Formation dynamics and nature of tryptophan's primary photoproduct in aqueous solution

Literature Information

Publication Date 2010-08-16
DOI 10.1039/C0CP00615G
Impact Factor 3.676
Authors

J. Léonard, D. Sharma, B. Szafarowicz, K. Torgasin, S. Haacke


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Abstract

The excited state quenching and photoproduct formation of tryptophan in water is studied by femtosecond transient absorption experiments covering the near-UV and Vis range of wavelengths. The quenching of the excited state absorption occurs simultaneously with the rise of a photoproduct characterized by two absorption bands at 350 nm and 425 nm. Both processes are characterized by the same biexponential kinetics, and the time constants found are in excellent agreement with previous time-resolved fluorescence measurements. By varying the pH and comparing with the transient spectra of Trp incorporated in a peptide where electron transfer is the dominant quenching mechanism, we suggest that the photoproduct is a zwitterionic form of Trp with the indole moiety protonated, formed via excited state proton transfer from the side chain amine group, in agreement with conclusions drawn from nanosecond experiments. The present work thus fills the gap between ultrafast fluorescence decay and nanosecond flash photolysis experiments, and pinpoints Trp's fluorescence quenching mechanism at acidic and neutral pH.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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