Experimental and theoretical study of the mechanism of hydrolysis of substituted phenyl hexanoates catalysed by globin in the presence of surfactant

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dc.contributor.authorErcan, Selami
dc.contributor.authorArslan, Nevin
dc.contributor.authorKocakaya, Safak Ozhan
dc.contributor.authorPirinccioglu, Necmettin
dc.contributor.authorWilliams, Andrew
dc.date.accessioned2024-04-24T16:01:59Z
dc.date.available2024-04-24T16:01:59Z
dc.date.issued2014
dc.departmentDicle Üniversitesien_US
dc.description.abstractThe bimolecular rate constants for the globin-and alkali-catalysed hydrolysis of substituted phenyl hexanoates in the absence and presence of cetyltrimethylammonium bromide (CTAB) obey Bronsted equations with beta(1g)=-0.53 (globin-catalysed), -0.68 (globin-catalysed in CTAB), -0.34 (in water) and -0.74 (in CTAB), respectively. The slopes indicate that the microsolvation environments associated with the transition states of the catalysed reactions are different from those that occur in aqueous medium. The slope (-0.74) for the reaction in CTAB implies that it proceeds in a less polar medium. The larger beta(1g) value (-0.53) obtained for the globin-catalysed reaction compared to that for the uncatalysed one may be attributed to either the less polar microenvironments of the transition states or the involvement of one of the imidazole groups as a nucleophile. The results from a study of the effect of pH on the reactivity provide evidence for the latter assumption. All of the ligands were docked into the hydrophobic pocket of the protein, and the resulting docking scores ranged from -30.76 to -23.61 kcal mol(-1). Molecular dynamic simulations and MM-PBSA/GBSA calculations performed for the complexes gave insight into the binding modes of globin to the esters, which are consistent with experimental results. The calculations yielded comparable free energies of binding to the experimental ones for 4-nitrophenyl and 4-chloro-2-nitrophenyl hexanoates. In conclusion, information obtained from the linear free-energy relationship is still very useful for elucidating the mechanisms of organic reactions, including enzyme-catalysed reactions. This approach is further supported by the utilization of computational tools.en_US
dc.description.sponsorshipUniversity of Dicleen_US
dc.description.sponsorshipThe University of Dicle is thanked for the studentship (NP). We are also grateful to TUBITAK (Scientific and Technological Council of Turkey) for their computational facilities and to DA Case (University of California, San Francisco) for a waiver licence for AMBER (v.9 and v.11).en_US
dc.identifier.doi10.1007/s00894-014-2096-9
dc.identifier.issn1610-2940
dc.identifier.issn0948-5023
dc.identifier.issue3en_US
dc.identifier.pmid24562853
dc.identifier.scopus2-s2.0-84899070394
dc.identifier.scopusqualityQ2
dc.identifier.urihttps://doi.org/10.1007/s00894-014-2096-9
dc.identifier.urihttps://hdl.handle.net/11468/14548
dc.identifier.volume20en_US
dc.identifier.wosWOS:000332180100008
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoenen_US
dc.publisherSpringeren_US
dc.relation.ispartofJournal of Molecular Modeling
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectCatalysisen_US
dc.subjectGlobinen_US
dc.subjectEnzyme Mimicen_US
dc.subjectPolar Substituent Effecten_US
dc.subjectMechanismen_US
dc.subjectPhenyl Hexanoatesen_US
dc.subjectMicellesen_US
dc.subjectMolecular Dynamicsen_US
dc.subjectMm-Pbsa/Gbsaen_US
dc.subjectDockingen_US
dc.titleExperimental and theoretical study of the mechanism of hydrolysis of substituted phenyl hexanoates catalysed by globin in the presence of surfactanten_US
dc.titleExperimental and theoretical study of the mechanism of hydrolysis of substituted phenyl hexanoates catalysed by globin in the presence of surfactant
dc.typeArticleen_US

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