Print Email Facebook Twitter Fueling biomass-degrading oxidative enzymes by light-driven water oxidation Title Fueling biomass-degrading oxidative enzymes by light-driven water oxidation Author Bissaro, Bastien (Norwegian University of Life Sciences (NMBU); INRA Institut National de La Recherche Agronomique) Forsberg, Zarah (Norwegian University of Life Sciences (NMBU)) Ni, Y. (TU Delft BT/Biocatalysis) Hollmann, F. (TU Delft BT/Biocatalysis) Vaaje-Kolstad, Gustav (Norwegian University of Life Sciences (NMBU)) Eijsink, Vincent G H (Norwegian University of Life Sciences (NMBU)) Date 2016 Abstract Photosynthesis may be described as light-driven oxidation of water and subsequent use of the generated reducing equivalents to fix CO2 and synthesize higher energy organic compounds, such as carbohydrates. The transposition of the sustainable and atom-efficient strategy of water oxidation to in vitro controlled biocatalytic reactions is poorly studied but is of high interest for the development of photobiocatalysis, and eco-friendly catalytic tools in a wider sense. Here we demonstrate that light-driven oxidation of water catalysed by vanadium-doped TiO2 (V-TiO2), a re-usable photocatalyst, can provide the electrons that lytic polysaccharide monooxygenases (LPMOs) need to oxidatively deconstruct biomass polysaccharides. The demonstration that electrons may be generated by water oxidation alleviates the need for an externally added electron donor, which so far has been a prerequisite for LPMO activity. Importantly, photocatalytic LPMO activation was achieved in the absence of redox mediators, which represents the first demonstration of mediator-free electron transfer from V-TiO2 particles to a redox enzyme, expanding the repertoire of known and conceivable photobiocatalytic reactions. Fundamentally, this photobiocatalytic system allows activation and tight control of LPMO activity, thus offering new tools for mechanistic studies of these industrially important and ubiquitous enzymes. The latter is illustrated by real-time studies of the redox state of an LPMO, using the controllable light-V-TiO2 technology for LPMO reduction and a novel fluorescence method for monitoring re-oxidation. We also show that the light-V-TiO2 technology may be used to study pre-activation of LPMOs. To reference this document use: http://resolver.tudelft.nl/uuid:cbd2d15a-f811-4ebf-a4f5-a9aa24194cff DOI https://doi.org/10.1039/c6gc01666a Embargo date 2017-07-08 ISSN 1463-9262 Source Green Chemistry, 18 (19), 5357-5366 Bibliographical note Accepted Author Manuscript Part of collection Institutional Repository Document type journal article Rights © 2016 Bastien Bissaro, Zarah Forsberg, Y. Ni, F. Hollmann, Gustav Vaaje-Kolstad, Vincent G H Eijsink Files PDF manuscript_Bissaro_et_al_ ... marked.pdf 1.2 MB Close viewer /islandora/object/uuid:cbd2d15a-f811-4ebf-a4f5-a9aa24194cff/datastream/OBJ/view