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1
The Initial Photochemical Process of Retinal in Bacter
iorhodopsin
MIYASAKA Lab.Tetsuro KATAYAMA
2
Contents
(1)“Probing the ultrafast charge translocation of photoexcited retinal in bacteriorhodopsin”
(1) S.Schenkl, F. van Mourik, G. vander Zwan, S. Haacke, M. Chergui. Science, 2005, 309, 917
Photoisomerization ;光異性化反応
Introduction ・ Bacteriorhodopsin ・ Photoisomerization Experimental ・ Pump-probe spectroscopy Result and Discussion
・ Probing Tryptophan residues Summary
3
Organisms which can convert light energy into chemical energy
Halobacterium halobium
Purple membrane consists of bacteriorhodopsin
Halobacteria in the Pink Salt Lakes http://www.striderusa.com/salt.html
http://www.unigiessen.de/~gf1265/GROUPS/KLUG/extrem_halophile.html
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Bacteriorhodopsin resembles photosynthesis and rhodopsin
Bacterio-rhodopsin
Photosynthesis Rhodopsin
Function
Light to energy
Light to energy Light to signal
Initial process
Isomerization of retinal
Charge separation and electron transfer
Isomerization of retinal
Existingplace
Plasma membrane
Chloroplast Retina
Plasma membrane ; 細胞膜Chloroplast ; 葉緑体Retina ; 網膜
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Mechanism of bacteriorhodopsin’s photoisomerization is different from that of rhodopsin
F. Gai et al. , Science, 1998, 279, 1886
Schiff base
Rhodopsin
D.W. McCamant et al. , Science, 2005, 310, 1006
Bacteriorhodopsin
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Cycle of isomerization of retinal
F. Garczarek et al. , Nature , 2006, 439, 109
~ 1μs
~ 100μs
>ms
Process of isomerization to K
BR
J
K
>ms
~ 500fs
~ 3ps
S. O. Smith et al. , Proc. Natl. Acad. Sci. USA , 1984, 81, 2055
7H. Luecke et al. , Science, 1999, 286, 255
Cytosol
Extracellular space
Extracellular space ; Cytosol ; 細胞胞質ゾル細胞外側
Bacteriorhodopsin is a part of solar energy transducer
(1)Deprotonation of the Schiff base, protonation of Asp85
(2)proton release to the extracellular surface (3)reprotonation of the Schiff base, deprotonation of Asp96
(4)reprotonation of Asp96
(5)deprotonation of Asp85 reprotonation of the proton release site.
8
Time-dependence of the transient absorption can observed by pump-probe spectroscopy
Probe
Pump
Detector
Delay TimeSampleτ
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What kinds of signals are observed ?
0 t
Photoinduced Absorption
En
erg
y
Equilibrium Nuclear Position
Excitedstate
Groundstate
Equilibrium Nuclear Position : 平衡核間位置 Photoinduced Absorption : 光誘起吸収 Photo-bleaching : ブリーチングStimulated Emission : 誘導放出
0 t
A
⊿
Photo-bleachingStimulated Emission
0 t
A
⊿
10
Absorption spectrum of bacteriorhodopsin consists of Trp and retinal absorbance
560nm Retinal absorbance
265 ~ 280nmTryptophan absorbance
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Transient absorption spectra of retinal
F. Gai et al. , Science, 1998, 279, 1886
At 0.316ps
At 31.6ps
Absorbance spectrum
Photoisomerizationwas over
After 31.6psExcited-state absorption
and stimulated emission
disappearedBleach signal
and Photoproduct
absorptionremained
460nm
560nm
630nm
910nm
12
Initial process of photoisomerization The first event H→I occurs within 50-100fs
The second eventoccurs within 100-200fs.
The third event occurswithin 200-600fs
The fourth event occurswithin 700fs-3 ps
T. Kobayash.et al., Nature, 2001, 414, 531
J
13
Trp residues close to retinal Transition dipole of retinal and Trp86 are parallel
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What do components of signal indicate ?
Decay component was fitted to previous temporal transient absorption (420fs=relaxation to J,3.5ps= relaxation to K)A constant ,weak bleach signal is observed at the longest delay times
-1 0 1 2 3 10 Delay (ps)
15
What is rise component ?
Cross-correlation(FWHM=85fs)
Temporal derivativebleach transient(FWHM=150fs)
Rise time was observed
16
Exiciton-Coupling model
La,b La,b
S1
Sn
X1, X2, X3 ; Linear coupling of La,b - Sn XX1, XX2 ; Linear coupling of La,b, - S1
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Calculation of the effect of retinal dipole moment change
Bleach signal increase
Dipole moment of retinal increase
A* shifts redA doesn’t change
18
Conclusion
Charge translocationoccurs
The isomerization takes place after charge translocation.
K
J
19
Summary
Time scale of charge translocation and its interplay with the initial twisting and subsequent isomerization were confirmed.
20
Landau-zener equation