Light-driven lytic polysaccharide monooxygenase catalysis mediated by type I photosensitizers.
SEPULCHRO, Ana Gabriela Veiga; VACILOTTO, Milena Moreira; DIAS, Lucas Danilo; PELLEGRINI, Vanessa de Oliveira Arnoldi; VELASCO, Josman; INADA, Natalia Mayumi; SEGATO, Fernando; POLIKARPOV, Igor.
SEPULCHRO, Ana Gabriela Veiga; VACILOTTO, Milena Moreira; DIAS, Lucas Danilo; PELLEGRINI, Vanessa de Oliveira Arnoldi; VELASCO, Josman; INADA, Natalia Mayumi; SEGATO, Fernando; POLIKARPOV, Igor.
Abstract: The use of light as abundant, renewable, and clean energy source to boost lytic polysaccharide monooxygenase (LPMO) reactions represents an exciting and yet under-explored opportunity. Herein we demonstrated that photosensitizers, commonly used in photodynamic therapy, which act through the photocatalytic Type I mechanism can drive the oxidation of PASC by LPMOs, whereas Type II photosensitizers are not capable of promoting the LPMO activity. We analyzed Type I and Type II photosensitizers (methylene blue and tetraiodide salt of meso-tetrakis-(4-N-methylpyridyl) porphyrin, respectively) and demonstrated that, even without an addition of external reductant, Type I was capable of boosting Thermothelomyces thermophila MtLPMO9A activity in the presence of light. We also evaluated the photobiosystem in the presence and/or absence of molecular oxygen (O2) and hydrogen peroxide (H2O2), and investigated the role of superoxide radical in the methylene blue fueled reactions. Furthermore, we demonstrated that sodium bisulfite (NaHSO3), a chemical scavenger of H2O2, acts by safeguarding the enzyme from oxidative damage caused by accumulation of H2O2 early in photosensitizer-driven LPMO reactions. Finally, the results of the present work demonstrated that light-driven LPMO reactions mediated photodynamic therapy (PDT) Type I photosensitizers, which also includes molecules such as curcumin and riboflavin, is a general phenomenon.
@article={003225097,author = {SEPULCHRO, Ana Gabriela Veiga; VACILOTTO, Milena Moreira; DIAS, Lucas Danilo; PELLEGRINI, Vanessa de Oliveira Arnoldi; VELASCO, Josman; INADA, Natalia Mayumi; SEGATO, Fernando; POLIKARPOV, Igor.},title={Light-driven lytic polysaccharide monooxygenase catalysis mediated by type I photosensitizers},journal={ChemBioChem},note={v. 25, n. 23, p. e202400486},year={2024}}