Kinetic and Mechanistic Investigations on Some <i>N</i>,<i>N</i>‐Chelated Pt(II) Oxalate Complexes with Some “S” Containing Biorelevant Ligands at Physiological Condition

Ray, Sumanta; Karmakar, Parnajyoti; Chattopadhyay, Animesh; Nandi, Debabrata; Sarkar, R. K.; Ghosh, Aditi

doi:10.1002/kin.20995

Cited by 5 publications

(5 citation statements)

References 41 publications

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“…Evaluation of the rate constant k 1 . The rate constant of the first step (I → II in Scheme ) is dependent on the thione concentration, which is consistent with previous reports . At constant temperature, the rate constant ( k obsd1 ) for reaction of Tu or DIAZ with [Au( cis ‐DACH)Cl 2 ]Cl and [Au( cis ‐DACH) 2 ]Cl 3 was obtained from the slopes of the plots of ln Δ versus time ( t ) (Eq.…”

Section: Resultssupporting

confidence: 88%

“…The kinetics of the formation and equilibrium hydrolysis of [AuBr 4 ] − and [AuCl 4 ] − revealed a two‐term rate law and indicated that their hydrolysis was faster than the analogous Pt(II) complexes . Ray et al evaluated the activation parameters of kinetics for the substitution reactions of cis ‐[Pt(DACH)(H 2 O) 2 ] 2+ , DACH = cis ‐1,2‐diaminocyclohexane, with dipeptides containing glycine, glutathione, and penicillamine under pseudo–first‐order conditions depending on pH, ligand concentration, and complex formation .…”

Section: Introductionmentioning

confidence: 99%

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Spectroscopic and Electrochemical Studies of the Interaction of Some Gold(III) Complexes with Biologically Relevant Thiones

Sulaiman

Omer

Kawde

et al. 2018

Int J of Chemical Kinetics

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The interaction of gold(III) complexes, [Au(cis‐DACH)Cl2]Cl and [Au(cis‐DACH)2]Cl3 complexes (DACH = cis‐1,2‐diaminocyclohexane), with 13C, 15N‐enriched thiourea (Tu) and 1,3‐diazinane‐2‐thione ligands was investigated. The progress of these reactions was monitored by NMR (1H, 13C, and 15N) and UV–vis spectroscopy as well as square wave stripping voltammetry. The kinetic studies of the substitution reactions between the above‐mentioned complexes with thiones in aqueous solutions containing 30 mM KCl, which is used to suppress the hydrolysis of the chloride complexes, were conducted. These reactions were followed under pseudo–first‐order conditions as functions of ligand concentration, pH, and temperature. The activation parameters (ΔH#, ΔS#) were calculated from Eyring plots, and the negative values of ΔS≠ lend support for an associative mechanism. The kinetic data also indicated a relatively higher reactivity of [Au(cis‐DACH)Cl2]Cl than that of [Au(cis‐DACH)2]Cl3 toward the thiones.

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Section: Resultssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Spectroscopic and Electrochemical Studies of the Interaction of Some Gold(III) Complexes with Biologically Relevant Thiones

Sulaiman

Omer

Kawde

et al. 2018

Int J of Chemical Kinetics

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“…The recorded absorption at 681 cm −1 was also attributed to the Pt–N bond vibration (Figure 7). [ 87 ]…”

Section: Resultsmentioning

confidence: 99%

“…The recorded absorption at 681 cm −1 was also attributed to the Pt-N bond vibration (Figure 7). [87] F I G U R E 4 Elemental composition of the final product of (A) ZnO NPs@polymer shell compared to (B) ZnO NPs@polymer shell.…”

Section: Fesemmentioning

confidence: 99%

The advance anticancer role of polymeric core‐shell ZnO nanoparticles containing oxaliplatin in colorectal cancer

Alavi

Maghami

Pakdel

et al. 2023

J Biochem & Molecular Tox

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We evaluated the activity of core‐shell ZnO nanoparticles (ZnO‐NPs@polymer shell) containing Oxaliplatin via polymerization through in vitro studies and in vivo mouse models of colorectal cancer. ZnO NPs were synthesized in situ when the polymerization step was completed by co‐precipitation. Gadolinium coordinated‐ZnONPs@polymer shell (ZnO‐Gd NPs@polymer shell) was synthesized by exploiting Gd's oxophilicity (III). The biophysical properties of the NPs were studied using powder X‐ray diffraction (PXRD), Fourier transforms infrared spectroscopy, Ultraviolet‐visible spectroscopy (UV‐Vis), field emission electron microscopy (FESEM), transmission electron microscopy (TEM), atomic force microscopy, dynamic light scattering, and z‐potential. (3‐(4,5‐Dimethylthiazol‐2‐yl)−2,5‐diphenyltetrazolium bromide) (MTT) was used to determine the antiproliferative activity of ZnO‐Gd‐OXA. Moreover, a xenograft mouse model of colon cancer was exerted to survey its antitumor activity and effect on tumor growth. In the following, the model was also evaluated by histological staining (H‐E; Hematoxylin & Eosin and trichrome staining) and gene expression analyses through the application of RT‐PCR/ELISA, which included biochemical evaluation (MDA, thiols, SOD, CAT). The formation of ZnO NPs, which contained a crystallite size of 16.8 nm, was confirmed by the outcomes of the PXRD analysis. The Plate‐like morphology and presence of Pt were obtained in EDX outcomes. TEM analysis displayed the attained ZnO NPs in a spherical shape and a diameter of 33 ± 8.5 nm, while the hydrodynamic sizes indicated that the particles were highly aggregated. The biological results demonstrated that ZnO‐Gd‐OXA inhibited tumor growth by inducing reactive oxygen species and inhibiting fibrosis, warranting further research on this novel colorectal cancer treatment agent.

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“…The remaining sites are occupied by two monodentates or a bidentate ligand. Examples are Pt(II) complexes, which have N,N‐ or N,S‐ bidentate nonleaving ligands and these usually display a two‐step consecutive substitution of the labile leaving groups, with rates that are dependent on the electronic (σ‐donor/π‐acceptor) and steric demands of the resident ligand as well as the nucleophilicity of the labile ligands. Even in complexes where the coordinated bidentate ligand is symmetrical, substitution occurred consecutively .…”

Section: Introductionmentioning

confidence: 99%

Reactivity of cis‐platinum(II) complexes with 2‐(4‐substituted)phenylthiomethyl)quinoline nonleaving ligands toward thiourea nucleophiles

Mthiyane

Mambanda

Jaganyi

2018

Int J of Chemical Kinetics

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The sequential substitution of aqua ligands from quinoline}(H 2 O) 2 ]CF 3 SO 3 , Pt(L1), [Pt{2-(4-tert-butylphenylthiomethyl)quinoline}(H 2 O) 2 ]CF 3 SO 3 Pt(L2), and [Pt{2-(4-fluorophenylthiomethyl) quinoline}(H 2 O) 2 ]CF 3 SO 3 Pt(L3) by thiourea nucleophiles (Nu) was studiedunder pseudo-first-order conditions as a function of concentration and temperature using stopped-flow and UV-visible spectrophotometric techniques. The observed pseudo-first-order rate constants for the substitutions can be described by the rate law: k obs(1/2) = k 2(1/2) [Nu], where the subscript denotes the consecutive substitution steps. The first aqua ligand was substituted opposite to the strong -trans-directing thioether followed by the aqua ligand opposite to the quinoline or pyridine moieties. Second-order rate constants, k 2(1st) , for the substitution of the first aqua ligand by thiourea nucleophiles ranged between 9 and 22 M −1 s −1 for Pt(L1), 86 and 326 M −1 s −1 for Pt(L2), and 58 -287 M −1 s −1 for Pt(L3). The ranges of the second-order rate constant, k 2(2nd) , were always lower than the k 2(1st) 's and are 0.3-9 M −1 s -1 for Pt(L1), 2-20 M −1 s −1 for Pt(L2), and 0.3-5 M −1 s −1 for Pt(L3). Aqua substitution from Pt(L2) is slower for both steps than from Pt4, its pyridyl derivative from our previous study. A Job's method of continuous variation plot suggests a species with a metal-to-nucleophile ratio of 1:3 as the ultimate product of the chloride substitution from the Pt(II) complexes by the incoming thiourea nucleophiles. The high and negative activation entropy and low and positive activation enthalpy values support an associative mechanism of activation, characteristic of substitution reactions occurring in square-planar complexes. K E Y W O R D Sassociative mechanism, consecutive reaction, Pt(II) mononuclear complexes, substitution Int J Chem Kinet. 2018;50:531-543.

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Kinetic and Mechanistic Investigations on Some N,N‐Chelated Pt(II) Oxalate Complexes with Some “S” Containing Biorelevant Ligands at Physiological Condition

Cited by 5 publications

References 41 publications

Spectroscopic and Electrochemical Studies of the Interaction of Some Gold(III) Complexes with Biologically Relevant Thiones

Spectroscopic and Electrochemical Studies of the Interaction of Some Gold(III) Complexes with Biologically Relevant Thiones

The advance anticancer role of polymeric core‐shell ZnO nanoparticles containing oxaliplatin in colorectal cancer

Reactivity of cis‐platinum(II) complexes with 2‐(4‐substituted)phenylthiomethyl)quinoline nonleaving ligands toward thiourea nucleophiles

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