pH Dependence of charge transfer between tryptophan and tyrosine in dipeptides
Steven Y Reece1, Joanne Stubbe, Daniel G Nocera
1Department of Chemistry, 6-335, 77 Massachusetts Avenue, Massachusetts Institute of Technology, Cambridge, MA 02139-4307, USA.
Abstract:
Time-resolved absorption spectroscopy has been employed to study the directionality and rate of charge transfer in W-Y and Ac-W-Y dipeptides as a function of pH. Excitation with 266-nm nanosecond laser pulses produces both W (or [WH](+), depending on pH) and Y. Between pH 6 and 10, W to was found to oxidize Y with k(X)=9.0x10(4) s(-1) and 1.8x10(4) s(-1) for the W-Y and Ac-W-Y dipeptide systems, respectively. The intramolecular charge transfer rate increases as the pH is lowered over the range 6>pH>2. For 10
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