Sampling the protonation states: the pH-dependent UV absorption spectrum of a polypeptide dyad
Literature Information
Elisa Pieri, Vincent Ledentu, Miquel Huix-Rotllant, Nicolas Ferré
When a chromophore interacts with several titratable molecular sites, the modeling of its photophysical properties requires to take into account all their possible protonation states. We have developed a multi-scale protocol, based on constant-pH molecular dynamics simulations coupled to QM/MM excitation energy calculations, aimed at sampling both the phase space and protonation state space of a short polypeptide featuring a tyrosine–tryptophan dyad interacting with two aspartic acid residues. We show that such a protocol is accurate enough to help in the interpretation of the experimental tyrosine UV absorption spectrum at both acidic and basic pH. Moreover, it is confirmed that radical tryptophan probably contributes to the peptide spectrum, thanks to a UV-induced electron transfer from tyrosine to tryptophan, ultimately shedding light on the complex pH-dependent behavior of the peptide spectrum.
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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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