Enzyme e-map - Modernising Electrochemical Enzymology To Map Electron Transfer

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In Nature the production of hydrogen and methane fuel molecules from readily available starting materials such as water and carbondioxide is achieved selectively, efficiently and rapidly by electrocatalytic redox-metalloenzymes containing non-precious transitionmetal active sites. The outstanding recent scientific advances made in molecular biology have made the development of biofueltechnologies based on these enzymes a reality, but such applications require a complementary toolkit of physical chemistry methodsthat can dissect how DNA sequence and protein structure relates to function. Classic bio-electrochemistry methods developed in the1980s have been a powerful way to probe the active site reactivity of such enzymes, but they have been unable to map the electrontransfer processes which underpin the catalysis. Therefore, we have been limited to a narrowly active-site focussed view of enzymemechanism. This project will transform the state of the art in bio-electrochemistry to deliver a powerful new technique that can "see"the electron-transfer processes of the highly evolved and essential electron-transfer reaction centres in redox-enzymes, and deconvolutetheir role in electrocatalysis. This will be achieved by deploying advanced computational methods to integrate intelligentexperimental design into electrochemistry to develop a methodology that lets us separate and accurately model the electron transferprocesses of an enzyme bound to substrate, and chemical biology methods to develop linker molecules for light-activated electrograftingof proteins and enzymes onto electrodes. We will showcase the power of this new electrochemical enzymology toolkit byconducting previously impossible hypothesis-led investigations and enzyme-discovery projects into i) cellulose-degrading LPMOsthat play a crucial role in biorefinery enzyme cocktails and ii) hydrogenases, Ni+Fe or Fe-only metalloenzymes that are as rapid andefficient at hydrogen-catalysis as platinum.