Key Laboratory of Marine Drugs, Ministry of Education of China, School of Medicine and Pharmacy, Ocean University of China, Qingdao, 266003, China.
Laboratory for Marine Drugs and Bioproducts of Qingdao National Laboratory for Marine Science and Technology, Qingdao, 266237, China.
Microb Cell Fact. 2018 Jun 19;17(1):98. doi: 10.1186/s12934-018-0943-6.
Polyene antibiotics are important as antifungal medicines albeit with serious side effects such as nephrotoxicity. Reedsmycin (RDM) A (1), produced by marine-derived Streptomyces youssoufiensis OUC6819, is a non-glycosylated polyene macrolide antibiotic with antifungal activity comparable to that of clinically used nystatin. To elucidate its biosynthetic machinery, herein, the rdm biosynthetic gene cluster was cloned and characterized.
The rdm cluster is located within a 104 kb DNA region harboring 21 open reading frames (ORFs), among which 15 ORFs were designated as rdm genes. The assembly line for RDM A is proposed on the basis of module and domain analysis of the polyketide synthetases (PKSs) RdmGHIJ, which catalyze 16 rounds of decarboxylative condensation using malonyl-CoA as the starter unit (loading module), two methylmalonyl-CoA (module 1 and 2), and fourteen malonyl-CoA (module 3-16) as extender units successively. However, the predicted substrate specificity of AT0 in the loading module is methylmalonyl-CoA instead of malonyl-CoA. Interestingly, the rdm cluster contains a five-gene regulation system RdmACDEF, which is different from other reported polyene gene clusters. In vivo experiments demonstrated the XRE family regulator RdmA and the PAS/LuxR family regulator RdmF function in negative and positive manner, respectively. Notably, inactivation of rdmA and overexpression of rdmF led to increased production of RDM A by ~ 2.0-fold and ~ 2.5-fold, reaching yields of 155.3 ± 1.89 and 184.8 ± 9.93 mg/L, respectively.
Biosynthesis of RDM A is accomplished on a linear assembly line catalyzed by Rdm PKSs harboring a unique AT0 under the control of a complex regulatory system. These findings enable generation of new biologically active RDM derivatives at high yield and with improved properties by engineered biosynthesis.
多烯类抗生素是重要的抗真菌药物,尽管具有严重的副作用,如肾毒性。由海洋来源的链霉菌 youssoufiensis OUC6819 产生的雷多霉素(RDM)A(1)是一种非糖基化的多烯大环内酯抗生素,具有与临床使用的制霉菌素相当的抗真菌活性。为了阐明其生物合成机制,本文克隆和表征了 rdm 生物合成基因簇。
rdm 簇位于一个 104kb 的 DNA 区域内,包含 21 个开放阅读框(ORFs),其中 15 个 ORFs 被指定为 rdm 基因。根据多酮合酶(PKS)RdmGHIJ 的模块和结构域分析,提出了 RDM A 的装配线,该酶使用丙二酰辅酶 A 作为起始单元(加载模块),两个甲基丙二酰辅酶 A(模块 1 和 2)和 14 个丙二酰辅酶 A(模块 3-16)作为延伸单元,催化 16 轮脱羧缩合反应。然而,加载模块中 AT0 的预测底物特异性是甲基丙二酰辅酶 A 而不是丙二酰辅酶 A。有趣的是,rdm 簇包含一个由五个基因组成的调控系统 RdmACDEF,与其他报道的多烯基因簇不同。体内实验表明,XRE 家族调节剂 RdmA 和 PAS/LuxR 家族调节剂 RdmF 分别以负调控和正调控的方式发挥作用。值得注意的是,rdmA 的失活和 rdmF 的过表达导致 RDM A 的产量分别增加了约 2.0 倍和 2.5 倍,达到 155.3±1.89 和 184.8±9.93mg/L。
RDM A 的生物合成是在由 Rdm PKS 催化的线性装配线上完成的,该 PKS 含有一个独特的 AT0,并受一个复杂的调控系统控制。这些发现使通过工程化生物合成以高产率和改善的性质生成新的具有生物活性的 RDM 衍生物成为可能。