Interactions of Ascorbic Acid with Satraplatin and its trans Analog JM576: DFT Computational Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F18%3A10384675" target="_blank" >RIV/00216208:11320/18:10384675 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1002/ejic.201701334" target="_blank" >https://doi.org/10.1002/ejic.201701334</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/ejic.201701334" target="_blank" >10.1002/ejic.201701334</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Interactions of Ascorbic Acid with Satraplatin and its trans Analog JM576: DFT Computational Study

Popis výsledku v původním jazyce

Knowledge of the mechanisms for the reduction of Pt-IV anticancer prodrugs is of great importance, since the reduction process is considered as a necessary step for their activation. Therefore, in this study, we investigate the reduction of satraplatin {JM216, cis,trans,cis-[PtCl2(OAc)(2)(cha)(NH3)], cha = cyclohexylamine} by ascorbic acid (AA) where proton-assisted electron-transfer and outer-sphere electron-transfer mechanisms are employed. Also, the presence of an additional base, which should increase the concentration of the deprotonated AA(2-) form, is discussed. Structures are optimized at the B3LYP-GD3BJ/6-31+G(d)/MWB60/C-PCM/Klamt level and single-point calculations are performed in the larger 6-311++G(2df,2pd)/MWB60 basis set, together with the better implicit solvation model - IEF-PCM/scaled-UAKS. All three protonation states of ascorbic acid are taken into consideration. An effective rate constant of 2.6x10(-3) m(-1)s(-1) is obtained from the kinetic formalism for side reactions, as described recently. For the reduction of satraplatin by fully deprotonated ascorbic acid, changes of the electron-density distribution along the reaction coordinate are further investigated using NPA, QTAIM, and reaction electronic-flux analysis. Both electron-transfer mechanisms are also explored for the satraplatin trans analog JM576 {trans,trans,trans-[PtCl2(OAc)(2)(cha)(NH3)]}. The resulting effective rate constant of 5.1x10(-2) m(-1)s(-1) is compared with available experimental data.

Název v anglickém jazyce

Interactions of Ascorbic Acid with Satraplatin and its trans Analog JM576: DFT Computational Study

Popis výsledku anglicky

Knowledge of the mechanisms for the reduction of Pt-IV anticancer prodrugs is of great importance, since the reduction process is considered as a necessary step for their activation. Therefore, in this study, we investigate the reduction of satraplatin {JM216, cis,trans,cis-[PtCl2(OAc)(2)(cha)(NH3)], cha = cyclohexylamine} by ascorbic acid (AA) where proton-assisted electron-transfer and outer-sphere electron-transfer mechanisms are employed. Also, the presence of an additional base, which should increase the concentration of the deprotonated AA(2-) form, is discussed. Structures are optimized at the B3LYP-GD3BJ/6-31+G(d)/MWB60/C-PCM/Klamt level and single-point calculations are performed in the larger 6-311++G(2df,2pd)/MWB60 basis set, together with the better implicit solvation model - IEF-PCM/scaled-UAKS. All three protonation states of ascorbic acid are taken into consideration. An effective rate constant of 2.6x10(-3) m(-1)s(-1) is obtained from the kinetic formalism for side reactions, as described recently. For the reduction of satraplatin by fully deprotonated ascorbic acid, changes of the electron-density distribution along the reaction coordinate are further investigated using NPA, QTAIM, and reaction electronic-flux analysis. Both electron-transfer mechanisms are also explored for the satraplatin trans analog JM576 {trans,trans,trans-[PtCl2(OAc)(2)(cha)(NH3)]}. The resulting effective rate constant of 5.1x10(-2) m(-1)s(-1) is compared with available experimental data.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

<a href="/cs/project/GA16-06240S" target="_blank" >GA16-06240S: Struktura a dynamika organokovových komplexů v biologickém prostředí.</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2018

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

European Journal of Inorganic Chemistry

ISSN

1434-1948

e-ISSN

—

Svazek periodika

2018

Číslo periodika v rámci svazku

13

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

11

Strana od-do

1481-1491

Kód UT WoS článku

000430003700003

EID výsledku v databázi Scopus

2-s2.0-85042069732