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PreprintCC BYChemRxiv

Magnetic control of lipid–peroxyl termination yield under spin relaxation: from an optimised dipolar-scale field to a falsifiable kinetic criterion

  • Pablo R. Castello1,2,3
  • Pablo Jimenez4,5
  • Daniel R. Kattnig6,7
  • Carlos F. Martino8
8 affiliations
  1. 1Facultad de Ciencias Exactas y Naturales (FCEN
  2. 2Universidad de Belgrano
  3. 3CONICET
  4. 4Departamento de Física Médica
  5. 5Instituto Balseiro
  6. 6Living Systems Institute and Department of Physics and Astronomy
  7. 7University of Exeter
  8. 8Johns Hopkins University Applied Physics Laboratory
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Abstract

Lipid peroxidation, the radical-chain oxidation of membrane lipids, terminates in part through spin-selective encounters between lipid-peroxyl radicals. We ask how far a shaped magnetic field can steer this branch under spin relaxation and how that change propagates to the oxidation flux. Gradient-projection and bang–bang Pontryagin controls were evaluated with a stochastic-Schrödinger treatment of dipolar fluctuations and an independent Brownian-dynamics model. A best-found dipolar-scale field raises the triplet-initialised singlet termination yield from ΦS|T = 0.220 at 50 µT to 0.562 (+155%), with the bang–bang solution corroborating at 0.522; a bandwidth-filtered proxy retains 0.270. Under Brownian dynamics the control advantage remains positive throughout the sampled rotational-correlation-time range, and one field transfers across eight microdomain-size–diffusion parameter sets. Closing the spin calculation to classical autoxidation kinetics gives Ceff = −f/(1+f), where f is the fraction of peroxyl loss proceeding through bimolecular termination. Two limiting descriptions of the productive encounter population bracket the predicted suppression of oxidation flux in antioxidant-free liposomes at approximately 21–37%, and at approximately 4–10% for the bandwidth-filtered field. α-Tocopherol attenuates the response as interception comes to dominate, providing an internal experimental control. These values describe an elementary encounter and a minimal kinetic model, not whole-cell lipid peroxidation.

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Cite

BibTeXRIS
BibTeX
@misc{castello2026magnetic,
  title = {{Magnetic control of lipid–peroxyl termination yield under spin relaxation: from an optimised dipolar-scale field to a falsifiable kinetic criterion}},
  author = {Pablo R. Castello and Pablo Jimenez and Daniel R. Kattnig and Carlos F. Martino},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15007151/v2},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007151/v2},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Magnetic control of lipid–peroxyl termination yield under spin relaxation: from an optimised dipolar-scale field to a falsifiable kinetic criterion
AU  - Pablo R. Castello
AU  - Pablo Jimenez
AU  - Daniel R. Kattnig
AU  - Carlos F. Martino
PY  - 2026
DA  - 2026/10/06
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15007151/v2
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007151/v2
AB  - Lipid peroxidation, the radical-chain oxidation of membrane lipids, terminates in part through spin-selective encounters between lipid-peroxyl radicals. We ask how far a shaped magnetic field can steer this branch under spin relaxation and how that change propagates to the oxidation flux. Gradient-projection and bang–bang Pontryagin controls were evaluated with a stochastic-Schrödinger treatment of dipolar fluctuations and an independent Brownian-dynamics model. A best-found dipolar-scale field raises the triplet-initialised singlet termination yield from ΦS|T = 0.220 at 50 µT to 0.562 (+155%), with the bang–bang solution corroborating at 0.522; a bandwidth-filtered proxy retains 0.270. Under Brownian dynamics the control advantage remains positive throughout the sampled rotational-correlation-time range, and one field transfers across eight microdomain-size–diffusion parameter sets. Closing the spin calculation to classical autoxidation kinetics gives Ceff = −f/(1+f), where f is the fraction of peroxyl loss proceeding through bimolecular termination. Two limiting descriptions of the productive encounter population bracket the predicted suppression of oxidation flux in antioxidant-free liposomes at approximately 21–37%, and at approximately 4–10% for the bandwidth-filtered field. α-Tocopherol attenuates the response as interception comes to dominate, providing an internal experimental control. These values describe an elementary encounter and a minimal kinetic model, not whole-cell lipid peroxidation.
ER  -