Steryl and stanyl esters of fatty acids by solvent-free esterification and transesterification in vacuo using lipases from Rhizomucor miehei, Candida antarctica, and Carica papaya.
Sitostanol has been converted in high to near-quantitative extent to the corresponding long-chain acyl esters via esterification with oleic acid or transesterification with methyl oleate or trioleoylglycerol using immobilized lipases from Rhizomucor miehei (Lipozyme IM) and Candida antarctica (lipase B, Novozym 435) as biocatalysts in vacuo (20-40 mbar) at 80 degrees C, whereas the conversion was markedly lower at 60 and 40 degrees C. Corresponding conversions observed with papaya (Carica papaya) latex lipase were generally lower. High conversion rates observed in transesterification of sitostanol with methyl oleate at 80 degrees C using Lipozyme IM were retained even after 10 repeated uses of the biocatalyst. Saturated sterols such as sitostanol and 5alpha-cholestan-3beta-ol were the preferred substrates as compared to Delta(5)-unsaturated cholesterol in transesterification reactions with methyl oleate using Lipozyme IM. Transesterification of cholesterol with dimethyl 1,8-octanedioate using Lipozyme IM in vacuo yielded methylcholesteryl 1,8-octanedioate (75%) and dicholesteryl 1,8-octanedioate (5%). However, transesterification of cholesterol with diethyl carbonate and that of oleyl alcohol with ethylcholesteryl carbonate, both catalyzed by Lipozyme IM, gave ethylcholesteryl carbonate and oleylcholesteryl carbonate, respectively, in low yield (20%). Moreover, cholesterol was transesterified with ethyl dihydrocinnamate using Lipozyme IM to give cholesteryl dihydrocinnamate in moderate yield (56%), whereas the corresponding reaction of lanosterol gave lanosteryl oleate in low yield (14%).
Weber
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N
Institute for Biochemistry and Technology of Lipids, H. P. Kaufmann-Institute, Federal Centre for Cereal, Potato and Lipid Research, Piusallee 68, D-48147 Münster, Germany. ibtfett@uni-muenster.de
Weitkamp
P
P
Mukherjee
K D
KD
D002175:Candida / Q000201:enzymology*; D002855:Chromatography, Thin Layer; D004951:Esterification; D004952:Esters; D005227:Fatty Acids / Q000737:chemistry*; D007700:Kinetics; D008049:Lipase / Q000737:chemistry*; D019684:Magnoliopsida / Q000737:chemistry*; D015394:Molecular Structure; D020103:Rhizomucor / Q000201:enzymology*; D012997:Solvents
D004952:Esters; D005227:Fatty Acids; D012997:Solvents; D008049:Lipase