Aromatic and aliphatic mono- and bis-nitroxides: a study on their radical scavenging abilities.
Nitroxide radicals are an emerging class of interesting compounds with versatile antioxidant and radioprotective properties. All literature studies have so far concentrated on compounds bearing only one nitroxide function. Here, we now investigate and compare the radical scavenging behaviour and antioxidant activity of aromatic indolinonic and aliphatic piperidine bis-nitroxides, i.e compounds bearing two nitroxide functions. Their corresponding mono-derivatives were also studied for comparison. Radical scavenging activity was investigated using EPR and UV-Vis spectroscopy by following spectral changes in acetonitrile of the nitroxides in the presence of alkyl and peroxyl radicals generated, respectively, under anoxic or aerobic conditions from thermal decomposition of AMVN [2,2'-azobis(2,4-di-methylvaleronitrile)]. Antioxidant activity of the nitroxides was evaluated by monitoring conjugated dienes (CD) formation during methyl linoleate micelles peroxidation and by measuring carbonyl content in oxidized bovine serum albumin (BSA). The results show that: (a) each nitroxide moiety in bis-nitroxides scavenges radicals independent of each other; (b) aliphatic nitroxides do not scavenge peroxyl radicals, at least under the experimental conditions used here, whereas indolinonic aromatic ones do: their stoichiometric number is 1.14 and 2.17, respectively, for mono- and bis-derivatives; (c) bis-nitroxides are roughly twice more efficient at inhibiting lipid peroxidation compared to their corresponding mono-derivatives. Although this study provides only comparative information on the relative radical-scavenging abilities of mono- and bis-nitroxides, it helps in understanding further the interesting reactivity of these compounds especially with regards to peroxyl radicals where many controversies in the literature exist.
Damiani
Elisabetta
E
Istituto di Biochimica, Via Ranieri, Università Politecnica delle Marche, I-60131 Ancona, Italy. e.damiani@univpm.it
Castagna
Riccardo
R
Astolfi
Paola
P
Greci
Lucedio
L
D000097:Acetonitriles / Q000737:chemistry / Q000378:metabolism; D000818:Animals; D000975:Antioxidants / Q000737:chemistry / Q000378:metabolism* / Q000494:pharmacology; D001391:Azo Compounds / Q000378:metabolism; D002411:Cation Exchange Resins; D002417:Cattle; D003497:Cyclic N-Oxides / Q000737:chemistry* / Q000378:metabolism* / Q000494:pharmacology; D004578:Electron Spin Resonance Spectroscopy; D016166:Free Radical Scavengers / Q000737:chemistry / Q000378:metabolism* / Q000494:pharmacology; D005609:Free Radicals / Q000737:chemistry / Q000378:metabolism*; D015227:Lipid Peroxidation / Q000187:drug effects*; D009570:Nitriles / Q000378:metabolism; D010545:Peroxides / Q000737:chemistry / Q000378:metabolism; D012117:Resins, Synthetic; D012710:Serum Albumin, Bovine / Q000737:chemistry / Q000378:metabolism
D000097:Acetonitriles; D000975:Antioxidants; D001391:Azo Compounds; D002411:Cation Exchange Resins; D003497:Cyclic N-Oxides; D016166:Free Radical Scavengers; D005609:Free Radicals; C106553:Mono-S; D009570:Nitriles; D010545:Peroxides; D012117:Resins, Synthetic; C055792:2,2'-azobis(2,4-dimethylvaleronitrile); D012710:Serum Albumin, Bovine; C049375:perhydroxyl radical; C032159:acetonitrile