Phototriggering Electron Flow through ReI-modified Pseudomonas aeruginosa Azurins (pages 5350–5361)
Dr. Ana María Blanco-Rodríguez, Dr. Angel J. Di Bilio, Dr. Crystal Shih, Dr. Anna Katrine Museth, Dr. Ian P. Clark, Dr. Michael Towrie, Dr. Andrea Cannizzo, Dr. Jawahar Sudhamsu, Prof. Dr. Brian R. Crane, Dr. Jan Sýkora, Dr. Jay R. Winkler, Prof. Dr. Harry B. Gray, Dr. Stanislav Záliš and Prof. Dr. Antonín Vlček Jr.
Article first published online: 5 APR 2011 | DOI: 10.1002/chem.201002162
Time to accelerate! IR spectroscopic and DFT/time-dependent (TD)DFT analysis reveals factors underlying the dramatic acceleration of long-range electron transfer (ET) in mutants of Pseudomonas aeruginosa azurin labeled with a [ReI(CO)3(α-diimine)] chromophore next to a tryptophan (see scheme). The Re–tryptophan pair operates as a single photoactive unit that triggers several ET pathways (ET1, ET2), in fs–ns timescales and efficient hole-injection into the peptide.