Radical Rearrangement Chemistry in Ultraviolet Photodissociation of Iodotyrosine Systems: Insights from Metastable Dissociation,Infrared Ion Spectroscopy,and Reaction Pathway Calculations |
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| Authors: | Karnamohit Ranka Ning Zhao Long Yu John F Stanton Nicolas C Polfer |
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| Institution: | 1.Quantum Theory Project, Department of Chemistry,University of Florida,Gainesville,USA;2.Quantum Theory Project, Department of Physics,University of Florida,Gainesville,USA;3.Department of Chemistry and Center for Chemical Physics,University of Florida,Gainesville,USA |
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| Abstract: | We report on the ultraviolet photodissociation (UVPD) chemistry of protonated tyrosine, iodotyrosine, and diiodotyrosine. Distonic loss of the iodine creates a high-energy radical at the aromatic ring that engages in hydrogen/proton rearrangement chemistry. Based on UVPD kinetics measurements, the appearance of this radical is coincident with the UV irradiation pulse (8 ns). Conversely, sequential UVPD product ions exhibit metastable decay on ca. 100 ns timescales. Infrared ion spectroscopy is capable of confirming putative structures of the rearrangement products as proton transfers from the imine and β-carbon hydrogens. Potential energy surfaces for the various reaction pathways indicate that the rearrangement chemistry is highly complex, compatible with a cascade of rearrangements, and that there is no preferred rearrangement pathway even in small molecular systems like these. |
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