Electrochemical Study of Methyl 2-[p-Nitrophenyl(hydroxy)methyl]acrylate

Abstract

2:8, 0.18 mol L −1 , pH 9.6͒ and aprotic ͓dimethylformamide ͑DMF͒ + tetrabutylammonium perchlorate ͑TBAP͒, 0.1 mol L −1 ͔ media. The primary reduction behavior in aprotic medium was typical of nitroaromatics along with an additional wave related to the reduction of the acrylate function. Kinetic analysis carried out in aprotic and aqueous basic media pointed out to the high stability of the electrogenerated nitro radical anion, especially in DMF + TBAP. Reduced ͑GSH͒ and oxidized ͑GSSG͒ gluthatione in phosphate buffer influenced the reduction behavior of 1, due mainly to protonation effects. Direct reduction of 1, in the presence of GSH, led to a transient nitroso-GS adduct. In the presence of GSSG, hydrogen-bondingassociated GSSG-hydroxylamine was the main product. Electrochemical studies of 1, in the presence of oxygen, showed no chemical reactivity between O 2 and 1-•. These electrochemical results help in the understanding of the anticancer activity of 1 that can be considered a bioreductive agent with a glutathione depleting function.

Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

“…For instance, the reduction of molecules bearing two nitro groups has gained attention in recent years [5][6][7][8] mainly due to the effects occurring in the stabilization of the corresponding electrogenerated radical anions by interacting groups present in the structure, since this phenomenon is known to be dependent on the environment surrounding the radical anion and on the method employed for its formation [6][7][8][9]. This issue is relevant, in biological and pharmacological terms, once the stability of the electrogenerated radical species is related to the capacity of these species to induce the formation of reactive oxygen species, in the presence of oxygen and after reduction [2][3][4][10][11][12] that in vivo or in cell occurs via the action of nitroreductases [2,11,12].…”

An amperometric sensor based on electrochemically triggered reaction: Redox-active Ar–NO/Ar–NHOH from 4-nitrophthalonitrile-modified electrode for the low voltage cysteine detection

“…A definite characterization of the formed adduct is out of the scope of the present paper. Such nitrosothiol adducts are often invoked but rarely isolated because of their easy hydrolysis or degradation, mainly, in the presence of trace of metals [39][40][41][42]. …”

Inner reorganization during the radical–biradical transition in a nor-β-lapachone derivative possessing two redox centers

“…• − species, promoted in vivo by nitroreductases. 7,11, 12 Nitroquinones have been investigated with special toxicological concern. Electroreduction of nitro derivatives of quinones has been described, [13][14][15][16][17][18] but, in the majority of cases, without considering any relationship with pharmacological activities and any evidence of mechanistic complications, as demonstrated in the case of 2-nitronaphthothiophen-4,9-quinone, 19 which carries two different electrochemically reducible sites and presents a conjugate interaction.…”