TY - JOUR T1 - Bacteriorhodopsin O-state Photocycle Kinetics: A Surfactant Study JF - Photochemistry and Photobiology Y1 - 2010 A1 - Chu, L. K. A1 - El-Sayed, Mostafa A AB - The spectroscopy and dynamics of interaction between the O intermediate of bacteriorhodopsin (bR) and several surfactants (cetrimonium bromide [CTAB], sodium dodecyl sulfate [SDS] and diethylene glycol mono-n-hexyl ether [C6E2]) were investigated using steady-state UV-VIS spectrometry, circular dichroism spectroscopy and time-resolved absorption techniques. The steady-state spectral results show that bR can retain its trimeric state without severe damage in the molar concentration ratio of C6E2/bR ranging up to 4000. Time-resolved observations indicate that the rise and decay rates and transient populations of the O state can be increased in the presence of nonionic surfactant C6E2; however, these studies indicate the opposite phenomenon in the presence of the ionic surfactants CTAB and SDS. The observed 40% enhancement in the transient population of the O intermediate state that results from treatment of C6E2 is proposed to result from an expanding bR structure, which leads to more effective proton pumping efficiency in the photosynthetic system of bR. VL - 86 SN - 0031-8655 N1 - Chu, Li-Kang El-Sayed, Mostafa A. M3 - 10.1111/j.1751-1097.2009.00629.x ER - TY - JOUR T1 - Bacteriorhodopsin-based photo-electrochemical cell JF - Biosensors & Bioelectronics Y1 - 2010 A1 - Chu, L. K. A1 - Yen, C. W. A1 - El-Sayed, Mostafa A AB - A simple solution-based electrochemical cell has been constructed and successfully employed in the detection of the photoelectric response upon photoexcitation of bacteriorhodopsin (bR) without external bias. Commercially-available indium tin oxide (ITO) glasses served as the optical windows and electrodes. Small amounts of bR suspensions (similar to 100 mu L) were utilized as the photovoltaic medium to generate the proton gradient between two half-cells separated by a molecular porous membrane. Continuous broadband visible light (lambda >380 nm) and a short-pulse 532-nm laser were employed for the photoexcitation of bR. Upon the modulated cw broadband irradiation, an instantaneous rise and decay of the current was observed. Our observations of the pH-dependent photocurrent are consistent with previous reports in a bR thin film configuration, which also showed a polarity inversion at pH 5-6. This is due to the change of the priority of the proton release and proton uptake in the photocycle of bR. Studies on the ionic strength effect were also carried out at different KC1 concentrations, which resulted in the acceleration of the rise and decay of the photoelectric response. This was accompanied by a decrease in the stationary photocurrent at higher KC1 concentrations in the broadband excitation experiments. The solution-based electrochemical cell uses aqueous medium, which is required for the completion of the bR proton pumping function. Due to the generation of the stationary current, it is advantageous to convert solar energy into electricity without the need of film-based photovoltaic devices with external bias. (C) 2010 Elsevier B.V. All rights reserved. VL - 26 SN - 0956-5663 N1 - Chu, Li-Kang Yen, Chun-Wan El-Sayed, Mostafa A. M3 - 10.1016/j.bios.2010.07.013 ER - TY - JOUR T1 - Kinetics of the M-Intermediate in the Photocycle of Bacteriorhodopsin upon Chemical Modification with Surfactants JF - Photochemistry and Photobiology Y1 - 2010 A1 - Chu, L. K. A1 - El-Sayed, Mostafa A AB - The spectroscopic and kinetic studies of the interaction between bacteriorhodopsin in the M-intermediate and several surfactants (cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, diethylene glycol mono-n-hexyl ether, ethylene glycol mono-n-hexyl ether, sodium 1-decanesulfonate and sodium 1-heptanesulfonate) have been investigated using steady-state UV-VIS spectrometry and time-resolved absorption techniques. The steady-state spectral results show that bR retains its trimeric state. Time-resolved observations indicate that the rate of deprotonation of the protonated Schiff base increases in the presence of the cationic surfactants, whereas insignificant changes are observed in the neutral or anionic surfactants. The rate of the reprotonation of the Schiff base in the transition M -> N is accelerated in anionic and neutral surfactants, but is decelerated in the presence of the cationic surfactants. Surfactants with a longer hydrocarbon tail have a greater effect on the kinetics when compared with surfactants having shorter hydrocarbon tails. The opposite effect is observed when the hydrophilic head of the surfactants contains opposite charges. These distinct kinetics are discussed in terms of the difference in the modified surface hydrophilicity of the bR and the possible protein configurational changes upon surfactant treatments. VL - 86 SN - 0031-8655 N1 - Chu, Li-Kang El-Sayed, Mostafa A. M3 - 10.1111/j.1751-1097.2009.00666.x ER - TY - JOUR T1 - On the Mechanism of the Plasmonic Field Enhancement of the Solar-to-Electric Energy Conversion by the Other Photosynthetic System in Nature (Bacteriorhodopsin): Kinetic and Spectroscopic Study JF - Journal of Physical Chemistry C Y1 - 2010 A1 - Chu, L. K. A1 - Yen, C. W. A1 - El-Sayed, Mostafa A AB - We have recently reported Ag nanoparticles (AgNPs) plasmonic field enhancement of the Bacteriorhodopsin (bR) photocurrent observed during its proton pump photocycle in solution. We proposed a mechanism based on the plasmonic field enhancement of the blue light effect which bypasses the slow part of the photocycle and increases the rate of proton production and thus the observed photocurrent. In this present work, we studied the AgNPs plasmonic field effect on the spectroscopy and kinetics of the bR proton pumping photocycle. We examined the blue light effect on both the recovery rate of bR and the decay rate of the M intermediate by using 532-nm short-pulsed laser excitation of bR in the presence of AgNPs and continuous-wave blue light exposure. Our observation showed that the recovery of bR and the decay of the M intermediate are both greatly accelerated in the presence of both AgNPs and blue light simultaneously. This gives support for the proposed mechanism of the enhanced proton current in the presence of AgNPs with a plasmon band in the blue region. It was found experimentally that the 40 nm-AgNPs enhancement of the blue light effect on the decay rate is around 400x larger than that of 8 nm-AgNPs. This is found to be in agreement with the known dependence of the plasmonic field on size and the overlap of the plasmonic extinction band with the absorption band of the M intermediates. VL - 114 SN - 1932-7447 N1 - Chu, Li-Kang Yen, Chun-Wan El-Sayed, Mostafa A. M3 - 10.1021/jp105468x ER - TY - JOUR T1 - Plasmonic Field Enhancement of the Bacteriorhodopsin Photocurrent during Its Proton Pump Photocycle JF - Journal of the American Chemical Society Y1 - 2010 A1 - Yen, C. W. A1 - Chu, L. K. A1 - El-Sayed, Mostafa A AB - The proton pump photocycle of bacteriorhodopsin (bR) produces photocurrent on a microsecond time scale which is assigned to the deprotonation step forming the M(412) intermediate. The return of the M(412) intermediate to the bR ground state (bR(570)) has two pathways: (1) thermally via multiple intermediates (which takes 15 ms) or (2) by a more rapid and direct process by absorbing blue light (which takes hundreds of nanoseconds). By using nanoparticles (Ag, Ag-Au, and Au NPs) having different surface plasmon resonance extinction spectra, it is found that Ag NPs whose spectrum overlaps best with the M(412) absorption regions enhance the stationary photocurrent 15 times. This large enhancement is proposed to be due to the accelerated photoexcitation rate of the M(412) (in the presence of the plasmon field of the light in this region) as well as short-circuiting of the photocycle, increasing its duty cycles. VL - 132 SN - 0002-7863 N1 - Yen, Chun-Wan Chu, Li-Kang El-Sayed, Mostafa A. M3 - 10.1021/ja101301u ER -