N-Carboxyanhydride-Mediated Fatty Acylation of Amino Acids and Peptides for Functionalization of Protocell Membranes
N-Carboxyanhydride-Mediated Fatty Acylation of Amino Acids and Peptides for Functionalization of Protocell Membranes
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DOI：
10.1021/jacs.6b08801
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发表时间：
2016-12-28
影响因子：
15
通讯作者：
Szostak, Jack W.
中科院分区：
文献类型：
--
作者：
Izgu, Enver Cagri;Bjorkbom, Anders;Szostak, Jack W.
早期的原始细胞很可能是由RNA、肽和脂分子自组装而来的，这些分子是在地球早期有利的地质环境中产生和集中的。这些成分在提供化学能源的益生菌环境中的反应可能会产生更多的物种，这些物种的特性有利于原细胞的出现。环状氨基酸N-羧酸酐(NCAs)的形成是由羰基硫化物对氨基酸的地球化学性质的激活而产生的短肽。在这里，我们证明了在脂肪酸存在下，Valine-NCA的聚合通过混合酸化中间体产生了酰化氨基酸和多肽。值得注意的是，精氨酸和油酸在Valine-NCA存在下反应的产物N-α-油精氨酸自发地分配到囊泡膜中，并介导RNA与囊泡的结合。我们的结果表明，在早期原细胞的形成过程中，激活的氨基酸可以使脂肪酸膜的化学功能多样化，并使RNA与囊泡共存。
Early protocells are likely to have arisen from the self-assembly of RNA, peptide, and lipid molecules that were generated and concentrated within geologically favorable environments on the early Earth. The reactivity of these components in a prebiotic environment that supplied sources of chemical energy could have produced additional species with properties favorable to the emergence of protocells. The geochemically plausible activation of amino acids by carbonyl sulfide has been shown to generate short peptides via the formation of cyclic amino acid N-carboxyanhydrides (NCAs). Here, we show that the polymerization of valine-NCA in the presence of fatty acids yields acylated amino acids and peptides via a mixed anhydride intermediate. Notably, N-alpha-oleoylarginine, a product of the reaction between arginine and oleic acid in the presence of valine-NCA, partitions spontaneously into vesicle membranes and mediates the association of RNA with the vesicles. Our results suggest a potential mechanism by which activated amino acids could diversify the chemical functionality of fatty acid membranes and colocalize RNA with vesicles during the formation of early protocells.