Nitroxyl radicals antioxidant action

Irg 1076, AO-3 (CB), are used in combination with metal dithiolates, e.g., NiDEC, AO-30 (PD), due to the sensitized photoxidation of dithiolates by the oxidation products of phenols, particularly stilbenequinones (SQ, see reaction 9C) (Table 3). Hindered piperidines exhibit a complex behavior when present in combination with other antioxidants and stabilizers they have to be oxidized initially to the corresponding nitroxyl radical before becoming effective. Consequently, both CB-D and PD antioxidants, which remove alkyl peroxyl radicals and hydroperoxides, respectively, antagonise the UV stabilizing action of this class of compounds (e.g.. Table 3, NiDEC 4- Tin 770). However, since the hindered piperidines themselves are neither melt- nor heat-stabilizers for polymers, they have to be used with conventional antioxidants and stabilizers. 

Nitroxyl radicals as alkyl radical acceptors are known to be very weak antioxidants due to the extremely fast addition of dioxygen to alkyl radicals (see Chapter 2). They retard the oxidation of solid polymers due to specific features of free radical reactions in the solid polymer matrix (see Chapter 19). However, the combination of two inhibitors, one is the peroxyl radical acceptor (phenol, aromatic amine) and another is the alkyl radical acceptor (nitroxyl radical) showed the synergistic action [44-46]. The results of testing the combination of nitroxyl radical (>NO ) (2,2,6,6-tetramethyl-4-benzoylpiperidine-l-oxyl) + amine (phenol) in the autoxidation of nonene-1 at 393 K are given here ([>NO ]o + [InH]o = 1.5 x 10 4mol L 1 p02 98 kPa) [44]. 

This equation seems to be a key reaction point in the antioxidant action of these amines—>N radicals in the presence of oxygen are transformed via peroxy radical intermediates into nitroxyl radicals. The nitroxyl radicals are very persistent and react efficiently with radicals produced on polyolefine degradation. Such radical interception blocks the chain in radical oxidation and therefore causes the antioxidant activity of sterically hindered amines (Brede et al. 1998). 

The antioxidant action of nitroxyl radicals is due to their ability to react with alkyl radicals as in Reaction 9. Because of their reactivity with alkyl radicals, nitroxyls are better photooxidation inhibitors than the inhibitors of other classes. The rate constant for the reaction of nitroxyls with hydroxyl radical (Equation 10) is 10 L/mol. sec. This reaction can be of particular importance for the inhibition of polymer photooxidation. 

H. Ohshima, Y. Yoshie, S. Auriol and I. Gilibert, Antioxidant and pro-oxidant actions of flavonoids effects on DNA damage induced by nitric oxide, per-oxynitrite and nitroxyl anion, Free Radic. Biol. Med., 25 (1998) 1057-1065. M.K. Johnson and G. Loo, Effects of egpigallocatechin gallate and quercetin on oxidative damage to cellular DNA, Mutat. Res., 459 (2000) 211-218. 

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