| Summary: | The synthesis of phospholipids with defined fatty acid and polar head composition catalysed by lipases and phospholipases was investigated. Lipases from Rhizopus arrhizus and Candida antarctica were used for the direct acylation of DL-a-glycerophosphate and L-a-glycerophosphatidylcholine, with different fatty acids. Esterification reactions can be carried out in systems with low water activity, in which the equilibrium is favoured towards synthesis, and hydrolysis is minimised. For optimisation of the processes, it is important to consider various reaction parameters, principally the water content of the media. In the acylation of glycerophosphate and glycerophosphorylcholine, fatty acid vinyl esters gave better yields (>95%) than free fatty acid, in the formation of lysophosphatidic acid and phosphatidic acid or lysophosphatidylcholine and phosphatidylcholine. Solvent free systems were chosen for both reactions, but in some cases conversions could be easily improved by the addition of a small amount of solvent, such as t -butanol. The choline polar head group of lysophosphatidylcholine was exchanged with glycerol in a reaction catalysed by a phospholipase D from Savoy cabbage, in an aqueous micellar system. Characterisation of this reaction and of the hydrolysis showed that both reactions are similar in their Ca 2+ ion dependence, kinetic parameters and pH optima. Contrary to the action of the enzyme towards phosphatidylcholine, phospholipase D does not need detergents or solvents to display optimum activity, with lysophosphatidylcholine as substrate. A combination of two phospholipases was used for the formation of lysophosphatidic acid and the analogue, 1-acyl-dihydroxyacetonephosphate, in diethyl ether-aqueous two-phase systems. Microbial phospholipase D from Streptomyces sp. was used in the transesterification of egg phosphatidylcholine with 1-lauroyl-glycerol or 1-lauroyl-dihydroxyacetone, to form two complex phospholipids, 1-lauroyl-phosphatidylglycerol and 1-lauroyl-phosphatidyldihydroxyacetone, ...
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