Kinetics and mechanism of the interaction of<scp>DL</scp>-penicillamine with<i>cis</i>-diaqua(<i>cis</i>-1,2-diaminocyclohexane)platinum(II) perchlorate in aqueous medium

Karmakar, Parnajyoti; Bera, Biplab K.; Barik, Kanai Lal; Mukhopadhyay, Sourav; Ghosh, Aniruddha

doi:10.1080/00958972.2010.498910

Cited by 13 publications

(5 citation statements)

References 25 publications

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“…The small band observed at 530 cm −1 corresponds to the formation of a Ru–N bond in the product. 48 Therefore, the spectrum suggests that ruthenium(II) is likely to be coordinated through the nitrogen atom of the pyridine ring due to the strong coordinating ability of the nitrogen atom.…”

Section: Resultsmentioning

confidence: 99%

Kinetics and mechanism of formation of the complex [Ru(CN)₅INH]³⁻ through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Yadav

Naik

2019

Progress in Reaction Kinetics and Mechanism

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The formation kinetics of the complex, [Ru(CN) 5 INH] 32 , formed through the ligand substitution reaction between isoniazid (INH) and aquapentacyanoruthenate(II) ([Ru(CN) 5 H 2 O] 32 ), have been investigated, under pseudo first-order conditions, as a function of concentrations of [INH] and [Ru(CN) 5 H 2 O] 32 , ionic strength and temperature at pH = 4.0 6 0.02 in 0.2 M NaClO 4 spectrophotometrically at 502 nm (l max of intense yellow colour product [Ru(CN) 5 INH] 32 ) corresponding to metal-to-ligand charge-transfer transitions, in aqueous medium. The pseudo first-order condition was maintained by taking at least 10% excess of [INH] over [Ru(CN) 5 H 2 O] 32 . The stoichiometry of the reaction product was found to be 1:1 which was further supported and characterized using elemental analysis, infrared, nuclear magnetic resonance and mass spectrometric techniques. Thermodynamic and kinetic parameters have also been computed, using the Eyring equation, and the values of DH 6 ¼ , E a , DG 6 ¼ and DS 6 ¼ were found to be 47.3 kJ mol 21 , 49.8 kJ mol 21 , 28.62 kJ mol 21 and 187.6 J K 21 mol 21 , respectively. The reaction was found to obey first-order kinetics with respect to [INH]. It exhibited a negative salt effect on the rate upon variation of ionic strength of the medium. A tentative mechanistic scheme was proposed on the basis of experimental findings.

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Section: Resultsmentioning

confidence: 99%

Kinetics and mechanism of formation of the complex [Ru(CN)₅INH]³⁻ through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Yadav

Naik

2019

Progress in Reaction Kinetics and Mechanism

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“…In continuation with our earlier work [12], we now present the kinetic and mechanistic aspects of the interaction of cis-[Pt(cis-dach)(OH 2 ) 2 ] 2+ with the three dipeptides.…”

Section: S Ray R Sarkar (Sain) a Chattopadhyay And Ak Ghoshmentioning

confidence: 88%

“…Preparation of the title complex has been described in an earlier paper [12]. The product of the reaction between complex (1) and the ligands (glycyl-Lvaline(L 1 -L′H), glycyl-L-isoleucine(L 2 -L′H) and glycyl-L-glutamine(L 3 -L′H)) were prepared separately by mixing the reagents at pH 4.0 in different molar ratios, namely 1 : 1, 1 : 2, 1 : 3, 1 : 4 and 1 : 5, and equilibrating the mixtures at 60 °C for 48 h. The absorption spectra of the resulting complexes were recorded and found to exhibit maximum absorption at 230, 229 and 228 nm respectively.…”

Section: Methodsmentioning

confidence: 99%

“…So at pH 4.0, amide deprotonation is difficult to occur for dipeptides and the reaction becomes slower. The higher enthalpy of activation of the dipeptides can be explained by their weak ability to form hydrogen bonds during substitution (outer sphere association) with the leaving aqua ligand, whereas glutathione [19] and DL-penicillamine [12] are able to form such hydrogen bonds by the -SH group On the basis of the experimental results described above, we propose a plausible mechanism for the interaction reaction in Figure 8.…”

Section: Mechanism and Conclusionmentioning

confidence: 98%

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Kinetic and Mechanistic Aspects of Ligand Substitution on cis- Diaqua (cis-1,2-Diaminocyclohexane)Platinum(II) with Three Glycine-Containing Dipeptides

Ray

Sarkar

Chattopadhyay

et al. 2014

Progress in Reaction Kinetics and Mechanism

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The kinetics of the interaction of glycyl-L-valine(L 1 -L′H), glycyl-L-isoleucine (L 2 -L′H) and glycyl-L-glutamine(L 3 -L′H) with cis-[Pt(cis-dach)(OH 2 ) 2 ] 2+ (dach = 1,2-diaminocyclohexane) have been studied spectrophotometrically as a function of [cis-[Pt(cis-dach)(OH 2 ) 2 ] 2+ ], [ligand], pH and temperature at constant ionic strength, where the complex exists predominantly as the diaqua species and the dipeptides as a zwitterion. The substitution reactions show two consecutive steps: the initial is the ligand-assisted anation and the subsequent step is chelation. The activation parameters for both steps were evaluated using Eyring's equation. The low ∆H 1 ≠ and large negative value of ∆S 1 ≠ as well as ∆H 2 ≠ and ∆S 2 ≠ indicate an associative mode of activation for both the aqua ligand substitution processes. The products of the reactions have been characterised using IR and ESI-mass spectroscopic analysis. The title complex is already established as an anticancer drug; but its reactivity with all biomolecules will confirm its therapeutic activity (i.e. its efficacy versus toxicity).Ligand substitution on cis-diaqua platinum www.prkm.co.uk 123 neurotoxicity, nausea, vomiting, and myelosuppression [7,8]. The continuing interest and stimulation has been triggered and guided by two objectives: first, to develop new metal complexes having superior spectra of activities, lower toxicities, better therapeutic indices, and higher solubilities than the presently existing drugs; and second, to understand the mechanistic features of the actions of metal complexes in vivo from the model reactions in vitro. Thus, further investigations have been carried out to synthesise "the second generation platinum drugs" with improved toxicological profiles and "third generation drugs" overcoming cisplatin resistance. Besides cisplatin, the second-generation drug, carboplatin (diamine[1,1cyclobutane-dicarboxylato(2-)]-O,O´-platinum(II)) has been introduced into oncotherapy and the third generation drug, oxaliplatin (cis-oxalato-trans-l-1,2-diaminocyclohexaneplatinum(II)) has been approved for clinical use in Europe, China and, for colorectal cancer, the USA [9]. Dach-Pt compounds have been intensively studied because of their potential efficacy against cisplatin-resistant tumours and their reduced nephrotoxicity and myelotoxicity compared to cisplatin and carboplatin. Since dach-Pt compounds can overcome cisplatin resistance in some cancer cell lines but not in others, it is important to understand the mechanism which determine the carrier ligand specificity of resistance. The ultimate target for Pt is DNA and certain platinated DNA adducts trigger DNA degradation and apoptosis (programmed cell death) [10,11]. Although intensive efforts of various research groups in the recent past have contributed significantly towards understanding the antitumour activity of platinum complexes, most of the studies focused on the structural identification of the binding of the DNA constituents to the metal centre using NMR, HPLC, ESI-MS and X-...

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“…The conversion from O,S-to N,S-chelate complex is irreversible. The coordination of Pt(II) and Pd(II) with methionine in an aqueous solution reveals coordination through the sulfur atom, and chelation through the amino group in a second, slow step [52,53].…”

Section: Interaction Of [Pd(nˆn)(h 2 O) 2 ] 2+ Complexes With Amino A...mentioning

confidence: 99%

Equilibrium Studies on Pd(II)–Amine Complexes with Bio-Relevant Ligands in Reference to Their Antitumor Activity

Shoukry

Eldik

2023

IJMS

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This review article presents an overview of the equilibrium studies on Pd-amine complexes with bio-relevant ligands in reference to their antitumor activity. Pd(II) complexes with amines of different functional groups, were synthesized and characterized in many studies. The complex formation equilibria of Pd(amine)2+ complexes with amino acids, peptides, dicarboxylic acids and DNA constituents, were extensively investigated. Such systems may be considered as one of the models for the possible reactions occurring with antitumor drugs in biological systems. The stability of the formed complexes depends on the structural parameters of the amines and the bio-relevant ligands. The evaluated speciation curves can help to provide a pictorial presentation of the reactions in solutions of different pH values. The stability data of complexes with sulfur donor ligands compared with those of DNA constituents, can reveal information regarding the deactivation caused by sulfur donors. The formation equilibria of binuclear complexes of Pd(II) with DNA constituents was investigated to support the biological significance of this class of complexes. Most of the Pd(amine)2+ complexes investigated were studied in a low dielectric constant medium, resembling that of a biological medium. Investigations of the thermodynamic parameters reveal that the formation of the Pd(amine)2+ complex species is exothermic.

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Kinetics and mechanism of the interaction ofDL-penicillamine withcis-diaqua(cis-1,2-diaminocyclohexane)platinum(II) perchlorate in aqueous medium

Cited by 13 publications

References 25 publications

Kinetics and mechanism of formation of the complex [Ru(CN)₅INH]³⁻ through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Kinetics and mechanism of formation of the complex [Ru(CN)₅INH]³⁻ through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Kinetic and Mechanistic Aspects of Ligand Substitution on cis- Diaqua (cis-1,2-Diaminocyclohexane)Platinum(II) with Three Glycine-Containing Dipeptides

Equilibrium Studies on Pd(II)–Amine Complexes with Bio-Relevant Ligands in Reference to Their Antitumor Activity

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Kinetics and mechanism of the interaction ofDL-penicillamine withcis-diaqua(cis-1,2-diaminocyclohexane)platinum(II) perchlorate in aqueous medium

Cited by 13 publications

References 25 publications

Kinetics and mechanism of formation of the complex [Ru(CN)5INH]3− through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Kinetics and mechanism of formation of the complex [Ru(CN)5INH]3− through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Kinetic and Mechanistic Aspects of Ligand Substitution on cis- Diaqua (cis-1,2-Diaminocyclohexane)Platinum(II) with Three Glycine-Containing Dipeptides

Equilibrium Studies on Pd(II)–Amine Complexes with Bio-Relevant Ligands in Reference to Their Antitumor Activity

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Kinetics and mechanism of formation of the complex [Ru(CN)₅INH]³⁻ through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid

Kinetics and mechanism of formation of the complex [Ru(CN)₅INH]³⁻ through the ligand substitution reaction between the aquapentacyanoruthenate(II) anion and isoniazid