化学与精细化工广东省实验室蔡秋泉团队报道了C4二醇气媒仿生合成聚羟基烷酸酯。相关研究成果发表在2024年12月23日出版的《德国应用化学》。

聚（4-羟基丁酸酯）（P4HB）是一种高性能、可回收和可生物降解的聚羟基烷酸酯（PHA）。然而，均聚物P4HB的传统生物生产涉及复杂且昂贵的C4原料工艺，特别是1,4-丁二醇（BDO）和基因工程细菌中的酶辅酶系统。利用BDO的空气氧化的替代细胞外化学途径具有成本和能源效益，但转化效率很低。

受伯醇高效细胞内氧化的启发，研究人员提出了一种模拟酶辅酶功能的钌膦协同催化系统。该系统有效地催化了BDO的空气介导、无溶剂氧化，生成γ-丁内酯（γ-BL）和低聚P4HB，时空产率（10.37 g[γ-BL单位]g^-1催化剂h^-1）超过了之前方法的值（<5.5）。含低聚物的产物通过开环聚合可逆地转化为γ-BL，然后转化为P4HB（28.9 kDa），超过了报告值（<16 kDa）。

该项研究为从各种非颗粒基二醇大规模合成高价值PHA提供了潜力，具有经济和环境优势。

附：英文原文

Title: Air-Mediated Biomimetic Synthesis of Polyhydroxyalkanoate with C4 Diol

Author: Huilin Xie, Kaibin Zhong, Shihao Niu, Xiaoxu Li, Zexu Hu, Guang Xiao, Yifu Huang, Hongjie Zhang, Yuan Liu, Hefeng Zhang, Qiuquan Cai

Issue&Volume: 2024-12-23

Abstract: Poly(4-hydroxybutyrate) (P4HB) is a high-performance, well-recyclable, and biodegradable polyhydroxyalkanoate (PHA). However, conventional bioproduction of homopolymeric P4HB involves complex and costly processes with C4 feedstocks, particularly 1,4-butanediol (BDO), and enzyme-coenzyme systems in genetically engineered bacteria. An alternative extracellular chemical route utilizing aerial oxidation of BDO offers cost and energy benefits but struggle with conversion efficiency. Inspired by efficient intracellular oxidation of primary alcohols, we propose a ruthenium-phosphine synergistic catalytic system that mimics enzyme-coenzyme functionality. This system effectively catalyzed the air-mediated, solvent-free oxidation of BDO to produce γ-butyrolactone (γ-BL) and oligomeric P4HB, with a space-time yield (10.37 g [γ-BL unit] g-1 catalyst h-1) surpassing the values (<5.5) of previous approaches. The oligomer-containing products were reversibly converted to γ-BL and then to P4HB (28.9 kDa) via ring-opening polymerization, exceeding reported values (<16 kDa). This study provides the potential for large-scale synthesis of high-value PHAs from diverse non-grain-based diols, offering economic and environmental advantages.

DOI: 10.1002/anie.202417660

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202417660