desired products were found in ionic liquids than in molecular solvents. The conversion of cyclohexane exhibits a decrease from 15.8% to 10.8% with the increase of Si/Al ratio of the HZSM-5 catalyst, and all the catalysts exhibit good selectivity of monofunctional oxidation products at around 97%. The activity of catalyst is found strongly de-pendent on the alkyl chain length of ionic liquid.     

Electrodeposition of aluminium and aluminium/platinum alloys from AlCl3/benzyltrimethylammonium chloride room temperature ionic liquids

This paper shows that aluminium and aluminium/platinum alloys can be deposited from room temperature ionic liquids formed from an adduct of aluminium trichloride with benzyltrimethyl ammonium chloride. The advantages of this ionic liquid over the majority of those previously investigated is that it is less water sensitive, easier to purify and form and significantly more cost effective. Voltammetry and chronoamperometry were used to investigate the deposition and stripping of aluminium on Pt, Al and Fe electrodes. Hull cell tests were performed to obtain the optimum deposition conditions and bulk electrolysis showed that uniform, adherent, crack-free aluminium deposits could be obtained from such ionic liquids. Co-electrodeposition of Al with Pt was also studied and the nucleation mechanism was found to change significantly when Pt complexes were added to the ionic solution. The platinum ligands were found to change the solubility of the complex, but had little effect on the morphology of the deposited film.     

[BMIM]Cl/AlCl3离子液体低温电沉积铝过程

采用玻碳/铂为惰性阳极,以1-丁基-3-甲基咪唑氯盐([BMIM]Cl/AlCl₃)离子液体体系为电解液,研究了离子液体电解铝工艺,优化了电解工艺条件,探讨了电解影响因素。结果表明,当电解液[BMIM]Cl∶AlCl₃摩尔比为1∶2.00时,随着温度的升高,铝的沉积槽电压逐渐减小,电流密度增加,但电解液的稳定性减弱,当温度达到90℃时,电解液分解明显。当电解温度一定时,随着[BMIM]Cl∶AlCl₃摩尔比的增加[(1∶1.25)~(1∶2.00)],电流密度增加。通过赫尔槽实验,SEM、XRD分析了电解铝的沉积形貌和晶相结构。随电流密度的逐渐减小,沉积层变薄,晶相结构变化不大;相同电流密度区随温度的升高,沉积层逐渐变得粗糙。计算了不同槽间距下的槽压与电流密度的关系。     

Ionic liquids as electrolytes

Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However, ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing, conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application in aluminium electroplating, lithium batteries and in electrochemical capacitors.     

The effect of additives on zinc electrodeposition from deep eutectic solvents

The electrodeposition of metals using ionic liquids has received considerable attention during the last ten years. Recent developments have taken these novel electrolytes from laboratory to commercial scale. One of the factors limiting the development into practical plating systems is the understanding of how brighteners function. In this study we describe the addition of three polar additives and their effect upon the nucleation mechanism of zinc and the resultant morphology. It is shown that the structure of the zinc deposits is controlled by double layer properties and it is proposed that the brightening effect of ethylene diamine and ammonia are caused by their ability to inhibit the adsorption of chloride at the electrode surface. The deposition of most metals using ionic liquids results in apparently amorphous deposits, which tend to be actually nano-crystalline. The additives used in this study produce macro-crystalline deposits, which resemble those obtained from aqueous solutions.     

TMPAC-AlCl3离子液体中恒电流电沉积铝

合成了不同TMPAC和AlCl₃摩尔比的TMPAC-AlCl₃离子液体,并测定了其在不同温度下的电导率。在摩尔比为1:2的TMPAC-AlCl₃离子液体中进行了恒电流电沉积实验,研究了温度、电流密度、搅拌速度和添加剂甲苯等对沉积层的影响。结果表明:在相同条件下摩尔比为1:2的TMPAC-AlCl₃离子液体电导率最大,当温度为80℃,电流密度为20 mA·cm^-2,搅拌速度为500 r·min^-1时,沉积层质量较好且电流效率较高;甲苯的加入,增大了TMPAC-2AlCl₃离子液体的电导率,降低了槽电压,当添加甲苯的体积分数为50%,电流密度为23 mA·cm^-2时,可以得到较为致密、色泽良好、平整而均匀的沉积层。     

铝合金化学镀Ni-P-B的研究

以二甲基胺硼烷（DMAB）为还原剂,在铝合金上获得了化学镀镍低磷低硼镀层,研究了硫酸镍、次磷酸钠、DMAB、络合剂、pH值和稳定剂对镀层的沉积速度、显微硬度和微观形貌的影响。通过正交实验和单因素实验,确定了最佳工艺配方为：24g／L硫酸镍,适量DMAB,12g／L次磷酸钠,3mg／L硫脲,30mL／L络合剂。所获得的化学镀镍镀层中P、B、Ni的质量分数分别为：1．8l％、0．26％和97．93％。该镀层与基体的结合力良好,硬度在550～710Hp。范围内,在铝质活塞上应用获得了满意的效果。     

氯铝酸离子液体催化苯与1-己烯的烷基化反应

研究了在具有 Lewis酸性的氯铝酸离子液体体系中进行的苯与 1 -己烯的烷基化反应。以溴化 1 -乙基 - 3 -甲基咪唑 (emim Br) ,溴化 1 -丁基 - 3 -甲基咪唑 (bmim Br) ,盐酸三乙胺 (Et3NHCl) ,溴化四丁基铵 (C4 H9NBr) ,十六烷基三甲基溴化铵 (C19H4 2 Br N)分别与 Al Cl3原位合成法制备离子液体催化体系。结果表明以上各种离子液体均有很高的催化活性 ,反应转化率在短时间内达到1 0 0 %。其中 Et3NHCl- Al Cl3离子液体单烷基选择性达到 98.1 %。而且催化剂易于分离并能重复使用 ,反应转化率没有明显降低     

离子液体体系电解铝技术的研究与应用进展

指出了传统高温电解铝工艺存在的严重问题,在此基础上总结了新型低温熔盐?离子液体的结构和性质,重点综述了近年来离子液体低温电解铝技术的特点、基础研究与应用进展. 通过系统分析表明,离子液体法的反应温度可降至100℃以下乃至室温附近,反应能耗一般低于10 kW×h/kg,同时也减少了CO2, CO和氟化氢等有害物质的排放. 以铝为阳极时,该技术还能应用于低温铝精炼、铝合金与纳米铝的制备,不仅提高了反应效率和产物纯度,也扩展了铝产品种类和研究领域. 这主要归功于离子液体良好的物理化学性能和较强的结构可调性. 未来应进一步加深对体系构效关系的认识,建立电极反应的调控机制,实现技术的集成放大.     

A promising method for electrodeposition of aluminium on stainless steel in ionic liquid

A promising method for aluminium deposition was proposed by using AlCl₃/[bmim]Cl (1‐butyl‐3‐methylimidazolium chloride) ionic liquid as electrolyte. By using this novel method, the volatile and flammable organic solvent systems and the high corrosive inorganic molten salts with high temperature can be substituted, and the deposit microstructure can be easily adjusted by changing the current density, temperature and electrolyte composition. The study was performed by means of galvano‐static electrolysis and the optimum operating conditions were determined based on the systematic studies of the effects of current density, temperature, molar ratio of AlCl₃ to [bmim]Cl, stirring speed and deposition time on the quality of deposited coatings. The electrical conductivities of electrolytes were also investigated as a function of temperature (298–358 K) and molar ratio of AlCl₃ to [bmim]Cl (from 0.1:1 to 2.0:1). Dense, bright and adherent aluminium coatings were obtained over a wide range of temperature (298–348 K), current densities (8–44 mA/cm²) and molar ratio (1.6:1–2.0:1). Results from the analysis of crystal structure show that all of the electrodeposits exhibit a preferred (200) crystallographic orientation. Temperature has significant influence on the crystallographic orientation and there does not appear to be an apparent impact of current density on it. Analyses of the chronoamperograms indicate that the deposition process of aluminium on stainless steel was controlled by three‐dimension nucleation with diffusion‐controlled growth and there is a conversion from progressive nucleation to instantaneous nucleation. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Electroplated bright aluminium coatings for anticorrosion and decorative purposes

This paper is dedicated to the study of electrodeposited aluminium layers as anticorrosion protective coatings on metallic substrates. The aim of this approach is to propose a non-toxic alternative to the traditional nickel–chromium coating, for anticorrosive and decorative purposes. Aluminium was electrodeposited on carbon steel substrates from chloroaluminate based ionic liquids with and without the addition of 1,10-phenantroline. In the first case, the Al deposits are dense but dull, while in the latter homogeneous and bright coatings suitable for decorative purposes were achieved.