Ultrafast vibrational spectroscopic Studies on the photoionization of the α-Tocopherol analogue Trolox C

Parker, AW; Bisby, RH; Greetham, GM; Kukura, P; Scherer, KM; Towrie, M

Abstract

The initial events after photoexcitation and photoionization of α-tocopherol (vitamin E) and the analogue Trolox C have been studied by femtosecond stimulated Raman spectroscopy, transient absorption spectroscopy and time-resolved infrared spectroscopy. Using these techniques it was possible to follow the formation and decay of the excited state, neutral and radical cation radicals and the hydrated electron that are produced under the various conditions examined. α Tocopherol and Trolox C in methanol solution appear to undergo efficient homolytic dissociation of the phenolic –OH bond to directly produce the tocopheroxyl radical. In contrast, Trolox C photochemistry in neutral aqueous solutions involves intermediate formation of a radical cation and the hydrated electron which undergo geminate recombination within 100 ps in competition with deprotonation of the radical cation. The results are discussed in relation to recently proposed mechanisms for the reaction of α-tocopherol with peroxyl radicals, which represents the best understood biological activity of this vitamin.

Citation

Parker, A., Bisby, R., Greetham, G., Kukura, P., Scherer, K., & Towrie, M. (2014). Ultrafast vibrational spectroscopic Studies on the photoionization of the α-Tocopherol analogue Trolox C. Journal of Physical Chemistry B, 118(42), 12087-12097. https://doi.org/10.1021/jp505113k

• Journal Article Type: Article
• Publication Date: Oct 23, 2014
• Deposit Date: Oct 31, 2014
• Publicly Available Date: Apr 5, 2016
• Journal: The Journal of Physical Chemistry B
• Print ISSN: 1520-6106
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 118
• Issue: 42
• Pages: 12087-12097
• DOI: https://doi.org/10.1021/jp505113k
• Keywords: Vitamin E, α-tocopherol, Trolox C, ultrafast, stimulated Raman, time-resolved, infrared, photoionization
• Publisher URL: http://dx.doi.org/10.1021/jp505113k
• Related Public URLs: http://pubs.acs.org/journal/jpcbfk