Ionic Liquid-Assisted Solubilization for Improved Enzymatic Esterification of Phenolic Acids

Abstract

Lipophilic derivatives of phenolic acids could greatly extend their applications in the lipophilic bio-environment and food processing, therefore, develo** an efficient lipophilization reaction system constitutes an interesting topic of biocatalysis. Low solubility of phenolic acids in most enzyme-benign solvents represents the main reason for the inefficiency of enzymatic production of lipophilic phenolic derivatives. This work reports a novel approach to improve Candida antartica lipase B (Novozym 435) catalyzed lipophilization of phenolic acids by means of ionic liquids (IL), trioctylmethylammonium trifluoroacetate (tOMA.TFA) assisted solubilization of the substrate. In this approach, the IL plays two major roles, namely, to dissolve phenolic acids at high concentration so as to create a homogeneous system with another substrate—1-octanol, and to be benign to the enzyme to keep the biocatalyst active; which is proved itself to be a correct strategy as improved conversion and volumetric productivity are obtained. The results showed that dosage of IL (denoted as the volume ratio of 1-octanol/tOMA.TFA), concentration of dihydrocaffeic acid (DHCA) and temperature are the key parameters governing the reaction efficiency. A maximum conversion of DHCA was achieved at the ratio of 1-octanol/tOMA.TFA 12:1 (v/v) (1-octanol/DHCA, 38:1 (mol/mol)). A temperature of 70 °C was correct to obtain optimal conversion of DHCA. Even though the conversion of DHCA was higher at lower concentrations of DHCA, the overall volumetric productivity (reaction rate) was much higher when a high concentration of DHCA (1.6 M) was applied, due to IL-assisted solubilization of DHCA. Remarkable enhancement of the conversions of ferulic and caffeic acids were achieved, when the same reaction approach (tOMA.TFA assisted solubilization) was applied to these two phenolic acids, indicating the general applicability of this novel approach.