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Insights into the nature of the hydrogen bonding of ·Tyr272 in apo-galactose oxidase

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Benisvy,  Laurent
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Neese,  Frank
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;
Institut für Physikalische and Theoretische Chemie, Universität Bonn;

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Bothe,  Eberhard
Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society;

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Citation

Benisvy, L., Hammond, D., Parker, D. J., Davies, E. S., Garner, C. D., McMaster, J., et al. (2007). Insights into the nature of the hydrogen bonding of ·Tyr272 in apo-galactose oxidase. Journal of Inorganic Biochemistry, 101(11-12), 1859-1864. doi:10.1016/j.jinorgbio.2007.07.013.


Cite as: https://hdl.handle.net/21.11116/0000-0008-34F9-5
Abstract
The synthesis and structure of an o-methylthio-phenol-imidazole, 2-(2′-(4′-tert-butyl-6′-methylsulfanyl)-hydroxyphenyl))-4,5-diphenyl-imidazole (MeSLH), is reported; X-ray crystallographic studies have shown that MeSLH involves an O–H···N+ hydrogen bond between the phenol and an imidazole nitrogen. MeSLH undergoes a reversible, one-electron, oxidation to form the radical cation [MeSLH]·+ the EPR spectrum of which is remarkably similar to that of ·Tyr272 in Cu-free, oxidized, apo-GO. Density Functional Theory calculations, have shown that the proton-transferred (R–O····H–N+) form of [MeSLH]·+ has a spin density distribution – with a substantial delocalization of the unpaired electron spin density onto the ortho sulfur atom – and EPR properties that are in good agreement with those of ·Tyr272 in Cu-free, oxidized, apo-GO whereas the non-proton-transferred (R–O·+–H···N) form does not. The results reported herein are a further demonstration of the influence of hydrogen bonding on the nature and properties of phenoxyl radicals and strongly suggest that the phenoxyl oxygen of ·Tyr272 in Cu-free, oxidized, apo-GO is involved in a O····H–O/N hydrogen bond.