Gevers W, Kleinkauf H, Lipmann F
Proc Natl Acad Sci U S A. 1969 Aug;63(4):1335-42. doi: 10.1073/pnas.63.4.1335.
The biosynthesis of the peptide antibiotic gramicidin S involves successive peptidyl transfer reactions between intermediates bound in thioester linkages to two active enzyme fractions, I and II. Fraction II activates and recemizes phenylalanine, and then initiates peptidyl transfer by catalyzing a reaction between the carboxyl group of D-phenylalanine, bound to an enzymic sulfhydryl group, and the free imino group of L-proline, one of four L-amino acids all linked by their carboxyl functions to separate sulfhydryl groups on fraction I. Successive reactions of this type in the active centers of the multienzyme complex of fraction I lead to the formation of thioester-bonded nascent peptide chains and, ultimately, of the antibiotic product.
短杆菌肽S这种肽抗生素的生物合成涉及中间体与两种活性酶组分I和II以硫酯键相连时的连续肽基转移反应。组分II激活苯丙氨酸并使其消旋，然后通过催化与酶的巯基相连的D-苯丙氨酸的羧基与L-脯氨酸的游离亚氨基之间的反应来启动肽基转移，L-脯氨酸是四种L-氨基酸之一，它们都通过羧基官能团与组分I上不同的巯基相连。在组分I的多酶复合物的活性中心中进行的这种类型的连续反应导致形成硫酯键连接的新生肽链，并最终形成抗生素产物。
