TY - CONF
T1 - Nucleophilic reactivity of biothiols toward coumarin-based derivatives containing a chalcone moiety
PY - 2012/11/1
Y1 - 2012/11/1
N2 - TheMichael addition reactions of the biothiols cysteine (Cys), glutathione (GSH), homocysteine (Hcy) and cysteinylglycine (Cys-Gly) with (E)-3-(3-(2-methoxyphenyl)acryloyl)-7-methoxy-2H-chromen-2-one and (E)-3-(3-(3-methoxyphenyl) acryloyl)-7-methoxy-2H-chromen-2-one (ChC2 and ChC3, respectively) in aqueous solution (25 °C, ionic strength 0.2M KCl) were followed fluorimetrically and evaluated kinetically. With a large excess of biothiol, pseudo-first-order rate coefficients (kobsd) were found. Plots of kobsd versus [biothiolate] are linear, with a pH-independent slope (kN). With the kinetic results obtained, the following conclusions can be drawn: (i) the reactivity increases in the sequence Cys-Gly<Hcy GSH<Cys; (ii) similar reactivity toward biothiols was found for ChC2 and ChC3, and both probes are more reactive than (E)-3-cinnamoyl-7- methoxy-2H-chromen-2-one (ChC1); (iii) ChC2 and ChC3 display a highly selective fluorescence enhancement with biothiols, allowing these probes to be used for fluorimetric biothiol determination in SH-SY5Y cells. Copyright © 2012 John Wiley & Sons, Ltd.
AB - TheMichael addition reactions of the biothiols cysteine (Cys), glutathione (GSH), homocysteine (Hcy) and cysteinylglycine (Cys-Gly) with (E)-3-(3-(2-methoxyphenyl)acryloyl)-7-methoxy-2H-chromen-2-one and (E)-3-(3-(3-methoxyphenyl) acryloyl)-7-methoxy-2H-chromen-2-one (ChC2 and ChC3, respectively) in aqueous solution (25 °C, ionic strength 0.2M KCl) were followed fluorimetrically and evaluated kinetically. With a large excess of biothiol, pseudo-first-order rate coefficients (kobsd) were found. Plots of kobsd versus [biothiolate] are linear, with a pH-independent slope (kN). With the kinetic results obtained, the following conclusions can be drawn: (i) the reactivity increases in the sequence Cys-Gly<Hcy GSH<Cys; (ii) similar reactivity toward biothiols was found for ChC2 and ChC3, and both probes are more reactive than (E)-3-cinnamoyl-7- methoxy-2H-chromen-2-one (ChC1); (iii) ChC2 and ChC3 display a highly selective fluorescence enhancement with biothiols, allowing these probes to be used for fluorimetric biothiol determination in SH-SY5Y cells. Copyright © 2012 John Wiley & Sons, Ltd.
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U2 - 10.1002/poc.2975
DO - 10.1002/poc.2975
M3 - Paper
SP - 946
EP - 952
T2 - Journal of Physical Organic Chemistry
Y2 - 1 November 2012
ER -