文献类型：期刊文献

英文题名：Selective amide bond formation in redox-active coacervate protocells

作者：Wang, Jiahua[1,2];Abbas, Manzar[1];Wang, Junyou[3];Spruijt, Evan[1]

机构：[1]Radboud Univ Nijmegen, Inst Mol & Mat, Heyendaalseweg 135, NL-6525 AJ Nijmegen, Netherlands;[2]Shanghai Jiao Tong Univ, Dept Radiol, Affiliated Sixth Peoples Hosp, Sch Med, Shanghai 200233, Peoples R China;[3]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：14

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001129103900004)】；

基金：This work was financially supported by the European Research Council (ERC) under grant number 851963 to E.S., and the Fundamental Research Funds for the Shanghai Sixth People's Hospital (X-2430 to J.W.). The authors would like to thank Dr. Karina Nakashima for synthesis of the N-acetyl glycine thioacid and helpful discussions about the project goals, Haibin Qian for preliminary experiments on EDC-mediated amide bond formation in pGlu/pLys(Me)3 coacervates and the methylation protocol for pLys, Dr. Tiemei Lu for help with preparing the methylated pLys, and Wojciech Lipinski for help with the FRAP measurements and amino acid partitioning experiments.

语种：英文

摘要：Coacervate droplets are promising protocell models because they sequester a wide range of guest molecules and may catalyze their conversion. However, it remains unclear how life's building blocks, including peptides, could be synthesized from primitive precursor molecules inside such protocells. Here, we develop a redox-active protocell model formed by phase separation of prebiotically relevant ferricyanide (Fe(CN)63-) molecules and cationic peptides. Their assembly into coacervates can be regulated by redox chemistry and the coacervates act as oxidizing hubs for sequestered metabolites, like NAD(P)H and gluthathione. Interestingly, the oxidizing potential of Fe(CN)63- inside coacervates can be harnessed to drive the formation of new amide bonds between prebiotically relevant amino acids and alpha-amidothioacids. Aminoacylation is enhanced in Fe(CN)63-/peptide coacervates and selective for amino acids that interact less strongly with the coacervates. We finally use Fe(CN)63--containing coacervates to spatially control assembly of fibrous networks inside and at the surface of coacervate protocells. These results provide an important step towards the prebiotically relevant integration of redox chemistry in primitive cell-like compartments. Coacervate droplets are promising protocells that sequester nutrients, but how new peptides could be synthesized inside coacervates remains a mystery. Here, the authors develop redox-active coacervates that facilitate the formation of new peptide bonds.