Chemical and enzymatic transacylation of amide‐linked FA of buttermilk gangliosides

• Published in: Lipids 2003-08, Vol.38 (8), p.855-864
• Main Authors: Beermann, Christopher, Röhrig, Anne‐Katrin, Boehm, Günther
• Format: Article
• Language: English
• Subjects: Acylation; Amides - chemistry; Animals; Cattle; Chromatography, High Pressure Liquid; Chromatography, Thin Layer; Cultured Milk Products - chemistry; Fatty acids; Fatty Acids - chemistry; G(M3) Ganglioside - chemistry; Heterogeneity; Hydrolysis; Ionization; Molecular Structure; Spectrometry, Mass, Electrospray Ionization
• ISSN: 0024-4201; 1558-9307
• DOI: 10.1007/s11745-003-1136-3

The goal of this work was to alter the composition of amide‐linked FA of bovine buttermilk gangliosides, particularly the disialoganglioside GD3, to adjust lipid sources to special food specifications and pharamacological or cosmetic applications. The chemical transacylation of amide‐linked FA of buttermilk gangliosides with free arachidic acid (20∶0) by a combination of basic hydrolysis and diethylphosphorylcyanide/triethylamine‐catalyzed reacylation was compared to an enzymatic sphingolipid ceramide N‐deacylase (EC 3.5.1.23)‐catalyzed FA exchange by GC analysis and nano electrospray ionization‐MS. The buttermilk predominantly contained the disialoganlioside GD3 and the monosialoganglioside GM3. The heterogeneity of FA that are incorporated into gangliosides, mainly palmitic acid (29.4 wt%), stearic acid (16.9 wt%), oleic acid (17.8 wt%), and myristic acid (8.5 wt%), was effectively altered by both transes‐terification techniques. Arachidic acid, which was not integrated into the initial buttermilk gangliosides, was transacylated to total gangliosides with 23.2 wt% (GD3, 6.7 wt%) by the chemical process and with 8.7 wt% (GD3, 13.8 wt%) when catalyzed enzymatically. Mainly behenic acid and lignoceric acid of GD3 were exchanged chemically, and stearic acid was exchanged by the enzymatic process. This observation might depend on hydrolytic sensitivities of amide‐linked very long chain saturated FA or specific enzyme subtrate affinities, respectively. Results of chemical hydrolysis indicated there was a risk of sialic acid decomposition and unspecific degradations. Regarding specificity and avoidance of critical agents, the enzymatic transesterification is recommended for industrial‐scale production of consumer goods.