Recently there has been an increased interest in the development of small molecule electrooxidation catalysts such as (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), for use in the anodic compartment of a biofuel cell. Some TEMPO derivatives are capable of electrochemically oxidizing short chain alcohols and various sugars to the corresponding aldehydes and carboxylic acids under physiological aqueous conditions. However, building libraries of such a catalyst is difficult due to the limited number of commercially available TEMPO derivatives and the lack of modular synthetic pathways to more complicated TEMPO structures. A promising alternative to the physical preparation of such libraries is the use of computational modeling to allow for in silico catalytic screening of a much wider range of TEMPO compounds.

Based on experimental results, we have developed a computational model to probe the structure-function relationships that determine the catalytic activity of a diverse range of water-soluble nitroxyl radical compounds. A strong correlation was found between the difference in the electrochemical oxidation potentials of a compound and its electrocatalytic activity. The newly developed computational model is able to accurately predict the electrochemical potential and catalytic activity of a wide range of nitroxyl radical derivatives.