刺孢霉素，一种促进链霉菌次级代谢和形态发生的化学物质。II. 结构测定。

Goadsporin, a chemical substance which promotes secondary metabolism and Morphogenesis in streptomycetes. II. Structure determination.

作者信息

Igarashi Y, Kan Y, Fujii K, Fujita T, Harada K, Naoki H, Tabata H, Onaka H, Furumai T

机构信息

Biotechnology Research Center, Toyama Prefectural University, Kosugi, Japan.

出版信息

J Antibiot (Tokyo). 2001 Dec;54(12):1045-53. doi: 10.7164/antibiotics.54.1045.

DOI:10.7164/antibiotics.54.1045

PMID:11858659

Abstract

The structure of goadsporin was determined by using spectroscopic techniques. NMR analysis revealed that goadsporin consists of 19 amino acids, two of which are dehydroalanines (Deala), and six of which are cyclized to oxazoles (Oxz) and thiazoles (Thz) by dehydrative cyclization and dehydrogenation from serine, threonine and cysteine. NMR analysis established seven partial structures, and their sequence was determined by CID-MS/MS. Negative mode FAB-MS/MS gave product ions arising from charge-remote fragmentation that allowed determination of the sequence of the amino acid components as AcNH-Ala-MeOxz-Val-Deala-MeOxz-Ile-Leu-Thz-Ser-Gly-Gly-MeOxz-Leu-Deala-Oxz-Ala-Gly-Thz-Val-OH. The chiral amino acids were determined by the advanced Marfey's method to have L-configurations.

摘要

通过光谱技术确定了刺孢霉素的结构。核磁共振（NMR）分析表明，刺孢霉素由19个氨基酸组成，其中两个是脱氢丙氨酸（Deala），六个通过丝氨酸、苏氨酸和半胱氨酸的脱水环化和脱氢反应环化为恶唑（Oxz）和噻唑（Thz）。NMR分析确定了七个部分结构，并通过串联碰撞诱导解离质谱（CID-MS/MS）确定了它们的序列。负离子模式快原子轰击串联质谱（FAB-MS/MS）产生了电荷远程碎裂产生的产物离子，从而确定了氨基酸成分的序列为AcNH-Ala-MeOxz-Val-Deala-MeOxz-Ile-Leu-Thz-Ser-Gly-Gly-MeOxz-Leu-Deala-Oxz-Ala-Gly-Thz-Val-OH。通过先进的马尔费方法确定手性氨基酸具有L-构型。