A1 Refereed original research article in a scientific journal
Sulfurization of H-Phosphonate Diesters by Elemental Sulfur under Aqueous Conditions
Authors: Lönnberg Tuomas
Publisher: American Chemical Society
Publication year: 2017
Journal: ACS Omega
Journal name in source: ACS OMEGA
Volume: 2
Issue: 8
First page : 5122
Last page: 5127
Number of pages: 6
ISSN: 2470-1343
DOI: https://doi.org/10.1021/acsomega.7b00970
Web address : http://pubs.acs.org/doi/10.1021/acsomega.7b00970
Self-archived copy’s web address: https://research.utu.fi/converis/portal/detail/Publication/27873577
Abstract
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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