Mesh : Peptides / chemistry metabolism Amyloid / chemistry metabolism Oxidoreductases / metabolism chemistry Nanotubes / chemistry Oxidation-Reduction

来  源:   DOI:10.1038/s41467-024-48930-w   PDF(Pubmed)

Abstract:
In extant biology, large and complex enzymes employ low molecular weight cofactors such as dihydronicotinamides as efficient hydride transfer agents and electron carriers for the regulation of critical metabolic processes. In absence of complex contemporary enzymes, these molecular cofactors are generally inefficient to facilitate any reactions on their own. Herein, we report short peptide-based amyloid nanotubes featuring exposed arrays of cationic and hydrophobic residues that can bind small molecular weak hydride transfer agents (NaBH4) to facilitate efficient reduction of ester substrates in water. In addition, the paracrystalline amyloid phases loaded with borohydrides demonstrate recyclability, substrate selectivity and controlled reduction and surpass the capabilities of standard reducing agent such as LiAlH4. The amyloid microphases and their collaboration with small molecular cofactors foreshadow the important roles that short peptide-based assemblies might have played in the emergence of protometabolism and biopolymer evolution in prebiotic earth.
摘要:
在现存的生物学中,大型和复杂的酶使用低分子量的辅因子,如二氢烟酰胺作为有效的氢化物转移剂和电子载体,用于调节关键的代谢过程。在没有复杂的当代酶的情况下,这些分子辅因子通常不能促进任何反应。在这里,我们报道了短的基于肽的淀粉样蛋白纳米管,其特征是阳离子和疏水残基的暴露阵列,可以结合小分子弱氢化物转移剂(NaBH4),以促进水中酯底物的有效还原。此外,负载有硼氢化物的顺晶淀粉样蛋白相表现出可回收性,底物选择性和受控还原,超过标准还原剂如LiAlH4的能力。淀粉样蛋白微相及其与小分子辅因子的合作预示了基于短肽的组装体可能在益生元地球中原代谢和生物聚合物进化的出现中发挥的重要作用。
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