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Cited by 39Origins and Evolution of LifeChemical Reaction MechanismsEnzyme Catalysis and Immobilization

Hydrogen Drives Part of the Reverse Krebs Cycle under Metal or Meteorite Catalysis

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Rauscher, Sophia A., Moran, Joseph·2022·Angewandte Chemie International Edition
DOI 10.1002/anie.202212932PMC PMC10100321
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Abstract

Hydrogen (H 2) is a geological source of reducing electrons that is thought to have powered the metabolism of the last universal common ancestor to all extant life, and that is still metabolized by various modern organisms. It has been suggested that H 2 drove a geochemical analogue of some or all of the reverse Krebs cycle at the emergence of the metabolic network, catalyzed by metals, but this has yet to be demonstrated experimentally. Herein, we show that three consecutive steps of the reverse Krebs cycle, converting oxaloacetate into succinate, can be driven without enzymes and in one‐pot by H 2 as the reducing agent under mild conditions compatible with biological chemistry. Low catalytic amounts of nickel (10–20 mol %) or platinum group metals (0.1–1 mol %) or even small amounts of ground meteorites were found to promote the reductive chemistry at temperatures between 5 and 60 °C and over a wide pH range, including pH 7. These results lend additional support to the hypothesis that geologically produced hydrogen and metal catalysts could have initiated early metabolic networks.

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  • The same group has shown that hydrogen drives part of the Krebs cycle, from oxaloacetate to succinate, assisted by rhodium or meteorite catalysis.

    “Indeed, the same group has shown that hydrogen drives part of the Krebs cycle, from oxaloacetate to succinate, assisted by rhodium or meteorite catalysis.114”

    From The protometabolic nature of prebiotic chemistry (2023) · cites this paper as [114]

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  1. [1]W. Martin, M. J. Russell, Philos. Trans. R. Soc. B 2007, 362, 1887– 1925. PMC2442388 17255002
  2. [2]G. Wächtershäuser, Microbiol. Rev. 1988, 52, 452– 484. 3070320 PMC373159
  3. [3]G. Wächtershäuser, Proc. Natl. Acad. Sci. USA 1990, 87, 200– 204. 2296579 PMC53229
  4. [4]V. Vasas, C. Fernando, M. Santos, S. Kauffman, E. Szathmáry, Biol. Direct 2012, 7, 1. 22221860 PMC3284417
  5. [5]R. Shapiro, IUBMB Life 2000, 49, 173– 176. 10868906
  6. [6]S. D. Copley, E. Smith, H. J. Morowitz, Bioorg. Chem. 2007, 35, 430– 443. 17897696
  7. [7]J. C. Fontecilla-Camps, Angew. Chem. Int. Ed. 2019, 58, 42– 48; 30168638 Angew. Chem. 2019, 131, 42– 48.
  8. [8]K. B. Muchowska, S. J. Varma, J. Moran, Chem. Rev. 2020, 120, 7708– 7744. 32687326
  9. [9]J. E. Goldford, D. Segrè, Curr. Opin. Syst. Biol. 2018, 8, 117– 124.
  10. [10]W. F. Martin, F. L. Sousa, N. Lane, Science 2014, 344, 1092– 1093. 24904143
  11. [11]M. C. Weiss, F. L. Sousa, N. Mrnjavac, S. Neukirchen, M. Roettger, S. Nelson-Sathi, W. F. Martin, Nat. Microbiol. 2016, 1, 16116. 27562259
  12. [12]J. L. E. Wimmer, J. C. Xavier, A. d. N. Vieira, D. P. H. Pereira, J. Leidner, F. L. Sousa, K. Kleinermanns, M. Preiner, W. F. Martin, Front. Microbiol. 2021, 12, 793664. 34966373 PMC8710812
  13. [13]J. E. Goldford, H. Hartman, R. Marsland, D. Segrè, Nat. Ecol. Evol. 2019, 3, 1715– 1724. 31712697 PMC6881557
  14. [14]C. Greening, Z. F. Islam, S. K. Bay, Trends Microbiol. 2022, 30, 330– 337. 34462186
  15. [15]P. M. Vignais, B. Billoud, Chem. Rev. 2007, 107, 4206– 4272. 17927159
  16. [16]M. J. Russell, A. J. Hall, W. Martin, Geobiology 2010, 8, 355– 371. 20572872
  17. [17]M. Preiner, J. C. Xavier, F. L. Sousa, V. Zimorski, A. Neubeck, S. Q. Lang, H. C. Greenwell, K. Kleinermanns, H. Tüysüz, T. M. McCollom, N. G. Holm, W. F. Martin, Life 2018, 8, 41. 30249016 PMC6316048
  18. [18]S. Le Caër, Water 2011, 3, 235– 253.
  19. [19]I. G. Draganić, Radiat. Phys. Chem. 2005, 72, 181– 186.
  20. [20]N. Getoff, In Vivo 2014, 28, 61– 66. 24425837
  21. [21]B. S. Lollar, T. C. Onstott, G. Lacrampe-Couloume, C. J. Ballentine, Nature 2014, 516, 379– 382. 25519136
  22. [22]S. A. Harrison, N. Lane, Nat. Commun. 2018, 9, 5176. 30538225 PMC6289992
  23. [23]R. Krishnamurthy, Chem. Eur. J. 2018, 24, 16708– 16715. 29870593
  24. [24]N. H. Horowitz, Proc. Natl. Acad. Sci. USA 1945, 31, 153– 157. 16578152 PMC1078786
  25. [25]M. Ralser, S. J. Varma, R. A. Notebaart, Curr. Opin. Syst. Biol. 2021, 28, 100402.
  26. [26]L. Noda-Garcia, W. Liebermeister, D. S. Tawfik, Annu. Rev. Biochem. 2018, 87, 187– 216. 29925259
  27. [27]M. Preiner, K. Igarashi, K. B. Muchowska, M. Yu, S. J. Varma, K. Kleinermanns, M. K. Nobu, Y. Kamagata, H. Tüysüz, J. Moran, W. F. Martin, Nat. Ecol. Evol. 2020, 4, 534– 542. 32123322
  28. [28]S. J. Varma, K. B. Muchowska, P. Chatelain, J. Moran, Nat. Ecol. Evol. 2018, 2, 1019– 1024. 29686234 PMC5969571
  29. [29]J. Yi, H. Kaur, W. Kazone, S. A. Rauscher, L. A. Gravillier, K. B. Muchowska, J. Moran, Angew. Chem. Int. Ed. 2022, 61, e202117211; PMC9325535 35304939 Angew. Chem. 2022, 134, e202117211. PMC9325535 35304939
  30. [30]R. J. Mayer, H. Kaur, S. A. Rauscher, J. Moran, J. Am. Chem. Soc. 2021, 143, 19099– 19111. 34730975
  31. [31]K. B. Muchowska, S. J. Varma, J. Moran, Nature 2019, 569, 104– 107. 31043728 PMC6517266
  32. [32]M. A. Keller, D. Kampjut, S. A. Harrison, M. Ralser, Nat. Ecol. Evol. 2017, 1, 0083. 28584880 PMC5455955
  33. [33]M. A. Keller, A. V. Turchyn, M. Ralser, Mol. Syst. Biol. 2014, 10, 725. 24771084 PMC4023395
  34. [34]R. T. Stubbs, M. Yadav, R. Krishnamurthy, G. Springsteen, Nat. Chem. 2020, 12, 1016– 1022. 33046840 PMC8570912
  35. [35]E. Smith, H. J. Morowitz, Proc. Natl. Acad. Sci. USA 2004, 101, 13168– 13173. 15340153 PMC516543
  36. [36]K. H. Tang, R. E. Blankenship, J. Biol. Chem. 2010, 285, 35848– 35854. 20650900 PMC2975208
  37. [37]A. L. McCully, M. C. Onyeziri, B. Lasarre, J. R. Gliessman, J. B. McKinlay, Microbiology 2020, 166, 199– 211. 31774392
  38. [38]X. V. Zhang, S. T. Martin, J. Am. Chem. Soc. 2006, 128, 16032– 16033. 17165745
  39. [39]N. Kitadai, R. Nakamura, M. Yamamoto, K. Takai, N. Yoshida, Y. Oono, Sci. Adv. 2019, 5, eaav7848. 31223650 PMC6584212
  40. [40]M. Yadav, S. Pulletikurti, J. R. Yerabolu, R. Krishnamurthy, Nat. Chem. 2022, 14, 170– 178. 35115655
  41. [41]K. B. Muchowska, S. J. Varma, E. Chevallot-Beroux, L. Lethuillier-Karl, G. Li, J. Moran, Nat. Ecol. Evol. 2017, 1, 1716– 1721. 28970480 PMC5659384
  42. [42]J. J. F. Scholten, A. P. Pijpers, A. M. L. Hustings, Catal. Rev. Sci. Eng. 1985, 27, 151– 206.
  43. [43]M. D. Hatch, H. W. Heldt, Anal. Biochem. 1985, 145, 393– 397. 4014670
  44. [44]R. Wolfenden, C. A. Lewis, Y. Yuan, J. Am. Chem. Soc. 2011, 133, 5683– 5685. 21434608 PMC3077560
  45. [45]A. S. Kashin, V. P. Ananikov, J. Org. Chem. 2013, 78, 11117– 11125. 24180285
  46. [46]S. S. Zalesskiy, V. P. Ananikov, Organometallics 2012, 31, 2302– 2309.
  47. [47]D. E. Ryan, J. Holzbecher, R. R. Brooks, Chem. Geol. 1990, 85, 295– 303.
  48. [48]F. Le Formal, N. Guijarro, W. S. Bourée, A. Gopakumar, M. S. Prévot, A. Daubry, L. Lombardo, C. Sornay, J. Voit, A. Magrez, P. J. Dyson, K. Sivula, Energy Environ. Sci. 2016, 9, 3448– 3455.
  49. [49]A. Gopakumar, I. Akçok, L. Lombardo, F. Le Formal, A. Magrez, K. Sivula, P. J. Dyson, ChemistrySelect 2018, 3, 10271– 10276.
  50. [50]B. M. Bizzarri, A. Fanelli, M. Kapralov, E. Krasavin, R. Saladino, RSC Adv. 2021, 11, 19258– 19264. 35478633 PMC9033569
  51. [51]R. Saladino, L. Botta, E. Di Mauro, Life 2018, 8, 6. 29470412 PMC5871938
  52. [52]V. Cabedo, J. Llorca, J. M. Trigo-Rodriguez, A. Rimola, Astron. Astrophys. 2021, 650, A160.
  53. [53]V. F. Buchwald, Handbook of Iron Meteorites, Univ. Calif. Press, Berkeley, 1975.
  54. [54]R. de Graaf, V. Sojo, R. Hudson, ChemRxiv 2022, 10.26434/chemrxiv-2022-xhmzj. This content is a preprint and has not been peer-reviewed. · DOI
  55. [55]M. Alfano, C. Cavazza, Protein Sci. 2020, 29, 1071– 1089. 32022353 PMC7184782
  56. [56]A. Pilchin, L. Eppelbaum, Nat. Resour. 2017, 8, 172– 233.
  57. [57]K. K. Bertine, M. Koide, E. D. Goldberg, Mar. Chem. 1993, 42, 199– 210.
  58. [58]V. Kalugin, V. Gusev, N. Tolstykh, A. Lavrenchuk, E. Nigmatulina, Minerals 2021, 11, 1258.
  59. [59]C. J. Capobianco, M. J. Drake, Geochim. Cosmochim. Acta 1990, 54, 869– 874.

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Authors
Rauscher, S. A., & Moran, J.
Affiliations
Centre National de la Recherche Scientifique (FR)
Corresponding author
Moran, Joseph
ORCID
Moran, Joseph
Venue
Angewandte Chemie International Edition
Publisher
Wiley
Published
2022-11-22
Volume
61
Issue
51
Pages
e202212932-e202212932
ISSN
  • 1433-7851 (ISSN-L)
  • 1521-3773
DOI
10.1002/anie.202212932
PMC
PMC10100321
OpenAlex
W4306643454
Cited by
39
References
13
Citations by year
2026: 8 · 2025: 5 · 2024: 8 · 2023: 15 · 2022: 3
FWCI
3.06
Type
journal article
Language
en
Open access
Licence
Locations
  • Angewandte Chemie International Edition (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • HAL (submittedVersion, other-oa)
Funders
  • H2020 European Research Council (101001752)
  • Volkswagen Foundation (96_742)
  • H2020 Marie Skłodowska-Curie Actions (813873)
Topics
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
  • Physical Sciences › Chemistry › Organic Chemistry › Chemical Reaction Mechanisms
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Enzyme Catalysis and Immobilization
Keywords
hydrogen, origin of life, last universal common ancestor, metal catalysis, nickel catalysis, platinum group metals, reductive metabolism, prebiotic chemistry
MeSH terms
Catalysis, Citric Acid Cycle, Hydrogen, Metals, Meteoroids, Oxaloacetic Acid

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