Sub-Millisecond Photoinduced Dynamics of Free and EL222-Bound FMN by Stimulated Raman and Visible Absorption Spectroscopies

0568516 - BTÚ 2024 RIV CH eng J - Článek v odborném periodiku
Liu, Yingliang - Chaudhari, Aditya S. - Chatterjee, Aditi - Andrikopoulos, Prokopis C. - Picchiotti, A. - Rebarz, M. - Kloz, M. - Lorenz-Fonfria, V. A. - Schneider, Bohdan - Fuertes, Gustavo
Sub-Millisecond Photoinduced Dynamics of Free and EL222-Bound FMN by Stimulated Raman and Visible Absorption Spectroscopies.
Biomolecules. Roč. 13, č. 1 (2023), č. článku 161. E-ISSN 2218-273X
Institucionální podpora: RVO:86652036
Klíčová slova: flavins * protein structural dynamics * light-oxygen-voltage (LOV) photosensors * femtosecond-stimulated Raman spectroscopy (FSRS) * photochemistry
Obor OECD: Biochemistry and molecular biology
Impakt faktor: 5.5, rok: 2022
Způsob publikování: Open access
https://www.mdpi.com/2218-273X/13/1/161

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 (similar to 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.
Trvalý link: https://hdl.handle.net/11104/0342657