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

Author(s)

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

• Document type: Journal article
• Source: CHEMBIOCHEM; v. N/A, p. 14-pg., 2024-11-11.

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. (AU)

• FAPESP's process: 21/08780-1 - Enzymatic degradation of microbial biofilm exopolisacharides: structural biophysics, molecular biotechnology and synthetic biochemistry of CAZymes in search for new enzymatic tools for antimicrobial treatments
• Grantee: Igor Polikarpov
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 24/00533-3 - Biorefining hemicelluloses and lignin from sugarcane bagasse
• Grantee: Igor Polikarpov
• Support Opportunities: Regular Research Grants
• FAPESP's process: 19/13569-8 - Study of the Mechanisms of Action in Photodynamic Therapy: From Photosensitizer to Practical Application
• Grantee: Lucas Danilo Dias
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 13/07276-1 - CEPOF - Optics and Photonic Research Center
• Grantee: Vanderlei Salvador Bagnato
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 14/50857-8 - National Institute in Basic Optics and Applied to Life Sciences
• Grantee: Vanderlei Salvador Bagnato
• Support Opportunities: Research Projects - Thematic Grants