Interfacial photoreactions and chemical capacitance in lipid bilayers.

The electrical response of a pigmented lipid bilayer to a short laser pulse is measured by a tunable voltage clamp method. In this method, a variable access impedance permits "tuning" of the observed relaxations for optimal measurements. Analysis of the data so obtained leads to an equivalent circuit that contains a novel chemical capacitance charged by the specific photoreaction across a single membrane-water interface. This chemical capacitance is distinct from the ordinary membrane capacitance. The intrinsic chemical rate constant obtained from the equivalent circuit analysis is shown to be the pseudo-first-order rate constant of the reverse dark reaction of the reduced acceptor and the oxidized pigment. The tunable voltage clamp method of measurement and analysis allows unambiguous separation of this rate constant into resistive and capacitative elements, which are interpreted in molecular terms.