1. Sub-Millisecond Photoinduced Dynamics of Free and EL222-Bound FMN by Stimulated Raman and Visible Absorption Spectroscopies.
- Author
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Liu, Yingliang, Chaudhari, Aditya S., Chatterjee, Aditi, Andrikopoulos, Prokopis C., Picchiotti, Alessandra, Rebarz, Mateusz, Kloz, Miroslav, Lorenz-Fonfria, Victor A., Schneider, Bohdan, and Fuertes, Gustavo
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OPTICAL spectroscopy , *FLAVIN mononucleotide , *RAMAN spectroscopy , *TIME-resolved spectroscopy , *INFRARED spectroscopy - Abstract
Time-resolved femtosecond-stimulated Raman spectroscopy (FSRS) provides valuable information on the structural dynamics of biomolecules. However, FSRS has been applied mainly up to the nanoseconds regime and above 700 cm−1, which covers only part of the spectrum of biologically relevant time scales and Raman shifts. Here we report on a broadband (~200–2200 cm−1) dual transient visible absorption (visTA)/FSRS set-up that can accommodate time delays from a few femtoseconds to several hundreds of microseconds after illumination with an actinic pump. The extended time scale and wavenumber range allowed us to monitor the complete excited-state dynamics of the biological chromophore flavin mononucleotide (FMN), both free in solution and embedded in two variants of the bacterial light-oxygen-voltage (LOV) photoreceptor EL222. The observed lifetimes and intermediate states (singlet, triplet, and adduct) are in agreement with previous time-resolved infrared spectroscopy experiments. Importantly, we found evidence for additional dynamical events, particularly upon analysis of the low-frequency Raman region below 1000 cm−1. We show that fs-to-sub-ms visTA/FSRS with a broad wavenumber range is a useful tool to characterize short-lived conformationally excited states in flavoproteins and potentially other light-responsive proteins. [ABSTRACT FROM AUTHOR]
- Published
- 2023
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