Bogojevic Oliver, Zhang Yan, Wolff Christian Daugaard, Nygaard Jens Vinge, Wiking Lars, Arevång Carl, Guo Zheng
Department of Biological and Chemical Engineering, Faculty of Technical Sciences, Aarhus University, Gustav Wieds Vej 10, 8000 Aarhus, Denmark.
Department of Food Science, CiFOOD, Aarhus University, Agro Food Park 48, 8200 Aarhus N, Denmark.
iScience. 2023 Jun 9;26(7):107075. doi: 10.1016/j.isci.2023.107075. eCollection 2023 Jul 21.
A sustainable and green approach was developed for the scalable synthesis of uncommon naturally occurring phospholipid species, Hemi-bis(monoacylglycero)phosphates (Hemi-BMPs) and bis(diacylglycero)phosphates (BDPs) via the phospholipase D (PLD) mediated transphosphatidylation. PLD from . showed great substrate promiscuity for both phospholipids from different biological sources, and alcohol donors with diverse regiochemistry; monoacylglycerols with diverse fatty acyl structures (C12-C22), affording 74-92 wt% yields in 2 h. Experimental results demonstrated that the reaction rate is rather independent of phosphatidyls but to a large extent governed by the size, shape and regiolocation of fatty acyls incorporated on the glycerol backbone, particularly for the regio-isomers of bulky diacylglycerols (-1,3 or -1,2), which displays great diversity. In addition, a plausible mechanism is proposed based on molecular simulations for an elaborated explanation of the reaction thermodynamic and kinetic favorability toward the synthesis of Hemi-BMPs and BDPs.
通过磷脂酶D（PLD）介导的转磷脂酰化反应，开发了一种可持续的绿色方法，用于可扩展地合成不常见的天然存在的磷脂种类，即半双（单酰甘油）磷酸酯（Hemi-BMPs）和双（二酰甘油）磷酸酯（BDPs）。来自……的PLD对来自不同生物来源的磷脂以及具有不同区域化学的醇供体表现出极大的底物选择性；具有不同脂肪酰基结构（C12-C22）的单酰甘油，在2小时内产率可达74-92 wt%。实验结果表明，反应速率在很大程度上与磷脂酰基无关，而主要受甘油主链上所结合脂肪酰基的大小、形状和区域位置的影响，特别是对于体积较大的二酰甘油的区域异构体（-1,3或-1,2），其表现出很大的多样性。此外，基于分子模拟提出了一种合理的机制，以详细解释合成Hemi-BMPs和BDPs反应的热力学和动力学有利性。
