Increased enantioselectivity and remarkable acceleration of lipase-catalyzed transesterification by using an imidazolium PEG-alkyl sulfate ionic liquid.
ABSTRACT Several types of imidazolium salt ionic liquids were prepared derived from poly(oxyethylene)alkyl sulfate and used as an additive or coating material for lipase-catalyzed transesterification in an organic solvent. A remarkably increased enantioselectivity was obtained when the salt was added at 3-10 mol % versus substrate in the Burkholderia cepacia lipase (lipase PS-C)-catalyzed transesterification of 1-phenylethanol by using vinyl acetate in diisopropyl ether or a hexane solvent system. In particular, a remarkable acceleration was accomplished by the ionic liquid coating with lipase PS in an iPr(2)O solvent system while maintaining excellent enantioselectivity; it reached approximately 500- to 1000-fold acceleration for some substrates with excellent enantioselectivity. A similar acceleration was also observed for IL 1-coated Candida rugosa lipase. MALDI-TOF mass spectrometry experiments of the ionic-liquid-coated lipase PS suggest that ionic liquid binds with lipase protein.
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ABSTRACT: The aim of this study is to develop an ionic liquid-containing system for efficient production of betulinic acid by cultured cells Armillaria luteo-virens Sacc ZJUQH100-6. Several parameters affecting betulinic acid formation in the IL-containing system were investigated. The addition of [EMIM][BF4] in hexane-containing reaction medium gave rise to better betulinic acid formation in comparison with other ILs used. The optimal concentration of IL in IL-containing co-solvent system is 50% (v/v). As a co-substrate, butanol is found to be useful for intracellular betulin-28-monooxygenase synthesis during the whole phase. The concentrations of substrate and resting cells have been found to exert a significant effect on betulinic acid. Moreover, the reaction time in this IL-containing system was less than that in the conventional one. The effect of the constructed IL-containing system on cell membrane structure was comparatively observed. Under the developed IL-containing system, the highest yield of product observed was 11.14% at 18h, higher than that in monophase aqueous one (P<0.05), whereas the activity of monooxygenase showed the same variation as betulinic acid formation. KeywordsIonic liquids–Betulinic acid–Biotransformation– Armillaria luteo-virens Sacc ZJUQH100-6European Food Research and Technology 04/2012; 233(3):507-515. · 1.44 Impact Factor
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ABSTRACT: In recent years, the designer nature of ionic liquids (ILs) has driven their exploration and exploitation in countless fields among the physical and chemical sciences. A fair measure of the tremendous attention placed on these fluids has been attributed to their inherent designer nature. And yet, there are relatively few examples of reviews that emphasize this vital aspect in an exhaustive or meaningful way. In this critical review, we systematically survey the physicochemical properties of the collective library of ether- and alcohol-functionalized ILs, highlighting the impact of ionic structure on features such as viscosity, phase behavior/transitions, density, thermostability, electrochemical properties, and polarity (e.g. hydrophilicity, hydrogen bonding capability). In the latter portions of this review, we emphasize the attractive applications of these functionalized ILs across a range of disciplines, including their use as electrolytes or functional fluids for electrochemistry, extractions, biphasic systems, gas separations, carbon capture, carbohydrate dissolution (particularly, the (ligno)celluloses), polymer chemistry, antimicrobial and antielectrostatic agents, organic synthesis, biomolecular stabilization and activation, and nanoscience. Finally, this review discusses anion-functionalized ILs, including sulfur- and oxygen-functionalized analogs, as well as choline-based deep eutectic solvents (DESs), an emerging class of fluids which can be sensibly categorized as semi-molecular cousins to the IL. Finally, the toxicity and biodegradability of ether- and alcohol-functionalized ILs are discussed and cautiously evaluated in light of recent reports. By carefully summarizing literature examples on the properties and applications of oxy-functional designer ILs up till now, it is our intent that this review offers a barometer for gauging future advances in the field as well as a trigger to spur further contemplation of these seemingly inexhaustible and--relative to their potential--virtually untouched fluids. It is abundantly clear that these remarkable fluidic materials are here to stay, just as certain design rules are slowly beginning to emerge. However, in fairness, serendipity also still plays an undeniable role, highlighting the need for both expanded in silico studies and a beacon to attract bright, young researchers to the field (406 references).Chemical Society Reviews 03/2012; 41(10):4030-66. · 24.89 Impact Factor
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ABSTRACT: Ionic liquids, also called molten salts, are mixtures of cations and anions that melt below 100°C. Typical ionic liquids are dialkylimidazolium cations with weakly coordinating anions such as (MeOSO3) or (PF6). Advanced ionic liquids such as choline citrate have biodegradable, less expensive, and less toxic anions and cations. Deep eutectic solvents are also included in the advanced ionic liquids. Deep eutectic solvents are mixtures of salts such as choline chloride and uncharged hydrogen bond donors such as urea, oxalic acid, or glycerol. For example, a mixture of choline chloride and urea in 1:2 molar ratio liquefies to form a deep eutectic solvent. Their properties are similar to those of ionic liquids. Water-miscible ionic liquids as cosolvents with water enhance the solubility of substrates or products. Although traditional water-miscible organic solvents also enhance solubility, they often inactivate enzymes, while ionic liquids do not. The enhanced solubility of substrates can increase the rate of reaction and often increases the regioor enantioselectivity. Ionic liquids can also be solvents for non-aqueous reactions. In these cases, they are especially suited to dissolve polar substrates. Polar organic solvent alternatives inactivate enzymes, but ionic liquids do not even when they have similar polarities. Besides their solubility properties, ionic liquids and deep eutectic solvents may be greener than organic solvents because ionic liquids are nonvolatile, and can be made from nontoxic components. This review covers selected examples of enzyme catalyzed reaction in ionic liquids that demonstrate their advantages and unique properties, and point out opportunities for new applications. Most examples involve hydrolases, but oxidoreductases and even whole cell reactions have been reported in ionic liquids. Keywordsionic liquids-deep eutectic solvents-hydrolases-oxidoreductases-polymerizationBiotechnology and Bioprocess Engineering 04/2012; 15(1):40-53. · 1.28 Impact Factor