ID 2.3.1.111 DE mycocerosate synthase. CA (1) 3 (R)-methylmalonyl-CoA + 9 H(+) + long-chain fatty acyl- CA [mycocerosate synthase] + 6 NADPH = 3 CO2 + 3 CoA + 3 H2O + 6 NADP(+) + CA trimethylated-mycocerosoyl-[mycocerosate synthase]. CA (2) 4 (R)-methylmalonyl-CoA + 12 H(+) + long-chain fatty acyl- CA [mycocerosate synthase] + 8 NADPH = 4 CO2 + 4 CoA + 4 H2O + 8 NADP(+) + CA tetramethylated-mycocerosoyl-[mycocerosate synthase]. CC -!- The enzyme, characterized from mycobacteria, is loaded with a long- CC chain acyl moiety by EC 6.2.1.49 and elongates it by incorporation of CC three or four methylmalonyl (but not malonyl) residues, to form tri- CC or tetramethyl-branched fatty-acids, respectively, such as 2,4,6,8- CC tetramethyloctacosanoate (C32-mycocerosate). CC -!- Since the enzyme lacks a thioesterase domain, the product remains CC bound and requires additional enzyme(s) for removal. CC -!- Even though the enzyme can accept C6 to C20 substrates in vitro, CC it prefers to act on C14-C20 substrates in vivo. DR Q02251, MCAS_MYCBO ; //