Bioinorganic Chemistry on Electrodes: Methods to Functional Modeling

One of the major goals of bioinorganic chemistry has been to mimic the function of elegant metalloenzymes. Such functional modeling has been difficult to attain in solution, in particular, for reactions that require multiple protons and multiple electrons (nH+ /ne-). Using a combination of heterogeneous electrochemistry, electrode and molecule design one may control both electron transfer (ET) and proton transfer (PT) of these nH+ /ne- reactions. Such control can allow functional modeling of hydrogenases (H+ + e- -> 1/2 H2), cytochrome c oxidase (O2 +4e- +4H+ -> 2 H2O), monooxygenases (RR ' CH2 + O2 +2e- + 2 H+ -> RR ' CHOH + H2O) and dioxygenases (S + O2 -> SO2; S = organic substrate) in aqueous medium and at room temperatures. In addition, these heterogeneous constructs allow probing unnatural bioinspired reactions and estimation of the inner- and outersphere reorganization energy of small molecules and proteins.

Automated summary

One of the major goals of bioinorganic chemistry is to mimic the function of metalloenzymes. By utilizing heterogeneous electrochemistry and molecule design, it is possible to control both electron and proton transfer reactions. This control enables functional modeling of various important reactions and provides insights into unnatural bioinspired reactions and reorganization energy estimation.