Nano-pulsed discharge plasma-induced abiotic oligopeptide formation from diketopiperazine
Nano-pulsed discharge plasma-induced abiotic oligopeptide formation from diketopiperazine
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DOI：
10.1007/s00114-022-01803-y
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发表时间：
2022-06
期刊：
影响因子：
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通讯作者：
M. Sasaki;Yuji Miyagawa;Kouki Nonaka;Ryota Miyanomae;A. Quitain;T. Kida;M. Goto;T. Honma;
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作者：
M. Sasaki;Yuji Miyagawa;Kouki Nonaka;Ryota Miyanomae;A. Quitain;T. Kida;M. Goto;T. Honma;
常规的寡肽合成技术涉及对环境有害的程序和材料。此外，关于生命起源的冥古宙地球环境下寡肽的有效积累仍然不清楚。在这些过程中，二酮哌嗪的形成是一个大问题，因为它强烈抑制了二肽以外的进一步延伸。水热介质能够实现环境友好的寡肽合成。然而，水热寡肽合成产生大量的二酮哌嗪（DKP），由于其热力学稳定性。DKP抑制二肽延伸，并且还构成常规寡肽合成中的抑制途径。在这里，我们展示了一种有效的寡肽形成的途径，使用一个专门设计的实验装置来运行热和非热放电等离子体，由纳米脉冲放电产生的16-23 kV电压和300-430 A电流在约1000 mA。500 ns。在pH 4.5的含有丙氨酸-DKP的水溶液中，在50 pps热等离子体照射20分钟后，DKP（14%）转化为二肽和更高级的寡肽。这是第一个研究报告有效的寡肽合成在水性介质中使用纳米脉冲等离子体（热等离子体比非热等离子体更有效）通过DKP开环。这一意想不到的发现对于评估寡肽如何在原始地球中利用高能等离子体源如雷电积累的途径以及促进寡肽的绿色合成是有意义的。
Conventional oligopeptide synthesis techniques involve environmentally harmful procedures and materials. In addition, the efficient accumulation of oligopeptides under Hadean Earth environments regarding the origin of life remains still unclear. In these processes, the formation of diketopiperazine is a big issue due to the strong inhibition for further elongation beyond dipeptides. Hydrothermal media enables environmentally friendly oligopeptide synthesis. However, hydrothermal oligopeptide synthesis produces large amounts of diketopiperazine (DKP), due to its thermodynamic stability. DKP inhibits dipeptide elongation and also constitutes an inhibitory pathway in conventional oligopeptide synthesis. Here, we show an efficient pathway for oligopeptide formation using a specially designed experimental setup to run both thermal and non-thermal discharge plasma, generated by nano-pulsed electric discharge with 16–23 kV voltage and 300–430 A current within ca. 500 ns. DKP (14%) was converted to dipeptides and higher oligopeptides in an aqueous solution containing alanine-DKP at pH 4.5, after 20 min of 50 pps thermal plasma irradiation. This is the first study to report efficient oligopeptide synthesis in aqueous medium using nano-pulsed plasma (with thermal plasma being more efficient than non-thermal plasma) via DKP ring-opening. This unexpected finding is implicative to evaluate the pathway how the oligopeptides could have accumulated in the primitive Earth with high-energy plasma sources such as thunder as well as to facilitate the green synthesis of oligopeptides.