Evidence map›Paper›PMID 26588933›Full record

ArticleJournal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry2015

Oxidation of 5'-dGMP, 5'-dGDP, and 5'-dGTP by a platinum(IV) complex.

Ioannis Kipouros, Sebastian Matias Fica-Contreras, Gregory Joon Kee Bowe, Sunhee Choi

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Article in Journal of biological inorganic chemistry : JBIC : a publication of the Society of Biological Inorganic Chemistry, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.

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1 · What the graph read from it

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4 · The record

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5 · Who and what money

Authors and funding

4 authors.

Ioannis KipourosDepartment of Chemistry and Biochemistry, Middlebury College, Middlebury, VT, 05753, USA.
Sebastian Matias Fica-ContrerasDepartment of Chemistry and Biochemistry, Middlebury College, Middlebury, VT, 05753, USA.
Gregory Joon Kee BoweDepartment of Chemistry and Biochemistry, Middlebury College, Middlebury, VT, 05753, USA.
Sunhee ChoiDepartment of Chemistry and Biochemistry, Middlebury College, Middlebury, VT, 05753, USA. choi@middlebury.edu.

Funding

No grant is acknowledged in the PubMed record.

6 · The paper itself

Abstract

We previously reported that a Pt(IV) complex, [Pt(IV)(dach)Cl4] [trans-d,l-1,2-diaminocyclohexanetetrachloroplatinum(IV)] binds to the N7 of 5'-dGMP (deoxyguanosine-5'-monophosphate) at a relatively fast rate and oxidizes it to 8-oxo-5'-dGMP. Here, we further studied the kinetics of the oxidation of 5'-dGMP by the Pt(IV) complex. The electron transfer rate constants between 5'-dGMP and Pt(IV) in [H8-5'-dGMP-Pt(IV)] and [D8-5'-dGMP-Pt(IV)] were similar, giving a small value of the kinetic isotope effect (KIE: 1.2 ± 0.2). This small KIE indicates that the deprotonation of H8 in [H8-5'-dGMP-Pt(IV)] is not involved in the rate-determining step in the electron transfer between guanine (G) and Pt(IV). We also studied the reaction of 5'-dGDP (deoxyguanosine-5'-diphosphate) and 5'-dGTP (deoxyguanosine-5'-triphosphate) with the Pt(IV) complex. Our results showed that [Pt(IV)(dach)Cl4] oxidized 5'-dGDP and 5'-dGTP to 8-oxo-5'-dGDP and 8-oxo-5'-dGTP, respectively, by the same mechanism and kinetics as for 5'-dGMP. The Pt(IV) complex binds to N7 followed by a two-electron inner sphere electron transfer from G to Pt(IV). The reaction was catalyzed by Pt(II) and occurred faster at higher pH. The electron transfer was initiated by either an intramolecular nucleophilic attack by any of the phosphate groups or an intermolecular nucleophilic attack by free OH(-) in the solution. The rates of reactions for the three nucleotides followed the order: 5'-dGMP > 5'-dGDP > 5'-dGTP, indicating that the bulkier the phosphate groups are, the slower the reaction is, due to the larger steric hindrance and rotational barrier of the phosphate groups.

Indexed as

Coordination ComplexesDeoxyguanine NucleotidesGuanine NucleotidesGuanosine DiphosphateGuanosine MonophosphateMagnetic Resonance SpectroscopyMolecular StructureOxidation-ReductionPlatinumTime Factors2'-deoxyguanosine 3',5'-diphosphateCoordination ComplexesDeoxyguanine Nucleotidesdeoxyguanosine triphosphateGuanine NucleotidesGuanosine DiphosphateGuanosine MonophosphatePlatinum5′-dGDP5′-dGMP5′-dGTPOxidationPlatinum(IV) complex

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Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.