A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
Sulfurization of H-Phosphonate Diesters by Elemental Sulfur under Aqueous Conditions
Tekijät: Lönnberg Tuomas
Kustantaja: American Chemical Society
Julkaisuvuosi: 2017
Journal: ACS Omega
Tietokannassa oleva lehden nimi: ACS OMEGA
Vuosikerta: 2
Numero: 8
Aloitussivu: 5122
Lopetussivu: 5127
Sivujen määrä: 6
ISSN: 2470-1343
DOI: https://doi.org/10.1021/acsomega.7b00970
Verkko-osoite: http://pubs.acs.org/doi/10.1021/acsomega.7b00970
Rinnakkaistallenteen osoite: https://research.utu.fi/converis/portal/detail/Publication/27873577
Tiivistelmä
To assess the plausibility of prebiotic nucleic acid polymerization by a sequential phosphitylation-sulfurization mechanism, the rates of hydrolysis and sulfurization of bis(2', 3'-O-methyleneadenosin-5'-yl)-H-phosphonate, a dinucleoside H-phosphonate diester, have been determined over a wide pH range (0.52-7.25) and in the presence of varying amounts (0-30 mg) of elemental sulfur. The pH-rate profile of hydrolysis resembled the one previously reported for the Hphosphonate analogue of thymidylyl-3', 5'-thymidine, with a relatively wide pH-independent region flanked by acid-and base-catalyzed regions. Sulfurization to the respective phosphorothioate diester, in turn, was found to be basecatalyzed over the entire pH range studied. Despite the facile hydrolysis of H-phosphonate diesters and the extremely low solubility of elemental sulfur in water, sulfurization and hydrolysis proceeded at comparable rates under neutral and mildly acidic conditions.
To assess the plausibility of prebiotic nucleic acid polymerization by a sequential phosphitylation-sulfurization mechanism, the rates of hydrolysis and sulfurization of bis(2', 3'-O-methyleneadenosin-5'-yl)-H-phosphonate, a dinucleoside H-phosphonate diester, have been determined over a wide pH range (0.52-7.25) and in the presence of varying amounts (0-30 mg) of elemental sulfur. The pH-rate profile of hydrolysis resembled the one previously reported for the Hphosphonate analogue of thymidylyl-3', 5'-thymidine, with a relatively wide pH-independent region flanked by acid-and base-catalyzed regions. Sulfurization to the respective phosphorothioate diester, in turn, was found to be basecatalyzed over the entire pH range studied. Despite the facile hydrolysis of H-phosphonate diesters and the extremely low solubility of elemental sulfur in water, sulfurization and hydrolysis proceeded at comparable rates under neutral and mildly acidic conditions.
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