Kudo Fumitaka, Kasama Yuko, Hirayama Toshifumi, Eguchi Tadashi
Department of Chemistry, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551, Japan.
J Antibiot (Tokyo). 2007 Aug;60(8):492-503. doi: 10.1038/ja.2007.63.
The biosynthetic gene (pct) cluster for an antitumor antibiotic pactamycin was identified by use of a gene for putative radical S-adenosylmethionine methyltransferase as a probe. The pct gene cluster is localized to a 34 kb contiguous DNA from Streptomyces pactum NBRC 13433 and contains 24 open reading frames. Based on the bioinformatic analysis, a plausible biosynthetic pathway for pactamycin comprising of a unique cyclopentane ring, 3-aminoacetophenone, and 6-methylsalicylate was proposed. The pctL gene encoding a glycosyltransferase was speculated to be involved in an N-glycoside formation between 3-aminoacetophenone and UDP-N-acetyl-alpha-D-glucosamine prior to a unique cyclopentane ring formation. The pctL gene was then heterologously expressed in Escherichia coli and the enzymatic activity of the recombinant PctL protein was investigated. Consequently, the PctL protein was found to catalyze the expected reaction forming beta-N-glycoside. The enzymatic activity of the PctL protein clearly confirmed that the present identified gene cluster is for the biosynthesis of pactamycin. Also, a glycosylation prior to cyclopentane ring formation was proposed to be a general strategy in the biosynthesis of the structurally related cyclopentane containing compounds.
利用假定的自由基S-腺苷甲硫氨酸甲基转移酶基因作为探针,鉴定出了抗肿瘤抗生素派克霉素的生物合成基因(pct)簇。pct基因簇定位于来自坚实链霉菌NBRC 13433的一段34 kb连续DNA上,包含24个开放阅读框。基于生物信息学分析,提出了一条合理的派克霉素生物合成途径,该途径由一个独特的环戊烷环、3-氨基苯乙酮和6-甲基水杨酸组成。推测编码糖基转移酶的pctL基因在独特的环戊烷环形成之前,参与3-氨基苯乙酮与UDP-N-乙酰-α-D-葡萄糖胺之间的N-糖苷形成。然后在大肠杆菌中异源表达pctL基因,并研究重组PctL蛋白的酶活性。结果发现,PctL蛋白催化形成β-N-糖苷的预期反应。PctL蛋白的酶活性清楚地证实了目前鉴定出的基因簇是用于派克霉素的生物合成。此外,还提出在环戊烷环形成之前进行糖基化是含环戊烷结构相关化合物生物合成中的一种普遍策略。