Lipase‐catalyzed synthesis of ferulate esters

Abstract

Four commercially available esterases were screened for their ability to esterify ferulic acid (4-hydroxy-3-methoxy cinnamate). Novozym ® 435 was found to be the only one of those screened to convert ferulic acid to ethyl and octyl ferulate at 20 and 14% yields, respectively. The highest percentage conversion was obtained using a 1:1 mole ratio of alcohol to ferulic acid in stirred batch reactions in anhydrous 2-methyl-2-propanol at 60°C using one equivalent (wt/wt based on ferulic acid) of Novozym 435. Increased water content and a higher alcohol/ethyl ferulate ratio had adverse effects on the lipase-catalyzed esterification. The Novozym 435 activity was tested in less polar solvents (anhydrous toluene and hexane) by monitoring the alcoholysis of ethyl ferulate with 1-octanol, which resulted in a 50% yield of octyl ferulate. The alcoholysis was improved to 83% by applying a 16 mm Hg vacuum for 5 min every 24 h to remove the ethanol co-product. The optimal alcoholysis parameters were applied to the alcoholysis of ethyl ferulate with monoolein and the transesterification with triolein. The transesterification of ethyl ferulate with triolein in anhydrous toluene produced a combined 44% yield of ferulyl monoolein and ferulyl diolein, a 20% greater yield than that obtained for alcoholysis using monoolein. The highest yield, 77%, of ferulyl monoolein and ferulyl diolein was achieved using a threefold excess of neat triolein. The lipase-catalyzed transesterification of ethyl ferulate with triolein appears to be a technically feasible route to ferulyl-substituted acylglycerols, which are potentially useful sunscreen ingredients.

High Efficient Synthesis of Enzymatic 2-Ethylhexyl Ferulate at Solvent-Free and Reduced Pressure Evaporation System

“…The water-soluble derivative of glyceryl ferulate was biosynthesized by esterification of FA with glycerol using pectinase [17]. Solvent-free enzymatic transesterification of EF with triolein (TO) with a higher EF conversion 77% [18]. However, the reaction rate for the condensation of FA with an alcoholic substrate is low because FA has conjugation with a carboxyl group and a bulky noncarboxylic region [19].…”

Improved enzymatic production of phenolated acylglycerols through alkyl phenolate intermediates

“…In terms of specific activity, Lipozyme TL IM (0.57 µmol g -1 min -1 ) was not so different from Lipozyme RM IM (0.44 µmol g -1 min -1 ), whereas Novozym 435 was significantly higher (9.57 µmol g -1 min -1 ). This fact again proved that Candida antartica lipase B (Novozym 435) was a robust lipase for synthesis application as observed in many different systems (Compton et al 2000;Sabally et al 2005;Compton et al 2006;Sabally et al 2006;Guyot et al 1997). Therefore, Novozym 435 was chosen as a biocatalyst for RSM optimization.…”

“…However, their applications in oil-based food processing and cosmetic industries are limited due to their low solubility in hydrophobic media (Buisman et al, 1998;Figueroa-Espinoza and Villeneuve 2005). To improve the lipophilicity of phenolic acids, an alternative method is incorporation of phenolic acids into triacylglycerols through enzymatic reactions (Compton et al 2000;Sabally et al 2005Sabally et al , 2006Sabally et al , 2007Laszlo and Compton 2006). However, direct transesterification of phenolic acids with triacylglycerols is generally suffered from long reaction time and low efficiency (Figueroa-Espinoza and Villeneuve 2005;Compton et al 2000).…”

“…To improve the lipophilicity of phenolic acids, an alternative method is incorporation of phenolic acids into triacylglycerols through enzymatic reactions (Compton et al 2000;Sabally et al 2005Sabally et al , 2006Sabally et al , 2007Laszlo and Compton 2006). However, direct transesterification of phenolic acids with triacylglycerols is generally suffered from long reaction time and low efficiency (Figueroa-Espinoza and Villeneuve 2005;Compton et al 2000). Thus, many efforts, for example, through medium engineering to improve solubility of phenolic acids (Sabally et al 2006;Lue et al 2005), and through chemoenzymatic approach (Sun et al, 2009), have been made to improve the efficiency of related reactions.…”

Enhanced Enzymatic Preparation of Lipophilic Feruloylated Lipids Using Distearin as Feruloyl Acceptors: Optimization by Response Surface Methodology

“…Feruloylated monoacylglycerols FMAG and feruloylated diacylglycerols FDAG are lipophilic feruloylated lipids of ferulic acid, which have been used as lipophilic antioxidants and UV absorbers in food and other fields 10,11 . As ferulic acid is a heat-sensitive phenolic acid and susceptible to oxidation, which makes enzymatic synthesis of FMAG and FDAG become an attractive alternative 5,8 .…”