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Influence of acid-base equilibrium on interactions of some monofunctional coumarin Pd(II) complexes with biologically relevant nucleophiles-comprehensive kinetic study.
Milanovic, Ziko; Markovic, Zoran; Kesic, Ana; Jovanovic Stevic, Snezana; Petrovic, Biljana; Avdovic, Edina.
Afiliación
  • Milanovic Z; University of Kragujevac, Institute of Information Technologies, Department of Science, Jovana Cvijica bb, 34000 Kragujevac, Serbia.
  • Markovic Z; University of Kragujevac, Institute of Information Technologies, Department of Science, Jovana Cvijica bb, 34000 Kragujevac, Serbia.
  • Kesic A; Department of Natural Science and Mathematics, State University of Novi Pazar, Vuka Karadzica bb, 36300, Novi Pazar, Serbia.
  • Jovanovic Stevic S; University of Kragujevac, Institute of Information Technologies, Department of Science, Jovana Cvijica bb, 34000 Kragujevac, Serbia.
  • Petrovic B; University of Kragujevac, Faculty of Medical Sciences, Department of Pharmacy, Svetozara Markovica 69, 34000 Kragujevac, Serbia.
  • Avdovic E; University of Kragujevac, Faculty of Science, Department of Chemistry, Radoja Domanovica 12, 34000 Kragujevac, Serbia.
Dalton Trans ; 53(19): 8275-8288, 2024 May 14.
Article en En | MEDLINE | ID: mdl-38659318
ABSTRACT
This aimed to develop a comprehensive theoretical protocol for examining substitution reaction processes. The researchers used a theoretical quantum-mechanical protocol based on the QM-ORSA approach, which estimates the kinetic parameters of thermodynamically favourable reaction pathways. This theoretical protocol was validated by experimentally investigating substitution mechanisms in two previously synthesised Pd(II) complexes chlorido-[(3-(1-(2-hydroxypropylamino)ethylidene)chroman-2,4-dione)]palladium(II) (C1) and chlorido-[(3-(1-(2-mercaptoethylamino)-ethylidene)-chroman-2,4dione)]palladium(II) (C2), along with biologically relevant nucleophiles, namely L-cysteine (l-Cys), L-methionine (l-Met), and guanosine-5'-monophosphate (5'-GMP). Reactions were investigated under pseudo-first-order conditions, monitoring nucleophile concentration and temperature changes using stopped-flow UV-vis spectrophotometry. All reactions were conducted under physiological conditions (pH = 7.2) at 37 °C. The reactivity of the studied nucleophiles follows the order l-Cys > l-Met > 5'-GMP, and the reaction mechanism is associative based on the activation parameters. The experimental and theoretical data showed that C2 is more reactive than C1, confirming that the complexes' structural and electronic properties greatly affect their reactivity with selected nucleophiles. The study's findings have confirmed that the primary interaction occurs with the acid-base species L-Cys, mostly through the involvement of the partially negative sulfur atom (87.2%). On the other hand, C2 has a higher propensity for reacting with L-Cys-, primarily through the partially negative oxygen atom (92.6%). The implementation of this theoretical framework will significantly restrict the utilization of chemical substances, hence facilitating cost reduction and environmental protection.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Paladio / Cumarinas / Cisteína / Complejos de Coordinación Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article Pais de publicación: Reino Unido
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Paladio / Cumarinas / Cisteína / Complejos de Coordinación Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article Pais de publicación: Reino Unido