Probing the catalytically active species in POM‐catalysed DNA‐model hydrolysis

Martins, F. F., Sánchez‐González, Á., Lanuza, J., Miras, H. N. , Lopez, X., Bandeira, N. A. and Gil, A. (2021) Probing the catalytically active species in POM‐catalysed DNA‐model hydrolysis. Chemistry: A European Journal, 27(35), pp. 8977-8984. (doi: 10.1002/chem.202004989) (PMID:33885198)

Abstract

Phosphoester hydrolysis is an important chemical step in DNA repair. One archetypal molecular model of phosphoesters is para-nitrophenylphosphate (pNPP). It has been shown previously that the presence of molecular metal oxide [Mo7O24]6− may catalyse the hydrolysis of pNPP through the partial decomposition of polyoxomolybdate framework resulting in a [(PO4)2Mo5O15]6− product. Real-time monitoring of the catalytic system using electrospray ionisation mass spectrometry (ESI-MS) provided a glance into the species present in the reaction mixture and identification of potential catalytic candidates. Following up on the obtained spectrometric data, Density Functional Theory (DFT) calculations were carried out to characterise the hypothetical intermediate [Mo5O15(pNPP)2(H2O)6]6− that would be required to form under the hypothesised transformation. Surprisingly, our results point to the dimeric [Mo2O8]4− anion resulting from the decomposition of [Mo7O24]6− as the active catalytic species involved in the hydrolysis of pNPP rather than the originally assumed {Mo5O15} species. A similar study was carried out involving the same species but substituting Mo by W. The mechanism involving W species showed a higher barrier and less stable products in agreement with the non-catalytic effect found in experimental results.

• Item Type: Articles
• Additional Information: This research was financially supported by the Fundação para a Ciência e a Tecnologia (FCT) by means of the projects PTDC/QUI-QFI/29236/2017, UID/MULTI/00612/2019, UID/MULTI/04046/2019, UIDB/04046/2020, UIDP/04046/2020 and by the Spanish Ministry of Economy, Industry and Competitiveness under the Maria de Maeztu Units of Excellence Programme – MDM-2016-0618. This research was also funded by Eusko Jaurlaritza (the Basque Government), through Consolidated Group Project No. IT1254-19, and the Spanish MINECO/FEDER Project No. PGC2018-097529-B-100.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Moiras, Professor Haralampos
• Authors: Martins, F. F., Sánchez‐González, Á., Lanuza, J., Miras, H. N., Lopez, X., Bandeira, N. A., and Gil, A.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Chemistry: A European Journal
• Publisher: Wiley
• ISSN: 0947-6539
• ISSN (Online): 1521-3765
• Published Online: 22 April 2021
• Copyright Holders: Copyright © 2021 Wiley-VCH GmbH
• First Published: First published in Chemistry: A European Journal 27(35):8977-8984
• Publisher Policy: Reproduced in accordance with the publisher copyright policy