Enhancing Control Over Nitric Oxide Photorelease via a Molecular Keypad Lock.

Based on Boolean logic, molecular keypad locks secure molecular information, typically with an optical output. Here we investigate a rare example of a molecular keypad lock with a chemical output. To this end, the light-activated release of biologically important nitric oxide from a ruthenium complex is studied, using proton concentration and photon flux as inputs. In a pH-dependent equilibrium, a nitritoruthenium(II) complex is turned into a nitrosylruthenium(II) complex, which releases nitric oxide under irradiation with visible light. The precise prediction of the output nitric oxide concentration as function of the pH and photon flux is achieved with an artificial intelligence approach, namely the adaptive neuro-fuzzy inference system. In this manner an exceptionally high level of control over the output concentration is obtained. Moreover, the provided concept to lock a chemical output as well as the output prediction may be applied to other (photo)release schemes.