The Chemical Reactivity of Membrane Lipids.

Although peroxyl radical fragmentation to HO 2 • only occurs for PUFAs and is rather slow, with an estimated rate constant of 0.04 s –1 , it may be significant for the transfer of the propagating chain between vesicles and micelles, a phenomenon that has been observed experimentally. 327 Simulations suggest that the polar regions of the oxidation intermediates migrate toward the ester regions of the lipids to adopt a disposition closer to the membrane int

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As a consequence, sulfonyl radical reactivity is only likely to be significant in exceptional circumstances, but these radicals nevertheless produce similar E / Z ratios to thiyl radicals by the general process outlined in Scheme 17 . 554 5.2 Nitrogen Radicals Isomerization of isolated alkenes by NO 2 • has been demonstrated in the gas phase, where radical addition competes w

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