Abstract
Molecular oxygen is paramagnetic and gives strong EPR signals in the gas phase. At sufficiently low pressure the number of observed lines is large indeed (see Figure 1 obtained at 180 micron pressure). Tinkham and Strandberg (1955a, 1955b) developed the theory for the spectrum of molecular oxygen and were able to assign 120 lines observed at X-band. As the pressure increases, the linewidths increase greatly. Even at atmospheric pressure, intense EPR signals can be detected from molecular oxygen (Figure 2). However, to the authors’ best knowledge no EPR spectra have been reported from oxygen dissolved in fluids near room temperature. Apparently lines are so broadened as to be undetectable. Thus there seems to be no possibility for the directdetection of oxygen in biological systems using magnetic resonance techniques. However, an indirect method does exist and is the subject of this chapter. Bimolecular collisions of oxygen with free radicals (and we consider particularly spin labels) alter the resonance characteristics of the radical. As will become apparent, it is a remarkable fact that effects can be detected at dissolved oxygen concentrations as low as 10−7M in a measurement that requires only a few seconds. This method has been called “spin-label oximetry.” The National Biomedical ESR Center has been active in the development of the field. A rigorous foundation has been laid down, and it is believed that the method can be applied with confidence to a wide range of biological systems.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Ankel, E., Felix, C. C., and Kalyanaraman, B., 1986, The use of spin-label oximetry in the study of photodynamic inactivation of Chinese hamster ovary cells, Photochem. Photobiol. 44:741–746.
Backer, J. M., Budker, V. G., Eremenko, S. I., and Molin, Yu. N., 1977, Determination of the kinetics of biochemical reactions with oxygen using exchange broadening in the ESR spectra of nitroxide radicals, Biochim. Biophys. Acta 460:152–156.
Belkin, S., Mehlhorn, R. J., and Packer, L., 1987, Determination of dissolved oxygen in photosynthetic systems by nitroxide spin-probe broadening, Arch. Biochem. Biophys. 252: 487–495.
Butler, K. W., Deslauriers, R., and Smith, I. C. P., 1986, Effects of antimalarial drugs on oxygen consumption by erythrocytes infected with Plasmodium berghei: An ESR study, Magn. Reson. Med. 3: 312–316.
Deguchi, Y., 1960, Proton hyperfine spectra of diphenyl picryl hydrazyl, J. Chem. Phys. 32:1584–1585.
Edelstein, N., Kwok, A., and Maki, A. H., 1964, Effects of hydrostatic pressure and temperature on spin exchange between free radicals in solution, J. Chem. Phys. 41:3473–3478.
Freed, J. H., 1976, Theory of slow tumbling ESR spectra for nitroxides, in Spin Labeling Theory and Applications (L. J. Berliner, ed.), pp. 53–132, Academic Press, New York.
Froncisz, W., Lai, C.-S., and Hyde, J. S., 1985, Spin-label oximetry: kinetic study of cell respiration using a rapid passage Tx sensitive ESR display, Proc. Natl. Acad. Sei. U.S.A. 82:411–415.
Gurbiel, R., Cieszka, K., Pajak, S., Subczynski, W. K., and Lukiewicz, S., 1980, Detectability of radiation damage to melanoma cells using ESR spectroscopy, Folia Histochem. Cytochem. 18:87–100.
Hausser, K. H., 1960, Über den einfluss des gelösten sauerstoffs auf die linienbreite der electron- spin-resonanz in Lösung,” Naturwissenschaften 47:251.
Himmelblau, D. M., 1964, Diffusion of dissolved gases in liquids, Chem. Rev. 64:527–550.
Hitchman, M. L., 1978, Measurement of Dissolved Oxygen, Wiley, New York.
Hyde, J. S., 1979, Saturation-recovery methodology, in Time Domain Electron Spin Resonance (L. Kevan and R. N. Schwartz, eds.), pp. 1–30, Wiley, New York.
Hyde, J. S., and Froncisz, W., 1986, Loop-gap resonators, in Electron Spin Resonance (M. C. R. Symons, ed.), Vol. 10, pp. 175–184, Specialist Periodical Reports, The Royal Society of Chemistry.
Hyde, J. S., and Hyde, D. A., 1981, Determination of T2 from analysis of wings of symmetrical inhomogeneous lines, J. Magn. Reson. 43:137–140.
Hyde, J. S., and Sarna, T., 1978, Magnetic interactions between nitroxide free radicals and lanthanides or Cu2+ in liquids, J. Chem. Phys. 68:4439–4447.
Hyde, J. S., and Subczynski, W. K., 1984, Simulation of ESR spectra of the oxygen-sensitive spin-label probe CTPO, J. Magn. Reson. 56:125–130.
Hyde, J. S., Swartz, H. M., and Antholine, W. E., 1979, The spin-probe—spin-label method, in Spin Labeling II. Theory and Applications (L. J. Berliner, ed.), pp. 71–113, Academic Press, New York.
Ingalls, R. B., and Pearson, G. A., 1961, A basis for the determination of dissolved oxygen by electron spin resonance spectroscopy, Anal. Chim. Acta 25:566–569.
Kalyanaraman, B., Feix, J. B., Sieber, F., Thomas, J. P., and Girotti, A. W., 1987, Photodynamic action of Merocyanine 540 on artificial and natural cell membranes: Involvement of singlet molecular oxygen, Proc. Natl. Acad. Sei. U.S.A. 84:2999–3003.
Korytowski, W., Sarna, T., Kalyanaraman, B., and Sealy, R. C., 1987, Tyrosinase-catalyzed oxidation of DOPA and related catechol(amine)s: a kinetic electron spin resonance investigation using spin-stabilization and spin label oximetry, Biochim. Biophys. Acta 924:383–392.
Kusumi, A., Subczynski, W. K., and Hyde, J. S., 1982, Oxygen transport parameter in membranes as deduced by saturation recovery measurements of spin-lattice relaxation times of spin labels, Proc. Natl. Acad. Sei. U.S.A. 79:1854–1858.
Lai, C.-S., Hopwood, L. E., Hyde, J. S., and Lukiewicz, S., 1982, ESR studies of 02 uptake by Chinese hamster ovary cells during the cell cycle, Proc. Natl. Acad. Sei. U.S.A. 79:1166–1170.
Lakowicz, J. R., 1982, Diffusive transport of oxygen through proteins and membranes quantified by fluorescence quenching, in Hemoglobin and Oxygen Binding, Vol. 1 (C. Ho et al., eds.), Elsevier, New York, pp. 443–448.
Molin, Yu. N., Salikhov, K. M., and Zamaraev, K. I., 1980, Spin Exchange, Springer-Verlag, Berlin.
Moro, G., and Freed, J. H., 1981, Calculation of ESR spectra and related Fokker-Planck forms by the use of the Lanczos algorithm, J. Chem. Phys. 74:3757–3773.
Morse II, P. D., and Swartz, H. M., 1985, Measurement of intracellular oxygen concentration using the spin label TEMPOL, Magn. Reson. Med. 2:114–127.
Nemzek, T. L., and Ware, W. R., 1975, Kinetics of diffusion-controlled reactions: transient effects in fluorescence quenching, J. Chem. Phys. 62:477–489.
Pajak, S., Hopwood, L. E., Hyde, J. S., Felix, C. C., Sealy, R. C., Kushnaryov, V. M., and Hatchell, M. C., 1983, Melanin endocytosis by cultured mammalian cells: A model for melanin in a cellular environment, Exp. Cell Res. 149:513–526.
Pajak, S., Subczynski, W., Panz, T., and Lukiewicz, S., 1980, Rate of oxygen consumption of hamster melanoma cells as a factor influencing their radio resistance, Folia Histochem. Cytochem. 18:33–40.
Pake, G. E., and Tuttle, T. R., Jr., 1959, Anomalous loss of resolution of paramagnetic resonance hyperfine structure in liquids, Phys. Rev. Lett. 3:423–425.
Popp, C. A., and Hyde, J. S., 1981, Effects of oxygen on EPR spectra of nitroxide spin-label probes of model membranes, J. Magn. Reson. 43:249–258.
Povich, M. J., 1975a, Measurement of dissolved oxygen concentrations and diffusion coefficients by electron spin resonance, Anal. Chem. 47:346–347.
Povich, M. J., 1975b, Electron spin resonance oxygen broadening, J. Phys. Chem. 79:1106–1109.
Reszka, K., and Sealy, R. C., 1984, Photooxidation of 3,4-dihydroxyphenylalanine by hemato-porphyrin in aqueous solutions: An electron spin resonance study using 2,2,6,6-tetramethyl-4- piperidone-l-oxyl (TEMPONE), Photochem. Photobiol. 39:293–299.
Salikhov, K. M., Doctorov, A. B., Molin, Yu. N., and Zamaraev, K. I., 1971, Exchange broadening of ESR lines for solutions of free radicals and transition metal complexes, J. Magn. Reson. 5:189–205.
Sarna, T., and Sealy, R. C., 1984, Photoinduced oxygen consumption in melanin systems. Action spectra and quantum yields for eumelanin and synthetic melanin, Photochem. Photobiol. 39:69–74.
Sarna, T., Duleba, A., Korytowski, W., and Swartz, H., 1980, Interaction of melanin with oxygen, Arch. Biochem. Biophys. 200:140–148.
Sarna, T., Menon, I. A., and Sealy, R. C., 1984, Photoinduced oxygen consumption in melanin systems—II. Action spectra and quantum yields for pheomelanins, Photochem. Photobiol. 39:805–809.
Sealy, R. C., Sarna, T., Wanner, E. J., and Reszka, K., 1984, Photosensitization of melanin: An electron spin resonance study of sensitized radical production and oxygen consumption, Photochem. Photobiol. 40:453–459.
St.-Denis, C. E., and Fell, C. J. D., 1971, Diffusivity of oxygen in water, Can. J. Chem. Eng. 49:885.
Strzalka, K., Sarna, T., and Hyde, J. S., 1986, ESR oximetry: Measurement of photosynthetic oxygen evolution by spin-probe technique, Photobiochem. Photobiophys. 12:67–71.
Subczynski, W. K., and Hyde, J. S., 1981, The diffusion-concentration product of oxygen in lipid bilayers using the spin-label T1 method, Biochim. Biophys. Acta 643:283–291.
Subczynski, W. K., and Hyde, J. S., 1983, Concentration of oxygen in lipid bilayers using a spin-label method, Biophys. J. 41:283–286.
Subczynski, W. K., and Hyde, J. S., 1984, Diffusion of oxygen in water and hydrocarbons using an electron spin resonance spin label technique, Biophys. J. 45:743–748.
Subczynski, W. K., and Kusumi, A., 1985, Detection of oxygen consumption during very early stages of lipid peroxidation by ESR nitroxide spin probe method, Biochim. Biophys. Acta 821:259–263.
Subczynski, W. K., Lukiewicz, S., and Hyde, J. S., 1986, Murine in-vivo L-band ESR spin-label oximetry with a loop-gap resonator, Magn. Reson. Med. 3:747–754.
Swartz, H. M., 1987, The use of nitroxides to measure redox metabolism in cells and tissues, J. Chem. Soc., Faraday Trans. 1, 83:191–202.
Tinkham, M., and Strandberg, M. W. P., 1955a, Theory of the fine structure of the molecular oxygen ground state, Phys. Rev. 97:937–951.
Tinkham, M., and Strandberg, M. W. P., 1955b, Interaction of molecular oxygen with a magnetic field, Phys. Rev. 97:951–966.
Windrem, D. A., and Plachy, W. Z., 1980, The diffusion-solubility of oxygen in lipid bilayers, Biochim. Biophys. Acta 600:655–665.
Yin, J.-J., and Hyde, J. S., 1987a, Application of rate equations to ELDOR and saturation recovery experiments on 14N–15N spin-label pairs, /. Magn. Reson. 74:82–93.
Yin, J.-J., and Hyde, J. S., 1987b, Spin-label saturation-recovery electron spin resonance measurements of oxygen transport in membranes, Z. Phys. Chem. (Frankfurt Am Main) 153:S, 57–65.
Yin, J.-J., Pasenkiewicz-Gierula, M., and Hyde, J. S., 1987, Lateral diffusion of lipids in membranes by pulse saturation recovery electron spin resonance, Proc. Natl. Acad. Sci. U.S.A. 84:964–968.
Yin, J.-J., Feix, J. B., and Hyde, J. S., 1988, Solution of the nitroxide spin label spectral overlap problem using pulse electron spin resonance, Biophys. J. 53:525–531.
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1989 Plenum Press, New York
About this chapter
Cite this chapter
Hyde, J.S., Subczynski, W.K. (1989). Spin-Label Oximetry. In: Berliner, L.J., Reuben, J. (eds) Spin Labeling. Biological Magnetic Resonance, vol 8. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-0743-3_8
Download citation
DOI: https://doi.org/10.1007/978-1-4613-0743-3_8
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4612-8060-6
Online ISBN: 978-1-4613-0743-3
eBook Packages: Springer Book Archive