The reaction of solvated electrons with cytosine, 5-methyl cytosine and 2'-deoxycytidine in squeous solution. The reaction of the electron adduct intermediates with water, p-nitroacetophenone and oxygen. A pulse spectroscopic and pulse conductometric study.
Using conductivity detection, pulse radiolysis experiments showed that solvent protonation of the electron adducts of cytosine, 5-methyl cytosine and 2'-deoxycytidine occurs with rate constants k greater than or equal to 2 x 10(4) M-1S-1. The protonated electron adducts transfer an electron to p-nitroactetophenone (PNAP) with rate constants ranging from 3.5 x 10(9) to 5.3 x 10(9) M-1S-1. The transfer is quantitative (G = 2.7), as shown by conductometric and spectroscopic measurements. In the presence of O2 no electron transfer to O2 takes place, implying that O2 adds to the protonated electron adduct radicals. No electron transfer from the H- and OH-adducts of the cytosine derivatives, either to PNAP or to O2, takes place near neutral pH. It is suggested that the differences in the reaction behaviour of the H-adduct radicals and the protonated electron adduct radicals towards PNAP can be accounted for if different radicals are formed by H-addition and protonation of the electron adduct. The H atoms most probably add to the C-5-C-6 double bonds, whereas the electron adducts are protonated at N-3 and/or 0-2.
D000098:Acetophenones; D000440:Butanols; D003217:Conductometry; D003596:Cytosine / Q000031:analogs & derivatives*; D003841:Deoxycytidine; D004563:Electrochemistry; D004583:Electrons; D006863:Hydrogen-Ion Concentration; D009596:Nitrophenols; D010100:Oxygen; D011675:Pulse Radiolysis; D012996:Solutions; D013057:Spectrum Analysis
D000098:Acetophenones; D000440:Butanols; D009596:Nitrophenols; D012996:Solutions; D003841:Deoxycytidine; D003596:Cytosine; D010100:Oxygen