Beermann Christopher, Röhrig Anne-Katrin, Boehm Günther
Numico Research Germany, D-61381 Friedrichsdorf, Germany.
Lipids. 2003 Aug;38(8):855-64. 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 pharmacological 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 disialoganglioside 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 transesterification 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.
这项工作的目标是改变牛乳乳清神经节苷脂中酰胺连接脂肪酸的组成，尤其是二唾液酸神经节苷脂GD3，以便根据特殊食品规格以及药理或化妆品应用来调整脂质来源。通过气相色谱分析和纳米电喷雾电离质谱，将牛乳乳清神经节苷脂酰胺连接脂肪酸与游离花生酸（20:0）进行化学转酰化反应（采用碱性水解和二乙基磷酰氰/三乙胺催化的再酰化反应相结合的方法），并与酶促鞘脂神经酰胺N-脱酰酶（EC 3.5.1.23）催化的脂肪酸交换反应进行比较。牛乳乳清主要含有二唾液酸神经节苷脂GD3和单唾液酸神经节苷脂GM3。通过两种酯交换技术，有效地改变了神经节苷脂中所包含脂肪酸的异质性，这些脂肪酸主要是棕榈酸（29.4 wt%）、硬脂酸（16.9 wt%）、油酸（17.8 wt%）和肉豆蔻酸（8.5 wt%）。花生酸未整合到初始牛乳乳清神经节苷脂中，通过化学方法将其转酰化至总神经节苷脂中的含量为23.2 wt%（GD3为6.7 wt%），酶促催化时含量为8.7 wt%（GD3为13.8 wt%）。GD3的主要山嵛酸和木蜡酸通过化学方法进行交换，硬脂酸则通过酶促过程进行交换。这一观察结果可能分别取决于酰胺连接的超长链饱和脂肪酸的水解敏感性或特定酶与底物的亲和力。化学水解结果表明存在唾液酸分解和非特异性降解的风险。考虑到特异性和避免使用关键试剂，对于消费品的工业规模生产，建议采用酶促酯交换反应。
