Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest

Aliaga, ME; Tiznado, W; Cassels, BK; Nunez, MT; Millán D.; Perez, EG.; Garcia-Beltran, O; Pavez P.

Abstract

The Michael addition reactions of the biothiols cysteine, homocysteine, cysteinyl-glycine, gamma-glutamylcysteine and glutathione with 3-cinnamoylcoumarin derivatives (ChC1-ChC4) in aqueous solution (30 degrees C, ionic strength 0.2 M KCI) were followed fluorimetrically and evaluated kinetically. The study was completed with a theoretical analysis based on the inverse of the Fukui potential (1/v(f) (r)), which is proposed for the first time as a local softness descriptor. Thus, considering both experimental results and theoretical analysis, the following conclusions can be drawn: (i) the reactivity of the tested probes towards Michael addition increases in the para-substitution sequence: H < OEt < SMe < Br < NO2, and is not correlated with the sigma(P) values of the substituents; (ii) in turn, the descriptor proposed here as local softness (1/v(f) (r)) appears as a promising reactivity index that is able to explain the higher k(N) values found for both electron-withdrawing and electron-donating groups; (iii) the nucleophilic reactivity of the biothiols employed increases in the sequence Cys-Gly < Hcy < GSH < Cys < gamma-Glu-Cys; and also finally (iv) we have demonstrated that these probes can be used for fluorimetric thiol determination in SH-SY5Y cells.

Más información

Título según WOS: Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest
Título según SCOPUS: Substituent effects on reactivity of 3-cinnamoylcoumarins with thiols of biological interest
Título de la Revista: RSC Advances
Volumen: 4
Número: 2
Editorial: ROYAL SOC CHEMISTRY
Fecha de publicación: 2014
Página de inicio: 697
Página final: 704
Idioma: English
URL: http://xlink.rsc.org/?DOI=c3ra44695f
DOI:

10.1039/c3ra44695f

Notas: ISI, SCOPUS