Abstract
Avoided level crossing muon spin resonance (ALC-μ SR) has been used to characterize muoniated radicals formed by the reaction of muonium (Mu) with cholesterol in the solid state and in solution. Mu adds to the secondary carbon of the C=C bond and the observed radical has Mu in the 6β position. The isotropic hyperfine coupling constant (Aμ) and dipolar muon hyperfine coupling constant (\(\boldsymbol {D}_{\boldsymbol {\mu }}^{\parallel }\)) were determined in solid cholesterol between 318 and 398 K from the position and shape of the Δ1 resonance. Aμ and \(\boldsymbol {D}_{\boldsymbol {\mu }}^{\parallel }\) decrease with increasing temperature; the former due to intramolecular motion and the latter due to both intramolecular motion and wobbling of the molecule. A Δ0 resonance due to the proton in the 4β position was observed in the ALC-μ SR spectra of dilute solutions of cholesterol in tetrahydrofuran and methanol. The position of the Δ0 resonance is sensitive to the polarity of the solvent and its width depends on the viscosity of the solution.
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References
Myant, N.B.: The Biology of Cholesterol and Related Steroids. Heinemann Medical Books, London (1981)
Marsan, M.P., Muller, I., Ramos, C., Rodriguez, F., Dufourc, E.J., Czaplicki, J., Milon, A.: Cholesterol orientation and dynamics in dimyristoylphosphatidylcholine bilayers: a solid state deuterium NMR analysis. Biophys. J. 76(1), 351–359 (1999). https://doi.org/10.1016/s0006-3495(99)77202-4
Marquardt, D., Kučerka, N., Wassall, S.R., Harroun, T.A., Katsaras, J.: Cholesterol’s location in lipid bilayers. Chem. Phys. Lipids 199, 17–25 (2016). https://doi.org/10.1016/j.chemphyslip.2016.04.001
McKenzie, I., Roduner, E.: Using polarized muons as ultrasensitive spin labels in free radical chemistry. Naturwissenschaften 96(8), 873–887 (2009). https://doi.org/10.1007/s00114-009-0538-5
McKenzie, I.: The positive muon and μ SR spectroscopy: powerful tools for investigating the structure and dynamics of free radicals and spin probes in complex systems. Annual Reports Section “C’ (Physical Chemistry) 109, 65 (2013). https://doi.org/10.1039/c3pc90005c
Blundell, S.J., De Renzi, R., Lancaster, T., Pratt, F.L. (eds.): Muon spectroscopy: An Introduction. Oxford University Press. ISBN: 9780198858959 (2021)
Percival, P.W., Brodovitch, J.-C., Leung, S.-K., Yu, D., Kie, R.F., Luke, G.M., Venkateswaran, K., Cox, S.F.J.: Intramolecular motion in the tert-butyl radical as studied by muon spin rotation and level-crossing spectroscopy. Chem. Phys. 127(1-3), 137–147 (1988). https://doi.org/10.1016/0301-0104(88)87113-1
Roduner, E.: The positive muon as a probe in free radical chemistry. Springer. https://doi.org/10.1007/978-3-642-51720-4 (1988)
Roduner, E.: Radical reorientation dynamics studied by positive-muon avoided level crossing resonance. Hyperfine Interactions 65(1-4), 857–871 (1991). https://doi.org/10.1007/bf02397738
Barker, S.A., Cottrell, S.P., Giblin, S.R., Jayasooriya, U.A.: Preliminary μ SR studies on the incorporation of steroidal drug molecules into liposomes. Physica B: Condensed Matter 374-375, 332–335 (2006). https://doi.org/10.1016/j.physb.2005.11.089
McKenzie, I., Scheuermann, R., Sedlak, K., Stoykov, A.: Molecular dynamics in rod-like liquid crystals probed by muon spin resonance spectroscopy. J. Phys. Chem. B 115(30), 9360–9368 (2011). https://doi.org/10.1021/jp203006w
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, Jr.J. A., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, O., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J.: Gaussian 09 revision e.01. Gaussian inc wallingford CT (2009)
Improta, R., Barone, V.: Interplay of electronic, environmental, and vibrational effects in determining the hyperfine coupling constants of organic free radicals. Chem. Rev. 104(3), 1231–1254 (2004). https://doi.org/10.1021/cr960085f
Takano, Y., Houk, K.N.: Benchmarking the conductor-like polarizable continuum model (cpcm) for aqueous solvation free energies of neutral and ionic organic molecules. J. Chem. Theory Comput. 1, 70–77 (2005). https://doi.org/10.1021/ct049977a
McKenzie, I., Scheuermann, R., Sedlak, K.: How do strain and steric interactions affect the reactions of aromatic compounds with free radicals? Characterization of the radicals formed by muonium addition to p-xylene and [2.2]paracyclophane by DFT calculations and muon spin spectroscopy. J. Phys. Chem. A 116(29), 7765–7772 (2012). https://doi.org/10.1021/jp305610g
Roduner, E., Reid, I.D., Riccò, M., Renzi, R.D.: Anisotropy of 2-norbornyl radical reorientational dynamics in the plastic phase of norbornene as determined by ALC-μ SR. Berichte der Bunsengesellschaft für Physikalische Chemie 93 (11), 1194–1197 (1989). https://doi.org/10.1002/bbpc.19890931109
Martyniak, A., Dilger, H., Scheuermann, R., Tucker, I.M., McKenzie, I., Vujosevic, D., Roduner, E.: Using spin polarised positive muons for studying guest molecule partitioning in soft matter structures. Phys. Chem. Chem. Phys. 8(41), 4723 (2006). https://doi.org/10.1039/b610414b
Reddoch, A.H., Konishi, S.: The solvent effect on di-tert-butyl nitroxide. a dipole-dipole model for polar solutes in polar solvents. J. Chem. Phys. 70, 2121–2130 (1979). https://doi.org/10.1063/1.437756
Wang, X., Dao, R., Yao, J., Peng, D., Li, H.: Modification of the onsager reaction field and its application on spectral parameters. Chem. Phys. Chem. 18, 763–771 (2017). https://doi.org/10.1002/cphc.201601093
Owenius, R., Terry, G.E., Williams, M.J., Eaton, S.S., Eaton, G.R.: Frequency dependence of electron spin relaxation of nitroxyl radicals in fluid solution. J. Phys. Chem. B 108(27), 9475–9481 (2004). https://doi.org/10.1021/jp036020f
Acknowledgments
ALC-μ SR measurements were performed under experiment M1628 at the Centre for Molecular and Material Science at TRIUMF. The CMMS staff are thanked for their assistance in running these experiments.
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We acknowledge the support of the Natural Sciences and Engineering Research Council of Canada (NSERC), [RGPIN-2019-04249]. This research was enabled in part by support provided by WestGrid (www.westgrid.ca) and Compute Canada (www.computecanada.ca). The authors have no conflicts to disclose. Raw data were generated at the TRIUMF μ SR facility. Derived data supporting the findings of this study are available from the corresponding author upon reasonable request. IM, JC and DCJ performed the ALC-μ SR measurements. IM and JC analyzed the ALC-μ SR spectra. IM performed the DFT calculations and wrote the paper.
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This article is part of the Topical Collection on Proceedings of the International Conference on Hyperfine Interactions (HYPERFINE 2021), 5-10 September 2021, Brasov, Romania
Edited by Ovidiu Crisan
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McKenzie, I., Cannon, J. & Cordoni-Jordan, D. Characterization of muoniated spin probes in cholesterol by avoided level crossing muon spin resonance. Hyperfine Interact 242, 13 (2021). https://doi.org/10.1007/s10751-021-01740-8
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DOI: https://doi.org/10.1007/s10751-021-01740-8