Biomolecular Oxidative Damage Activated by Enzymatic Logic Systems: Biologically Inspired Approach

Abstract Logical, responsible, practical . Enzymatic logic gates that process chemical input signals were used to trigger the release of redox‐active iron ions, which produce reactive oxygen species in a catalytic cascade, and thus result in oxidative damage in biomolecules. Functional coupling between enzymatic logic gates and oxidative damage systems resulted in “smart” biochemical ensembles that are activated upon receiving a certain pattern of biochemical signals.Systems that perform oxidative damage to biomolecules through catalytic cascades in the presence of iron‐redox labile species were activated by enzymatic logic gates that process chemical input signals according to built‐in logic operations. AND / OR enzymatic logic gates were composed of glucose oxidase (GOx) and GOx/esterase, respectively. The AND / OR logic functions of the enzyme gates were activated by application of glucose–oxygen and glucose–ethyl acetate input signals, respectively. The enzymatic logic gates, upon activation by specific patterns of the chemical input signals, produced acidic solutions and triggered release of redox labile iron species from a complex that is unstable under acidic conditions. This resulted in the activation of a catalytic cascade, which produced reactive oxygen species (ROS) and subsequently yielded oxidative damage in biomolecules. Functional integration of the enzyme‐based logic systems with the catalytic redox cascade that performs damage in biomolecules on demand is a first step towards “smart” systems capable of programmed detection, identification, and neutralization of potential biohazards.