Abstract

Enormous interest in biocatalysis in non-aqueous phase has recently been triggered due to the merits of good enantioselectivity, reverse thermodynamic equilibrium, and no water-dependent side reactions. It has been demonstrated that enzyme has high activity and stability in non-aqueous media, and the variation of enzyme activity is attributed to its conformational modifications. This review comprehensively addresses the stability and activity of the intact enzymes in various non-aqueous systems, such as organic solvents, ionic liquids, sub-/super-critical fluids and their combined mixtures. It has been revealed that critical factors such as Log P, functional groups and the molecular structures of the solvents define the microenvironment surrounding the enzyme molecule and affect enzyme tertiary and secondary structure, influencing enzyme catalytic properties. Therefore, it is of high importance for biocatalysis in non-aqueous media to elucidate the links between the microenvironment surrounding enzyme surface and its stability and activity. In fact, a better understanding of the correlation between different non-aqueous environments and enzyme structure, stability and activity can contribute to identifying the most suitable reaction medium for a given biotransformation.

Highlights

  • Since the 1980s, biocatalysis in non-aqueous media has undergone a tremendous development and numerous reactions have been proposed and optimized for synthetic applications

  • In comparison with conventional aqueous enzymology, biocatalysis in non-aqueous phase offers unique merits, such as the possibility of altering enzyme regio- and enantio-selectivity, to reverse thermodynamic equilibrium toward synthesis, to avoid water-dependent side reactions, and bacterial contamination [1,2]

  • P value of organic solvent shows no obvious effect on the backbone structure of enzyme, organic solvent will impact the water content urrounding the enzyme surface and active site region, which can been observed through the molecular dynamics (MD) simulation

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Summary

Introduction

Since the 1980s, biocatalysis in non-aqueous media has undergone a tremendous development and numerous reactions have been proposed and optimized for synthetic applications. Organic solvents are the most commonly used non-aqueous media for biocatalysis. We demonstrated that, apart from log P, functional groups and molecular structure of organic solvents would exert significant influences on enzymes activity [6]. This review aims to highlight the mechanisms of enzyme’s activity variance according to enzyme structure changes in four different common non-aqueous media, i.e., organic solvents, ILs, sub-/super-critical fluids, and their combination mixture systems. Some major factors affecting the microenvironment surrounding enzyme in non-aqueous media, such as log P, solvent type, functional group, molecular structure, cation and anion type, pressure and temperature, are comprehensively discussed in this review. Some specific applications of biocatalysis in non-aqueous phases are addressed in the corresponding section

Effect of Log P Value of Organic Solvent
Effect of the Functional Groups of Organic Solvent
Effect of Molecular Structure of Organic Solvent
Effect of Hydrophobicity of Ionic Liquid
Effects of Cation and Anion Types of Ionic Liquids
Biocatalysis in Mixture Solvents of Organic Solvent and Ionic Liquid
Effects of Pressure and Temperature on the Structure and Activity of Enzyme
Biocatalysis in Mixture Solvents of Organic Solvent and Supercritical Fluid
Findings
Remarks and Prospects
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