Electrostatic spectral tuning mechanism of the green fluorescent protein
Literature Information
Ville R. I. Kaila, Robert Send, Dage Sundholm
Understanding the mechanism of spectral tuning of biological chromophores is a major challenge in photobiology. We show here using large-scale full quantum chemical calculations of the green fluorescent protein that state-of-the-art coupled-cluster calculations provide accurate excitation energies and detailed insight about specific environmental effects. We obtain vertical excitation energies of 3.13 eV (396 nm) and 2.68 eV (463 nm), which are in quantitative agreement with the experimental absorption energies of 3.12 eV (397 nm) and 2.61 eV (475 nm) for the A- and B-forms of the protein. We find that the protein environment redshifts the absorption spectra by ∼0.56 eV and ∼0.22 eV for the two states, which can be attributed to ∼80% electrostatic effects and ∼20% steric effects.
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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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