Petkovic H, Thamchaipenet A, Zhou L H, Hranueli D, Raspor P, Waterman P G, Hunter I S
Department of Pharmaceutical Sciences, University of Strathclyde, Glasgow, Scotland G1 1XW, United Kingdom.
J Biol Chem. 1999 Nov 12;274(46):32829-34.
Oxytetracycline is a polyketide antibiotic made by Streptomyces rimosus. From DNA sequencing, the gene product of otcD1 is deduced to function as a bifunctional cyclase/aromatase involved in ring closure of the polyketide backbone. Although otcD1 is contiguous with the ketoreductase gene, they are located an unusually large distance from the genes encoding the "minimal polyketide synthase" of the oxytetracycline gene cluster. A recombinant, disrupted in the genomic copy of otcD1, made four novel polyketides, all of shorter chain length (by up to 10 carbons) than oxytetracycline. All four novel structures contained the unusual carboxamido group, typical of oxytetracycline. This implies that the carboxamido group is present at the start of biosynthesis of oxytetracycline, a topic that has been debated in the literature. Loss of the cyclase protein has a profound influence on the length of polyketide chain assembled, implying that OtcD1 plays a greater role in the overall integrity of the quaternary structure of the polyketide complex than hitherto imagined.
土霉素是由龟裂链霉菌产生的一种聚酮类抗生素。通过DNA测序推断,otcD1的基因产物作为一种双功能环化酶/芳香化酶,参与聚酮骨架的环化反应。尽管otcD1与酮还原酶基因相邻,但它们与土霉素基因簇中编码“最小聚酮合酶”的基因相距异常遥远。一个在otcD1基因组拷贝中被破坏的重组体产生了四种新型聚酮化合物,其链长均比土霉素短(最多短10个碳)。所有这四种新结构都含有土霉素特有的不寻常的羧酰胺基团。这意味着羧酰胺基团在土霉素生物合成开始时就已存在,这一话题在文献中一直存在争议。环化酶蛋白的缺失对所组装的聚酮链长度有深远影响,这表明OtcD1在聚酮复合物四级结构的整体完整性中所起的作用比迄今所想象的更大。