title: Operation of the proton wire in green fluorescent protein. A quantum dynamics simulation.
abstract: A nuclear quantum dynamical simulation of the proton shuttle operating in the green fluorescent protein has been carried out on a high-quality, high-dimensionality potential energy surface describing the photoactive pipi* excited state, and including motion of both the three protons and of the donor and acceptor atoms of the hydrogen bonds in a closed proton wire. The results of the simulations show that proton transfer along the wire is essentially concerted, synchronous, and very fast, with a substantial amount of the green fluorescent species forming within several tens of femtoseconds. In this regard, analysis of the population of the fluorescent species indicates that at least two dynamical regimes are present for its formation. Within the first hundreds of femtoseconds, dynamics is very fast and impulsive. Later on, a slower pace of formation appears. It is discussed that the two largest decay times for the protonated chromophore reported experimentally (Chattoraj, M.; King, B. A.; Bublitz, G. U.; Boxer, S. G. Proc. Natl. Acad. Sci. U.S.A. 1996, 93, 8362-8367) might correspond to some irreversible process occurring after formation of the fluorescent species, rather than to cleavage of the chromophore's phenolic O-H bond.
authors.affiliation: Departament de Química Universitat Autonoma de Barcelona, 08193 Bellaterra (Barcelona), Spain.
authors.forename: Oriol
authors.initials: O
authors.lastname: Vendrell
authors.forename: Ricard
authors.initials: R
authors.lastname: Gelabert
authors.forename: Miquel
authors.initials: M
authors.lastname: Moreno
authors.forename: José M
authors.initials: JM
authors.lastname: Lluch
mesh_terms: D003198:Computer Simulation; D049452:Green Fluorescent Proteins / Q000737:chemistry*; D008954:Models, Biological; D015394:Molecular Structure; D011522:Protons; D011789:Quantum Theory
chemical_list: D011522:Protons; D049452:Green Fluorescent Proteins