Abstract
The femtosecond time-resolved difference absorption spectra of all-trans-β-Apo-8′-carotenal have been recorded and analyzed by the singular-value decomposition (SVD) method followed by global fitting using a sequential model for the excited-state energy relaxation. With this model, we have obtained the excited-state absorption spectra and the lifetimes of the corresponding excited states both in nonpolar solvent n-hexane and polar solvent methanol. Three excited states, namely S3(170fs), S2(2.32ps) and S1(26ps) in n-hexane, and two excited states S2(190fs) and S1(9.4ps) in methanol have been observed. The excited-state absorption spectra of all-trans-β-Apo-8′-carotenal in methanol display a red shift and broadeness, while the lifetime of S1 state becomes shorter. It is proposed that these effects are related to the presence of a carbonyl functional group that leads to the solvent effect on the excited-state energy level. At the same time, it is shown that the SVD method is a useful tool in resolving the time-resolved absorption spectra.
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Macpherson, A. N., Gillbro, T., Solvent dependence of the ultrafast S2−S1 internal conversion rate of β-carotene, J. Phys. Chem. A, 1998, 102: 5049–5058.
Schulten, K., Karplus, M., On the origin of a low-lying forbidden transition in polyenes and related molecules, Chem. Phys. Lett., 1972, 14(3): 305–309.
Hudson, B., Kohler, B. A., Low-lying weak transition in the polyenea, ω-diphenyloctatetraene. Chem. Phys. Lett., 1972, 14: 299–304.
Akimoto, S., Yamazaki, I., Sakawa, T. et al., Temperature effects on excitation relaxation dynamics of the carotenoid β-Carotene and its analogue β-Apo-8′-carotenal, probed by femtosecond fluorescence spectroscopy, J. Phys. Chem. A, 2002, 106: 2237–2243.
Akimoto, S., Takaichi, S., Ogata, T. et al., Excitation energy transfer in carotenoid-chlorophy II protein complexes probed by femtosecond fluorescence decays, Chem. Phys. Lett., 1996, 260: 147–152.
Mimuro, M., Nishimura, Y., Yamazaki, I. et al., Fluorescence properties of the allenic carotenoid fucoxanthin analysis of the effect of Keto carbonyl group by using a model compound, all-transß-Apo-8′-carotenal, J. Lumin., 1992, 51: 1–10.
Zigmantas, D., Hiller, R. G., Yartsev, A. et al., Dynamics of excited states of the carotenoid peridinin in polar solvents: Dependence on excitation wavelength, viscosity, and temperature, J. Phys. Chem. B, 2003, 107: 5339–5348.
Clayton, R. K., Photosynthesis Physical Mechanisms and Chemical Patterns, London: Cambridge University Press, 1980, 147.
Sashima, T., Koyama, Y., Yamada, T. et al., The 1B +u , 1B −u , 2A −g energies of crystalline lycopene, β-carotene, and mini-9-β-carotene as determined by resonance-Raman excitation profiles: dependence of the 1B −u state energy on the conjugation length, J. Phys. Chem. B, 2000, 104: 5011–5019.
Krueger, B. P., Lampoura, S. S., van Stokkum, I. H. M. et al., Energy transfer in the peridinin chlorophyll-a protein of amphidinium carterae studied by polarized transient absorption and target analysis, Biophys. J., 2001, 80: 2843–2855.
Zigmantas, D., Hill, R. G., Sundström, V. et al., Carotenoid to chlorophyll energy ttransfer in the peridinin-chlorophyll-a-protein complex involves an intramolecular charge transfer state, Proc. Natl. Acad. Sci. USA, 2002, 99: 16760–16765.
Becker, R. S., Bensasson, R. V., Lafferty, J. et al., Triplet excited states of carbonyl-containing polyenes, J. Chem. Soc., Faraday Trans., 1978, 274: 2246–2255.
Miki, Y., Kameyama, T., Koyama, Y. et al., Carotenoid singlet levels newly identified by fluorescence and fluorescence-excitation spectroscopy of β-Apo-8′-carotenal at 160K. J. Phys. Chem., 1993, 97: 6142–6148.
Chen, W. G., Braiman, M. S., Kinetic analysis of time-resolved infrared difference spectra of the L and M intermediates of bacteriorhodopsin. Photochem. Photobiol., 1994, 54: 905–910.
Yamaguchi, S., Hamaguchi, H., Femtosecond ultraviolet-visible absorption study of all-trans→13-cis•9-cis photoisomerization of retinal. J. Chem. Phys., 1998, 109: 1397–1408.
Zhang, J. P., Inaba, T., Watanabe, Y. et al., Sub-picosecond time-resolved absorption spectroscopy of all-trans-neurosporene in solution and bound to the LH2 complex from Rhodobacter sphaeroides G1G, Chem. Phys. Lett., 2000, 331: 154–162.
Yamaguchi, S., Hamaguchi, H., Femtosecond time-resolved absorption spectroscopy of all-trans-retinal in hexane. J. Mol. Struct., 1996, 379: 87–92.
Shreve, A. P., Trautman, J. K., Owens, T. G. et al., Determination of the S2 lifetime of β-carotene, Chem. Phys. Lett., 1991, 178: 89–96.
Ricci, M., Bradforth, S. E., Jimenez, R. et al. Internal conversion and energy transfer dynamics of spheroidene in solution and in the LH-1 and LH-2 light-harvesting complexes, Chem. Phys. Lett., 1996, 259: 381–390.
El-Sayed, M. A., The Radiationless processes involving change of multiplicity in the diazenes, J. Chem. Phys., 1962, 36: 573–574.
El-Sayed, M. A., Spin-orbit coupling and the radiationless processes in nitogen heterocyclics, J. Chem. Phys., 1963, 38: 2834–2838.
Ros, M., Hogenboom, M. A., Kok, P. et al., Electronic structure of retinal and related polyenals in the lowest triplet state: an Electron Spin Echo Study, J. Phys. Chem., 1992, 96(7): 2975–2982.
Tavan, P., Schulten, K., Electronic excitation in finite and infinite polyenes, Phys. Rev. B, 1987, 36: 4337–4357.
Frank, H. A., Bautista, J. A., Josue, J. et al., Effect of the solvent environment on the spectroscopic properties and dynamics of the lowest excited states of carotenoids. J. Phys. Chem. B, 2000, 104: 4569–4577.
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Zhang, L., Quan, D., Wang, L. et al. Femtosecond time-resolved difference absorption spectroscopy of all-trans-β-Apo-8′-carotenal. Sci China Ser G: Phy & Ast 47, 208–222 (2004). https://doi.org/10.1360/03yw0241
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DOI: https://doi.org/10.1360/03yw0241