Artificial photosynthesis is significant for renewable energy generation,sustainable development,and environmental protection.Dye-protein hybrids are promising for developing photosynthesis mimics(e.g.,photo-biocataly...Artificial photosynthesis is significant for renewable energy generation,sustainable development,and environmental protection.Dye-protein hybrids are promising for developing photosynthesis mimics(e.g.,photo-biocatalysis),but their performances are far lower than the plant photosystems,partially because of the incompatibility between dye and the protein matrix that limits excited state electron transfer of the included dyes.Here,using ThT-insulin amyloid assembly as a model system,we proposed that increasing the dye-protein compatibility could lead to the improved photo-biocatalytic performance.A ThT derivative,ThTPD,was designed with the same electron acceptor but extended π-conjugated donor structure.When integrated into the insulin amyloid,the extended π-conjugated donor structure allowed increased binding affinity and energy with the amyloid matrix,thus better electron transport to the mediator to drive the photocatalytic reaction.Meanwhile,compared with ThT, ThTPD exhibited improved light absorption and longer excited state lifetime.The photo-biocatalytic performance of ThTPD-insulin amyloid was greatly improved as compared with that of ThT in reduced nicotinamide adenine dinucleotide(NADH) regeneration.When integrating with NADH-dependent L-glutamate reductase,the efficiency of the ThTPD-insulin amyloid hybrid was 2.8-fold higher than that of ThT in glutamate generation,showing promising feature in biocatalytic solar-to-chemical conversion.展开更多
基金financial support from the National Natural Science Foundation of China(22274102 and 22001182)the Sichuan Science and Technology Program(2022ZYD0027)+1 种基金the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2022A02)the Fundamental Research Funds for the Central Universities。
文摘Artificial photosynthesis is significant for renewable energy generation,sustainable development,and environmental protection.Dye-protein hybrids are promising for developing photosynthesis mimics(e.g.,photo-biocatalysis),but their performances are far lower than the plant photosystems,partially because of the incompatibility between dye and the protein matrix that limits excited state electron transfer of the included dyes.Here,using ThT-insulin amyloid assembly as a model system,we proposed that increasing the dye-protein compatibility could lead to the improved photo-biocatalytic performance.A ThT derivative,ThTPD,was designed with the same electron acceptor but extended π-conjugated donor structure.When integrated into the insulin amyloid,the extended π-conjugated donor structure allowed increased binding affinity and energy with the amyloid matrix,thus better electron transport to the mediator to drive the photocatalytic reaction.Meanwhile,compared with ThT, ThTPD exhibited improved light absorption and longer excited state lifetime.The photo-biocatalytic performance of ThTPD-insulin amyloid was greatly improved as compared with that of ThT in reduced nicotinamide adenine dinucleotide(NADH) regeneration.When integrating with NADH-dependent L-glutamate reductase,the efficiency of the ThTPD-insulin amyloid hybrid was 2.8-fold higher than that of ThT in glutamate generation,showing promising feature in biocatalytic solar-to-chemical conversion.
