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Issue 25, 2019
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On the magnetosensitivity of lipid peroxidation: two- versus three-radical dynamics

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Abstract

We present a theoretical analysis of the putative magnetosensitivity of lipid peroxidation. We focus on the widely accepted radical pair mechanism (RPM) and a recently suggested idea based on spin dynamics induced in three-radical systems by the mutual electron–electron dipolar coupling (D3M). We show that, contrary to claims in the literature, lipid peroxides, the dominant chain carriers of the autoxidation process, have associated non-zero hyperfine coupling interactions. This suggests that their recombination could, in principle, be magnetosensitive due to the RPM. While the RPM indeed goes a long way to explaining magnetosensitivity in these systems, we show that the simultaneous interaction of three peroxyl radicals via the D3M can achieve larger magnetic field effects (MFE), even if the third radical is remote from the recombining radical pair. For randomly oriented three-radical systems, the D3M induces a low-field effect comparable to that of the RPM. The mechanism furthermore immunizes the spin dynamics to the presence of large exchange coupling interactions in the recombining radical pair, thereby permitting much larger MFE at magnetic field intensities comparable to the geomagnetic field than would be expected for the RPM. Based on these characteristics, we suggest that the D3M could be particularly relevant for MFE at low fields, provided that the local radical concentration is sufficient to allow for three-spin radical correlations. Eventually, our observations suggest that MFEs could intricately depend on radical concentration and larger effects could ensue under conditions of oxidative stress.

Graphical abstract: On the magnetosensitivity of lipid peroxidation: two- versus three-radical dynamics

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Supplementary files

Article information


Submitted
28 Mar 2019
Accepted
07 May 2019
First published
18 Jun 2019

This article is Open Access

Phys. Chem. Chem. Phys., 2019,21, 13526-13538
Article type
Paper

On the magnetosensitivity of lipid peroxidation: two- versus three-radical dynamics

C. Sampson, R. H. Keens and D. R. Kattnig, Phys. Chem. Chem. Phys., 2019, 21, 13526
DOI: 10.1039/C9CP01746A

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