A Comparison of the Photoelectric Current Responses Resulting from the Proton Pumping Process of Bacteriorhodopsin under Pulsed and CW Laser Excitations

TitleA Comparison of the Photoelectric Current Responses Resulting from the Proton Pumping Process of Bacteriorhodopsin under Pulsed and CW Laser Excitations
Publication TypeJournal Article
Year of Publication1997
AuthorsWang, J, Song, L, Yoo, S-K, EL-Sayed, MA
JournalThe Journal of Physical Chemistry B
Volume101
Issue49
Pagination10599 - 10604
Date Published1997
ISBN Number1520-6106
Abstract

When excited with a pulsed laser, an electric field-oriented bacteriorhodopsin (bR) film on an indium−tin oxide (ITO) conductive electrode generates a photocurrent composed of at least three different components:  B1 (<100 ps), B2 (60 μs), and B3 (ms). When excited with an electronic shutter modulated CW light pulse (>200 ms in duration), a differential photocurrent (components D1 and D2 with decay times in milliseconds) is observed from the bR film. D1 is observed when the CW light is turned on, and D2 is observed when the CW light is turned off. In this paper, we compare the amplitudes and lifetimes of B2, B3, and D1 at various values of pH and ionic strength of the electrolyte solution in which the photocurrent is measured. It is found that changing the film orientation changes the polarity (sign) of B1 and B2, while it does not affect the polarity of B3 and D1. It is also found that B3 and D1 change their polarity upon changing the pH of electrolyte solution, whereas B1 and B2 do not. These results suggest that the origin of B3 and D1 is different from that of B1 and B2. Our results suggest that B3 and D1 are due to the formation of a transient proton capacitor between the two ITO electrodes resulting from the proton pumping in bR. The magnitude and sign of B3 and D1 are determined by the transient proton concentration change (accumulation or disappearance) occurring near the bR-modified ITO electrode interface on the millisecond time scale. The change of sign in B3 and D1 as a function of pH is due to the sequence of proton release/uptake in the bR photocycle:  It first releases protons into the aqueous solution at high pH, while it first takes up protons from the aqueous solution at low pH. The effects of buffer and ionic strength on B3 and D1 are discussed in terms of the kinetics of proton release/uptake and of the transportation of positive and negative ions in the electrolyte solution.

URLhttp://dx.doi.org/10.1021/jp972475r
Short TitleJ. Phys. Chem. B