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Molecules 2014, 19(11), 18351-18366; doi:10.3390/molecules191118351

Femtosecond Laser Spectroscopy of the Rhodopsin Photochromic Reaction: A Concept for Ultrafast Optical Molecular Switch Creation (Ultrafast Reversible Photoreaction of Rhodopsin)

1
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygin st.4, Moscow 119334, Russia
2
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygin st.4, Moscow 119991, Russia
3
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Academician Semenov avenue 1, Chernogolovka, Moscow region 142432, Russia
4
Biological Faculty, Lomonosov Moscow State University, Leninskie Gory 1, Moscow 119991, Russia
5
Faculty of Basic Medicine, Lomonosov Moscow State University, Lomonosovsky pr. 31/5, Moscow 119192, Russia
These authors contributed equally to this work.
*
Author to whom correspondence should be addressed.
Received: 8 October 2014 / Revised: 4 November 2014 / Accepted: 6 November 2014 / Published: 11 November 2014
(This article belongs to the Special Issue Molecular Switches)
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Abstract

Ultrafast reverse photoreaction of visual pigment rhodopsin in the femtosecond time range at room temperature is demonstrated. Femtosecond two-pump probe experiments with a time resolution of 25 fs have been performed. The first рump pulse at 500 nm initiated cis-trans photoisomerization of rhodopsin chromophore, 11-cis retinal, which resulted in the formation of the primary ground-state photoproduct within a mere 200 fs. The second pump pulse at 620 nm with a varying delay of 200 to 3750 fs relative to the first рump pulse, initiated the reverse phototransition of the primary photoproduct to rhodopsin. The results of this photoconversion have been observed on the differential spectra obtained after the action of two pump pulses at a time delay of 100 ps. It was found that optical density decreased at 560 nm in the spectral region of bathorhodopsin absorption and increased at 480 nm, where rhodopsin absorbs. Rhodopsin photoswitching efficiency shows oscillations as a function of the time delay between two рump pulses. The quantum yield of reverse photoreaction initiated by the second pump pulse falls within the range 15% ± 1%. The molecular mechanism of the ultrafast reversible photoreaction of visual pigment rhodopsin may be used as a concept for the development of an ultrafast optical molecular switch. View Full-Text
Keywords: rhodopsin; femtosecond spectroscopy; coherent reaction; photoreversibility; molecular switches rhodopsin; femtosecond spectroscopy; coherent reaction; photoreversibility; molecular switches
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Smitienko, O.; Nadtochenko, V.; Feldman, T.; Balatskaya, M.; Shelaev, I.; Gostev, F.; Sarkisov, O.; Ostrovsky, M. Femtosecond Laser Spectroscopy of the Rhodopsin Photochromic Reaction: A Concept for Ultrafast Optical Molecular Switch Creation (Ultrafast Reversible Photoreaction of Rhodopsin). Molecules 2014, 19, 18351-18366.

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