Resonance Raman 3-carotene

Hoskins L C 1984 Resonance Raman-spectroscopy of beta-carotene and lycopene—a physical-chemistry experiment J. Chem. Educ. 61 460-2... 

Mendelsohn, R. and R.W. Van Holten. 1979. Zeaxanthin ([3R,3 R]-beta, beta-carotene-3 -diol) as a resonance Raman and visible absorption probe of membrane structure. Biophys. J. 27 221-235. 

Okamoto H, Hamaguchi HO, and Tasumi M. 1989. Resonance Raman studies on tetradesmethyl-P-carotene aggregates. Journal of Raman Spectroscopy 20(11) 751-756. 

Selective Resonance Raman Detection of Carotenes and Lycopene in Human Skin.104... 

SELECTIVE RESONANCE RAMAN DETECTION OF CAROTENES AND LYCOPENE IN HUMAN SKIN... 

Hu, Y., Heshimoto, H., Moie, G., Hengartner, U., and Koyama, Y. 1997. Unique properties of the ll-cis and 11,11 -di-civ isomers of P-carotene as revealed by electronic absorption, resonance Raman and 1H and 13C NMR spectroscopy and by HPLC analysis of their thermal isomerization. J. Chem. Soc. Perkin Trans. 2 2699-2710. 

Koyama, Y., Kito, M., Takii, T., Saili, K., Tsukida, K., and Yamashita, J. 1983. Configuration of the carotenoid in the reaction centers of photosynthetic bacteria. 2. Comparison of the resonance Raman lines of the reaction centers with those of the 14 different cis-trans isomers of (i-carotene. Photobiochem. Photobiophys. 5 139-150. 

Sashima, T., Koyama, Y., Yamada, T., and Hashimoto, H. 2000. The lBu+, lBu", and 2Ag" energies of crystalline lycopene, P-carotene, and mini-9-P-carotene as determined by resonance-Raman excitation profiles Dependence of the I IUi state energy on the conjugation length../. Phys. Chem. B 104 5011-5019. 

Resonance Raman Spectroscopy. A review of the interpretation of resonance Raman spectra of biological molecules includes a consideration of carotenoids and retinal derivatives. Another review of resonance Raman studies of visual pigments deals extensively with retinals. Excitation profiles of the coherent anti-Stokes resonance Raman spectrum of j8-carotene have been presented. Resonance Raman spectroscopic methods have been used for the detection of very low concentrations of carotenoids in blood plasma and for the determination of carotenoid concentrations in marine phytoplankton, either in situ or in acetone extracts. ... 

Polyenes exhibit two strong Raman bands between 1600 and 1500 cm and between 1200 and 1100 cm , respectively. These are attributed to in-phase vibrations of the C=C and C-C bonds, respectively, throughout the entire chain. Examples include all-trans-retinol (Fig. 4.1-6B), /3-carotene, and carotene-containing proteins, obtained, for instance, from lobster shells (Rimai et al., 1973 Oseroff and Callender, 1974). Polyene sequences with approximately twenty conjugated double bonds, formed by HCl elimination from polyvinyl chloride as a result of aging, also show these Raman bands at 1495 and 1115 cm (Peitscher and Holtrup, 1975). These bands are enhanced as a consequence of the resonance Raman effect, which makes it possible to detect such groups in polymers and natural materials, even at low concentration. 

Infrared and Resonance Raman Spectroscopy. Reviewson the uses of resonance Raman spectroscopy in biochemistry and biology include sections on carotenoproteins, visual pigments, and bacteriorhodopsin. The resonance Raman spectrum of the lowest excited triplet state of /3-carotene has been reported.A resonance Raman method has been used for the quantitative analysis of /3-carotene and lutein (20) in tobacco.The mechanism of carotenoid-protein interactions in the carotenoproteins ovoverdin and /3-crustacyanin has been investigated by resonance Raman spectroscopy. " 2 axanthin (24) has been used as a resonance Raman probe of membrane structure. " The resonance Raman spectra have been reported of all-frans-anhydrovitamin A (194), " /3-ionone, retinals, and Schiff bases.The technique has been used extensively to study... 

The effect of oxygen on cyclic 1,3-diradicals shows that conformation can affect the triplet state lifetime ST Time resolved resonance Raman spectroscopy has been used to examine triplet states produced from different isomers of p-carotene. A theoretical study has also been reported on the a-cleavage of the triplet states of symmetric and non-symmetric ketones S mechanism for triplet state relaxation of aromatic molecules has been used to explain experimental data for substituted benzenes. The decay kinetics of triplet-triplet fluorescence in the mesitylene biradical (two sub-levels) have been measured between 10 and 77K in Shpolski matrices triplet state of dimesityl... 

Raman and Infrared Spectroscopy. Two reviews deal with resonance Raman spectroscopy of carotenoid-containing biomolecules and micro-organisms152 and of carotenoids and chlorophylls in photosynthetic bacteria.153 The resonance Raman excitation profile of lycopene in acetone has been determined.154 Calculations previously used for (3-carotene do not explain the lycopene data. Several papers report detailed studies of the time-resolved resonance Raman spectra of... 

H Fujiwara, H Hayashi, M Tasumi, M Kanji, YKoyamaand (Ki) Satoh (1987) Structural studies on a photosystem II reaction center complex consisting ofD-1 and D-2 polypeptides and cytochrome b-559 by resonance Raman spectroscopy and high-performance liquid chromatography. Chem Lett 10 2005-2008 GE Bialek-Bylka, T Tomo, (Ki) Satoh and Y Koyama (1995) 15-cis-carotene found in the reaction center of spinach photosystem II. FEES Lett 363 137-140... 

Resonance Raman Spectroscopy. This technique is finding increasing application in the carotenoid field. Details of the resonance Raman spectra of jS-caro-tene," y-carotene carotene (166)], and torulene [3, 4 -didehydro-/3, /f-carotene (167)]" have been given. Details of the Raman excitation profiles of... 

Frank HA, Chadwick BW, Taremi S, Kolaczkowski S and Bowman MK (1986) Singlet and triplet absorption spectra of carotenoids bound in the reaction centers of Rhodopseudomonas sphaeroides R26. FEBS Lett 203 157-163 Fujii R, Chen CH, MizoguchiTandKoyamaY (1998) H NMR, electronic-absorption and resonance-Raman spectra of isomeric okenone as compared with those of isomeric j3-carotene, canthaxanthin, /3-apo-8 -carotenal and spheroidene. Spectro-chim Acta A54 727-743... 

Correlations between the H-NMR, electronic-absorption and resonance-Raman spectra and the ds-trans configurations have been identified for j3-carotene and other carotenoids (1) the chemical shifts ofthe olefinic Hs in NMR, (2) the wavelength ofthe A absorption and the relative intensity ofthe A —> Ag vs. the A B, absorption in electronic absorption, and (3) the C=C stretching frequency, the relative intensity ofthe... 

Figure 1 shows the chemical structures ofcarotenoids which will be dealt with in this Section. The length and position of the conjugated system are different from one carotenoid to another. All the carotenoids, except for /3-apo-8 -carotenal, neurosporene, and spheroidene, contain a complete central structural motif which is terminated by the 6 and 6 carbon atoms. The dependence of the H-NMR, electronic absorption and resonance-Raman spectroscopic properties on the cis-trans configurations of the symmetric )3-carotene molecule can change when there is a lack of a complete central structural motif in a carotenoid or when the carotenoid is asymmetric. In the following three subsections, the spectroscopic properties of the carotenoid, )3-carotene, will be described first, and then those of other carotenoids will be mentioned. 

Fig. 8. Resonance-Raman spectra of T, spices of carotene genej-ated from the (a) (b) 7-cis, (c) 9-cis, (d)) 3-mand...

Fig. 12. Resonance-Raman excitation profiles (at 77 K) of (a) the C=C stretching (V ) mode of crystalline all-rrans- carotene, and (b) the C=C stretching (V ) mode and (c) the C-C stretching (V2) mode of crystalline all-tra/ts-spheroidene.

Hashimoto H and Koyama Y (1988) Time-resolved resonance Raman spectroscopy of triplet /3-carotene produced from aU-trans, 1-cis, 9-cis, 13-m, and 15-cw isomers and high-pressure liuid chromatography analyses of photoisomerization via the triplet state. J Phys Chem 92 2101-2108... 

Hashimoto H and Koyama Y (1989) The C=C stretching Raman lines of /3-carotene isomers in the S state as detected by pump-probe resonance Raman spectroscopy. Chem Phys Lett 154 321-325... 

Hashimoto H, Koyama Y and Mori Y (1997) Mechanism activatingthe 2 Ag state in all-/ram -)3-carotene crystal to resonance Raman scattering. Jpn J Appl Phys 36 916-918 Hauska G, Hager-Braun C, Schneebauer N, Schiitz M, Zimmermann R and Nelson N (1995) Biochemical aspects of the reaction center in green sulfur bacteria—comparison with otherFeS-types. In Mathis P(ed) Photosynthesis FromLight to Biosphere, Vol 11, pp 11-16. Kluwer Academic Publishers, Dordrecht... 

Resonance Raman spectra of all-trans, planar, jS-carotene molecules are generally obtained in resonance conditions with their main electronic transition (corresponding to B [left arrow] Ag transition of the polyene chain) or in preresonance conditions with this transition. They contain about 40 bands between 90 and 1610 cm , among which three groups are very intense, at ca. 1530 (v,), 1120-1200 (V2), and 1000(V3) cm" (Fig. 1). When exciting with ultra-violet lasers in the 260 nm region, in resonance with the 2 B <— Ag transition, spectra are then dominated by an intense band at about 1590 cm" (Saito et al., 1983). The enhancement of all these bands correspond to A-type resonance, i.e. involving only one excited electronic level. 

Fig. I. Resonance Raman spectra (800-1620 cm" ) of CP 47-bound /J-carotene (bottom) and FCP-bound fucoxanthin (top). Excitation conditions 488.0 nm. Temperature 77 K...

The influence ofthe molecular conformation on the resonance Raman spectra of /3-carotene was systematically determined for 14 different cis-trans isomers in the early 1980s (Koyama et al, 1982, 1983, 1988a). The conformation of 8 of these 14 isomers was determined by NMR spectroscopy, allowing the comparison ofresonance Raman spectra... 

More recently, applying these calculations, which were originally performed on the symmetric p-carotene molecule, to other carotenoids has been questioned. Resonance Raman spectra of spheroidene molecules selectively enriched in either C or were performed, and they led to quite surprising results. It was in particular shown that the 15 "C substitution had nearly no effect on spheroidene s resonance Raman spectra, while the 14 C substitution resulted in dramatic spectral perturbations (Kok et al., 1994). This is in good agreement with the conclusions drawn from normal mode analysis of all-trans /3-carotene, that the C,5=C,5 stretch is decoupled from the other C=C stretches However, the same calculations led to the conclusion that the main 1540 cm observed in the 15-cis isomers arises principally from the C, s=C, 5 stretching... 

The first resonance Raman spectra of /3-carotene in its triplet state were obtained in 1979, using excitation at 531 nm which is located near the main T<—T absorption transition at 515 nm. The triplet state was accumulated by pulse radiolysis, using naphthalene as a sensitizer, and this was one of the first examples of time-resolved resonance Raman spectroscopy applied to a molecular excited state (Dallinger et al.,... 

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