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Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides
A prevailing scenario of the origin of life postulates thioesters as key intermediates in protometabolism, but there is no experimental support for the prebiotic CO(2) fixation routes to thioesters. Here we demonstrate that, under a simulated geoelectrochemical condition in primordial ocean hydrothe...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814748/ https://www.ncbi.nlm.nih.gov/pubmed/36697522 http://dx.doi.org/10.1038/s42004-021-00475-5 |
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author | Kitadai, Norio Nakamura, Ryuhei Yamamoto, Masahiro Okada, Satoshi Takahagi, Wataru Nakano, Yuko Takahashi, Yoshio Takai, Ken Oono, Yoshi |
author_facet | Kitadai, Norio Nakamura, Ryuhei Yamamoto, Masahiro Okada, Satoshi Takahagi, Wataru Nakano, Yuko Takahashi, Yoshio Takai, Ken Oono, Yoshi |
author_sort | Kitadai, Norio |
collection | PubMed |
description | A prevailing scenario of the origin of life postulates thioesters as key intermediates in protometabolism, but there is no experimental support for the prebiotic CO(2) fixation routes to thioesters. Here we demonstrate that, under a simulated geoelectrochemical condition in primordial ocean hydrothermal systems (–0.6 to –1.0 V versus the standard hydrogen electrode), nickel sulfide (NiS) gradually reduces to Ni(0), while accumulating surface-bound carbon monoxide (CO) due to CO(2) electroreduction. The resultant partially reduced NiS realizes thioester (S-methyl thioacetate) formation from CO and methanethiol even at room temperature and neutral pH with the yield up to 35% based on CO. This thioester formation is not inhibited, or even improved, by 50:50 coprecipitation of NiS with FeS or CoS (the maximum yields; 27 or 56%, respectively). Such a simple thioester synthesis likely occurred in Hadean deep-sea vent environments, setting a stage for the autotrophic origin of life. |
format | Online Article Text |
id | pubmed-9814748 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-98147482023-01-10 Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides Kitadai, Norio Nakamura, Ryuhei Yamamoto, Masahiro Okada, Satoshi Takahagi, Wataru Nakano, Yuko Takahashi, Yoshio Takai, Ken Oono, Yoshi Commun Chem Article A prevailing scenario of the origin of life postulates thioesters as key intermediates in protometabolism, but there is no experimental support for the prebiotic CO(2) fixation routes to thioesters. Here we demonstrate that, under a simulated geoelectrochemical condition in primordial ocean hydrothermal systems (–0.6 to –1.0 V versus the standard hydrogen electrode), nickel sulfide (NiS) gradually reduces to Ni(0), while accumulating surface-bound carbon monoxide (CO) due to CO(2) electroreduction. The resultant partially reduced NiS realizes thioester (S-methyl thioacetate) formation from CO and methanethiol even at room temperature and neutral pH with the yield up to 35% based on CO. This thioester formation is not inhibited, or even improved, by 50:50 coprecipitation of NiS with FeS or CoS (the maximum yields; 27 or 56%, respectively). Such a simple thioester synthesis likely occurred in Hadean deep-sea vent environments, setting a stage for the autotrophic origin of life. Nature Publishing Group UK 2021-03-17 /pmc/articles/PMC9814748/ /pubmed/36697522 http://dx.doi.org/10.1038/s42004-021-00475-5 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Kitadai, Norio Nakamura, Ryuhei Yamamoto, Masahiro Okada, Satoshi Takahagi, Wataru Nakano, Yuko Takahashi, Yoshio Takai, Ken Oono, Yoshi Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides |
title | Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides |
title_full | Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides |
title_fullStr | Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides |
title_full_unstemmed | Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides |
title_short | Thioester synthesis through geoelectrochemical CO(2) fixation on Ni sulfides |
title_sort | thioester synthesis through geoelectrochemical co(2) fixation on ni sulfides |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814748/ https://www.ncbi.nlm.nih.gov/pubmed/36697522 http://dx.doi.org/10.1038/s42004-021-00475-5 |
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