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EPR Spectra and Electron Spin Relaxation of O2

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Abstract

It has been known from the pioneering and approximately simultaneous work of Freed and Frankel, Hausser and Deguchi (1959–1960) that collisions with O2 in fluid solutions broaden the electron paramagnetic resonance (EPR) spectra of free radicals. Freed showed Hausser the effect of degassing solutions on the hyperfine of DPPH. Hausser and Deguchi published spectra illustrating the effect. The effect of O2 on CW EPR spectra and on relaxation times has been applied to the problem of measuring O2 concentration in vivo. Various aspects of the effect of O2 on biological EPR and on the biological systems have been studied. A large literature has developed about in vivo O2 measurements using nitroxyl radicals, triarylmethyl radicals (trityl, TAM), carbon particles, and analogues of lithium phthalocyanine (LiPc). All of these measurements correctly assume that the O2 electron spin relaxation time is short relative to the relaxation time of the sensor molecules. There has been no prior review of the EPR spectra and electron spin relaxation of O2 in the gas phase, dissolved in fluid solution, and in frozen solutions. A summary of the relevant literature is presented here as a resource for the O2 measurement community.

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Acknowledgements

This review was stimulated by the celebration of the career of Professor Harold M. Swartz, who introduced the scientific community to the need and potential for EPR to monitor O2 concentration in vivo and especially in viable systems. His perspective is reflected in, for example, ref. [6, 46].

Funding

Funding for this work by National Institutes of Health NCI AIP Grant CA177744 and the University of Denver is gratefully acknowledged. Joseph McPeak (University of Denver) provided Fig. 6. Discussions with Prof. Howard J. Halpern (University of Chicago) and Prof. Joseph P. Y. Kao (University of Maryland) were important contributions to our understanding of the effects of O2.

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  1. Department of Chemistry and Biochemistry, University of Denver, 2101 E. Wesley Ave., Denver, CO, 80210, USA

    Sandra S. Eaton & Gareth R. Eaton

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Correspondence to Gareth R. Eaton.

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Eaton, S.S., Eaton, G.R. EPR Spectra and Electron Spin Relaxation of O2. Appl Magn Reson 52, 1223–1236 (2021). https://doi.org/10.1007/s00723-021-01353-y

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