Light-driven Lytic Polysaccharide Monooxygenase Catalysis Mediated by Type I Photosensitizers

Autor(es)

Sepulchro, Ana Gabriela Veiga ; Vacilotto, Milena Moreira ; Dias, Lucas D. ; Pellegrini, Vanessa O. A. ; Velasco, Josman ; Inada, Natalia M. ; Segato, Fernando ; Polikarpov, Igor

• Tipo de documento: Artigo Científico
• Fonte: CHEMBIOCHEM; v. N/A, p. 14-pg., 2024-11-11.

Resumo

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. (AU)

• Processo FAPESP: 21/08780-1 - Degradação enzimática de exopolissacharídeos de biofilmes microbianos: abordagens de biofísica estrutural, biotecnologia molecular e bioquímica sintética em estudos de CAZymes em busca de novas ferramentas enzimáticas para tratamentos antimicrobianos
• Beneficiário: Igor Polikarpov
• Modalidade de apoio: Auxílio à Pesquisa - Temático
• Processo FAPESP: 24/00533-3 - Biorrefino de hemiceluloses e lignina do bagaço de cana-de-açúcar
• Beneficiário: Igor Polikarpov
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 19/13569-8 - Estudo dos Mecanismos de Ação em Terapia Fotodinâmica: Do Fotossensibilizador à Aplicação Prática
• Beneficiário: Lucas Danilo Dias
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 13/07276-1 - CEPOF - Centro de Pesquisa em Óptica e Fotônica
• Beneficiário: Vanderlei Salvador Bagnato
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 14/50857-8 - INCT 2014 - de Óptica Básica e Aplicada às Ciências da Vida
• Beneficiário: Vanderlei Salvador Bagnato
• Modalidade de apoio: Auxílio à Pesquisa - Temático