Probing the Catalytically Active Species in POM‐Catalysed DNA‐Model Hydrolysis**

نویسندگان

چکیده

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

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ژورنال

عنوان ژورنال: Chemistry: A European Journal

سال: 2021

ISSN: ['0947-6539', '1521-3765']

DOI: https://doi.org/10.1002/chem.202004989