Lipase-catalysed synthesis of mono- and di-acyl esters of glyceryl caffeate in propylene carbonate and their antioxidant properties in tuna oil

Abstract

Development of new non-toxic antioxidants with diverse hydrophobic properties is important due to growing concerns about the toxicity of artificial oil-soluble antioxidants, the comparatively low effectiveness of natural options, and the complex role hydrophobicity plays in antioxidant effectiveness. Using caffeic acid, a naturally occurring phenolic acid with potent antioxidant activity, a range of glyceryl caffeate esters (decanoate and palmitate) were prepared using lipase-catalysed esterification reactions. Glyceryl-1-caffeate (GC) was prepared from ethyl caffeate and glycerol (acting as both the solvent and the substrate), catalysed by immobilised Candida Antarctica lipase B (Novozym-435) at 80 °C under vacuum. Esterification of GC with decanoic acid using immobilised Thermomyces lanuginosus lipase (TLIM) or Novozym-435 was found to be selective towards mono-acylated or di-acylated products, respectively. The reaction was performed in an unconventional solvent, propylene carbonate (PC), which has many of the attributes of a green solvent. Product conversions in PC were comparable to the best performing conventional solvents. In contrast to conventional volatile solvents, the low volatility of PC allowed the reaction to be performed under vacuum, without the need for molecular sieves for removal of water produced during the reaction. Diisopropyl ether was effective at extracting the more lipophilic products from PC. Both the lipase (Novozym-435) and PC were reused four times with only a small loss in conversion efficiency. Glyceryl caffeate esters performed much better than α-tocopherol at protecting bulk tuna oil from oxidation (analysed using Rancimat). A comparison of glyceryl caffeate esters (decanoate/palmitate and mono-/di-acylated) showed that their antioxidant effectiveness in bulk tuna oil was not affected by chain-length, but compounds containing only one fatty ester were slightly more effective than those containing two fatty esters.