Visible-light-driven production of fumarate from CO2 and pyruvate using a photocatalytic system with dual biocatalysts

Abstract

Fumaric acid is a very useful unsaturated dicarboxylic acid because it is a raw material for unsaturated polyester resin. Fumarate is mainly synthesized currently from petroleum resources, with a large amount of CO₂ emitted during its production. Thus, it is desirable to develop fossil-fuel-independent fumarate production methods, in particular those using renewable resources. In this work, visible-light-driven production of fumarate from CO₂ and pyruvate with a system consisting of triethanolamine, water-soluble zinc porphyrin, pentamethylcyclopentadienyl-coordinated rhodium complex, NAD⁺, malate dehydrogenase (NAD⁺-dependent oxaloacetate-decarboxylating) and fumarase was developed. Our work with this system was, to the best of our knowledge, the first example of achieving the fixation of CO₂ to pyruvate using electron accumulation in NAD⁺ with light energy as well as the conversion of the resulting fixed pyruvate to an unsaturated dicarboxylate.