{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T11:36:24Z","timestamp":1790508984501,"version":"4.1.0"},"reference-count":90,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2020,1,27]],"date-time":"2020-01-27T00:00:00Z","timestamp":1580083200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2020,2,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>In this manuscript we provide computational support to the catalytic role of water in all kinds of pseudopericyclic reactions operating in the reductive acid cycle, as well as in other metabolic processes. Water catalysis is not limited to those reactions where simple translocation of hydrogen atoms occurs, such as those represented by NuH+E\u2192Nu\u2010EH general equation. Indeed, water catalysis is more general and extremely important in tautomerization reactions of the type HX\u2212Y=Z\u2192X=Y\u2212ZH, which operate in the reductive citric acid cycle and metabolic processes. Moreover, the comprehensive theoretical study reported herein illustrates that these reactions appear to behave as authentic enzyme\u2010catalyzed reactions showing Michaelis\u2010Menten behavior, however with the abnormal singularity that the concentration of the catalytic \u201cwater clusters\u201d of different length and nature must be taken as a huge number. Overall, the results presented are suggestive of the workability of the so\u2010called \u201cmetabolism first\u201d proposal in a hot water world, as water catalysis eliminates the dilution problem frequently associated to this proposal.<\/jats:p>","DOI":"10.1002\/cphc.201901069","type":"journal-article","created":{"date-parts":[[2020,1,6]],"date-time":"2020-01-06T07:41:10Z","timestamp":1578296470000},"page":"313-320","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["On the Role of Water as a Catalyst in Prebiotic Chemistry"],"prefix":"10.1002","volume":"21","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7365-6690","authenticated-orcid":false,"given":"Jos\u00e9 M.","family":"Saa","sequence":"first","affiliation":[{"name":"Department of Chemistry Universitat de les Illes Balears  Crta. de Valldemossa km 7.5 07122 Palma de Mallorca (Baleares) SPAIN"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7840-2139","authenticated-orcid":false,"given":"Antonio","family":"Frontera","sequence":"additional","affiliation":[{"name":"Department of Chemistry Universitat de les Illes Balears  Crta. de Valldemossa km 7.5 07122 Palma de Mallorca (Baleares) SPAIN"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,1,27]]},"reference":[{"key":"e_1_2_4_1_1","unstructured":"M. Schidlowski in \u201cThe Chemistry of Life's Origins\u201d p. 389\u2013414 Ed. J.\u2005M. Greenberg C.\u2005X. Mendoza-G\u00f3mez V. 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Hyne J.\u2005T. Klinman H.-H. Limbach R.\u2005L. Schowen Wiley-VCH Verlag GmbH&Co. KGaA Weinheim 2007."},{"key":"e_1_2_4_14_1","unstructured":"For a detailed analysis of the Grotthuss mechanism (sometimes called the Moses's mechanism) see:"},{"key":"e_1_2_4_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(95)00905-J"},{"key":"e_1_2_4_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.199900051"},{"key":"e_1_2_4_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja002506n"},{"key":"e_1_2_4_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr100162c"},{"key":"e_1_2_4_19_1","unstructured":"E.\u2005V. Anslyn D.\u2005A. Dougherty \u201cModern Physical Organic Chemistry\u201d University Science Books2006."},{"key":"e_1_2_4_20_1","unstructured":"\u00a0"},{"key":"e_1_2_4_21_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.271.5245.59"},{"key":"e_1_2_4_22_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.271.5245.62"},{"key":"e_1_2_4_23_1","unstructured":"J.\u2005L. Finney in \u201cWater and Life\u201d Edt. by R.-M. Lynden-Bell S.\u2005C. Morris J.\u2005D. Barrow J.\u2005L. Finney C.\u2005L. Harper Jr. CRC Press Boca Raton Fl.2010."},{"key":"e_1_2_4_24_1","unstructured":"For a description of the role played by bound water in the catalytic action of bacteriorodopsin gramicidin A citochromes etc see: P. Ball in \u201cWater and Life\u201d Edt. by R.-M. Lynden-Bell S.\u2005C. Morris J.\u2005D. Barrow J.\u2005L. Finney C.\u2005L. 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Pombeiro Catalysis Series No. 36 The Royal Society of Chemistry2019.","DOI":"10.1039\/9781788016490-00066"},{"key":"e_1_2_4_34_1","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201800016"},{"key":"e_1_2_4_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/cbdv.200790050"},{"key":"e_1_2_4_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201103672"},{"key":"e_1_2_4_36_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201103672"},{"key":"e_1_2_4_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00430a060"},{"key":"e_1_2_4_38_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-007-0310-x"},{"key":"e_1_2_4_39_1","unstructured":"\u00a0"},{"key":"e_1_2_4_40_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.474659"},{"key":"e_1_2_4_41_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(98)00106-7"},{"key":"e_1_2_4_42_1","unstructured":"Gaussian 09 Revision B.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery Jr. J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov T. Keith R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels O. Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Gaussian Inc. Wallingford CT2010."},{"key":"e_1_2_4_43_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp802665d"},{"key":"e_1_2_4_44_1","unstructured":"The use of mixed cluster-continuum model has been reported by several research groups. See:"},{"key":"e_1_2_4_45_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp980229p"},{"key":"e_1_2_4_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp004192w"},{"key":"e_1_2_4_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp025928n"},{"key":"e_1_2_4_48_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1587122"},{"key":"e_1_2_4_49_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0382967"},{"key":"e_1_2_4_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp012536s"},{"key":"e_1_2_4_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp014533l"},{"key":"e_1_2_4_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0311512"},{"key":"e_1_2_4_53_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.477096"},{"key":"e_1_2_4_54_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1313793"},{"key":"e_1_2_4_55_1","unstructured":"The reducing power required to run the reductive citric acid cycle (RCC) might have been provided by ferrous or nickel sulfide\/CO\/SH2or CH3SH. See:"},{"key":"e_1_2_4_56_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.276.5310.245"},{"key":"e_1_2_4_57_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.281.5377.670"},{"key":"e_1_2_4_58_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.289.5483.1337"},{"key":"e_1_2_4_59_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0016-7037(01)00674-3"},{"key":"e_1_2_4_60_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr900209c"},{"key":"e_1_2_4_61_1","unstructured":"\u00a0"},{"key":"e_1_2_4_62_2","first-page":"252","volume":"3","author":"Wohler F.","year":"1832","journal-title":"Justus Liebigs Ann. Chem."},{"key":"e_1_2_4_63_2","first-page":"129","volume":"88","author":"Cannizzaro S.","year":"1853","journal-title":"ibid."},{"key":"e_1_2_4_64_2","first-page":"94","volume":"2","author":"Geissman T. A.","year":"1944","journal-title":"Org. React."},{"key":"e_1_2_4_65_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00507a023"},{"key":"e_1_2_4_66_1","first-page":"415","volume":"22","author":"Nemtsov M. S.","year":"1952","journal-title":"Zh. Obshch. Khim."},{"key":"e_1_2_4_67_1","doi-asserted-by":"publisher","DOI":"10.1038\/373683a0"},{"key":"e_1_2_4_68_1","unstructured":"Data provided as Supplementary Information."},{"key":"e_1_2_4_69_1","unstructured":"As suggested by a reviewer acid catalysis may facilitate the carboxylation step as some stabilization through a proton donor at the CO2moiety in the transition state should be expected."},{"key":"e_1_2_4_70_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar900013p"},{"key":"e_1_2_4_71_1","doi-asserted-by":"crossref","unstructured":"For a comprehensive analysis on the possible role of hydrothermal systems see \u201cMarine Hydrothermal Systems and the Origin of Life\u201d Ed. N.\u2005G. Holm Springer-Verlag+Business Media BV Dordrecht1992. See also W. Martin J. Baross D. Kelley M.\u2005J. Rusell Nature Reviews Microbiol.2008 6 805\u2013814. For an opposing view see the perspective of J.\u2005L. Bada A. Lazcano Science2002 296 1982\u20131983.","DOI":"10.1038\/nrmicro1991"},{"key":"e_1_2_4_72_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo00090a030"},{"key":"e_1_2_4_73_1","unstructured":"\u00a0"},{"key":"e_1_2_4_74_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.192568299"},{"key":"e_1_2_4_75_2","doi-asserted-by":"publisher","DOI":"10.1007\/s11084-007-9120-3"},{"key":"e_1_2_4_76_1","unstructured":"Several reports on the smooth reducing power of glycerol have appeared in the recent literature. See"},{"key":"e_1_2_4_77_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2013.04.057"},{"key":"e_1_2_4_78_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3gc36908k"},{"key":"e_1_2_4_79_2","doi-asserted-by":"publisher","DOI":"10.3390\/app3010055"},{"key":"e_1_2_4_80_1","unstructured":"The computed (M06-2X\/6-311++G(dp\/PCM(water) energy barriers for the redox reactions glycolaldehyde+glycolaldehyde hydrate\u2192glycol+glycolic acid (\u0394G*=33.7\u2005kcal\/mol); glyceraldehyde+glyceraldehyde hydrate\u2192glycerol+ glyceric acid (\u0394G*=33.4\u2005kcal\/mol); glycerol+dihydroxyacetone\u2192dihydroxyacetone+glycerol (\u0394G*=38.4\u2005kcal\/mol) suggest but do not prove that the Cannizzaro-like conversions1\u21922and6\u21927might be achievable. Not so for the conversion fumaric acid3into succinic acid4."},{"key":"e_1_2_4_81_1","doi-asserted-by":"publisher","DOI":"10.1128\/mr.52.4.452-484.1988"},{"key":"e_1_2_4_81_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0723-2020(88)80001-8"},{"key":"e_1_2_4_82_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar000056y"},{"key":"e_1_2_4_83_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar00052a003"},{"key":"e_1_2_4_84_1","doi-asserted-by":"publisher","DOI":"10.1016\/0006-3002(55)90079-2"},{"key":"e_1_2_4_84_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bioorg.2004.06.005"},{"key":"e_1_2_4_85_1","doi-asserted-by":"publisher","DOI":"10.1021\/bi9620722"},{"key":"e_1_2_4_86_1","first-page":"190","author":"Rode B. M.","year":"1999","journal-title":"Coord. Chem. 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