School of Marine Science and Technology, Harbin Institute of Technology at Weihai, Weihai, Shandong 264209, China.
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang 150090, China.
J Phys Chem Lett. 2021 Jun 24;12(24):5774-5780. doi: 10.1021/acs.jpclett.1c01083. Epub 2021 Jun 16.
The chemistry of abiotic synthesis of peptides in the context of their prebiotic origins is a continuing challenge that arises from thermodynamic and kinetic constraints in aqueous media. Here we reported a strategy of microdroplets' mass spectrometry for peptide bonds formed from pure amino acids or a mixture in the presence of phosphoric acids in aqueous microdroplets. In contrast to bulk experiments, the condensation reactions proceed spontaneously under ambient conditions. The microdroplet gave a negative free-energy change (Δ ∼ -1.1 kcal/mol), and product yields of ∼75% were obtained at the scale of a few milliseconds. Experiments in which nebulization gas pressure and external charge were varied established dependence of peptide production on the droplet size that has a high surface-to-volume ratio. It is concluded that the condensation reactions occurred at or near the air-water interfaces of microdroplets. This aqueous microdroplets approach also provides a route for chemistry synthesis in the prebiotic era.
在涉及生物前体起源的非生物合成肽的化学中,由于水介质中的热力学和动力学限制,这仍然是一个持续存在的挑战。在这里,我们报道了一种在水微滴中使用质谱法从纯氨基酸或混合物中形成肽键的策略,其中存在磷酸。与体相实验相比,在环境条件下缩合反应会自发进行。微滴给出了负的自由能变化(Δ∼-1.1 kcal/mol),并且在几毫秒的规模上获得了约 75%的产物产率。改变雾化气体压力和外部电荷的实验确定了产肽与具有高表面积与体积比的液滴尺寸的依赖性。可以得出结论,缩合反应发生在微滴的气-液界面处或附近。这种水微滴方法也为前生物时代的化学合成提供了一种途径。