Smitienko Olga, Nadtochenko Victor, Feldman Tatiana, Balatskaya Maria, Shelaev Ivan, Gostev Fedor, Sarkisov Oleg, Ostrovsky Mikhail
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygin st.4, Moscow 119334, Russia.
Faculty of Basic Medicine, Lomonosov Moscow State University, Lomonosovsky pr. 31/5, Moscow 119192, Russia.
Molecules. 2014 Nov 11;19(11):18351-66. doi: 10.3390/molecules191118351.
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.
室温下,视色素视紫红质在飞秒时间范围内的超快反向光反应得到了证实。已进行了时间分辨率为25飞秒的飞秒双泵浦探测实验。500纳米处的第一个泵浦脉冲引发视紫红质发色团11-顺式视黄醛的顺反异构化,在短短200飞秒内形成了初级基态光产物。620纳米处的第二个泵浦脉冲相对于第一个泵浦脉冲有200至3750飞秒的可变延迟,引发了初级光产物向视紫红质的反向光转变。这种光转换的结果在两个泵浦脉冲作用后100皮秒的时间延迟下获得的差分光谱上被观察到。发现在视紫红质吸收光谱区域,560纳米处的光密度降低,而在视紫红质吸收的480纳米处光密度增加。视紫红质的光开关效率随两个泵浦脉冲之间的时间延迟呈现振荡。第二个泵浦脉冲引发的反向光反应的量子产率在15%±1%的范围内。视色素视紫红质超快可逆光反应的分子机制可作为开发超快光学分子开关的概念。