Enzymatic synthesis of butyl hydroxycinnamates and their inhibitory effects on LDL-oxidation.
The potential of the Aspergillus niger type A feruloyl esterase (AnFaeA) for the synthesis of various phenolic acid esters was examined using a ternary-organic reaction system consisting of a mixture of n-hexane, 1- or 2-butanol and water. Reaction parameters including the type of methyl hydroxycinnamate, the composition of the reaction media, the temperature, and the substrate concentration were investigated to evaluate their effect on initial rate and conversion to butyl esters of sinapic acids. Optimisation of the reaction parameters lead to 78% and 9% yield for the synthesis of 1-butyl and 2-butyl sinapate, respectively. For the first time, a feruloyl esterase was introduced in the reaction system as cross-linked enzyme aggregates (CLEAs), after optimisation of the immobilisation procedure, allowing the recycling and reuse of the biocatalyst. The inhibition of copper-induced LDL oxidation by hydroxycinnamic acids and their corresponding butyl esters was investigated in vitro. Kinetic analysis of the antioxidation process demonstrates that sinapate derivatives are effective antioxidants indicating that esterification increases the free acid's antioxidant activity especially on dimethoxylated compounds such as sinapic acid compared to methoxy-hydroxy-compounds such as ferulic acid.
D001234:Aspergillus niger / Q000378:metabolism; D002265:Carboxylic Ester Hydrolases / Q000378:metabolism*; D002851:Chromatography, High Pressure Liquid; D003373:Coumaric Acids / Q000737:chemistry / Q000378:metabolism* / Q000494:pharmacology*; D008077:Lipoproteins, LDL / Q000378:metabolism*; D046529:Microscopy, Electron, Transmission; D015394:Molecular Structure; D010084:Oxidation-Reduction / Q000187:drug effects; D013696:Temperature
D003373:Coumaric Acids; D008077:Lipoproteins, LDL; D002265:Carboxylic Ester Hydrolases; C070196:feruloyl esterase