A QM/MM study on the fast photocycle of blue light using flavin photoreceptors in their light-adapted/active form

Literature Information

Publication Date 2010-06-08
DOI 10.1039/B925908B
Impact Factor 3.676
Authors

Keyarash Sadeghian, Marco Bocola, Martin Schütz


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Abstract

Based on QM/MM calculations using a combination of time-dependent Hartree–Fock and coupled cluster response theory a mechanism is proposed for the photocycle of blue light using flavin (BLUF) domains in the signaling/light adapted conformation. In analogy to the dark-adapted form, a charge transfer state drives proton transfer from the highly conserved tyrosine residue to the flavin chromophore. The latter step is mediated by the adjacent glutamine residue, which, in the light adapted conformation, exists as its imidic tautomer. However, before the proton transfer is even halfway completed, a conical intersection seam between the charge transfer and ground state is reached. Two channels for the decay back to the initial light-adapted conformation are open, a rapid one leading directly through the funnel of the conical intersection, bypassing the formation of the biradical intermediate, and a slower one via the biradical intermediate. The mechanism as proposed here: (i) explains the very rapid photocycle; and (ii) confirms the concept of photoirreversibility, both of which have been experimentally observed for BLUF domains in their light-adapted conformations.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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