title: Raman spectroscopy as a tool in differentiating conjugated polyenes from synthetic and natural sources.
abstract: This work presents the Raman spectroscopic characterization of synthetic analogs of natural conjugated polyenals found in octocorals, focusing the unequivocal identification of the chemical species present in these systems. The synthetic material was produced by the autocondensation reaction of crotonaldehyde, generating a demethylated conjugated polyene containing 11 carbon-carbon double bonds, with just a methyl group on the end of the carbon chain. The resonance Raman spectra of such pigment has shown the existence of enhanced modes assigned to ν₁(CC) and ν₂(CC) modes of the main chain. For the resonance Raman spectra of natural pigments from octocorals collected in the Brazilian coast, besides the previously cited bands, it could be also observed the presence of the ν₄(CCH₃), related to the vibrational mode who describes the vibration of the methyl group of the central carbon chain of carotenoids. Other interesting point is the observation of overtones and combination bands, which for carotenoids involves the presence of the ν₄ mode, whereas for the synthetic polyene this band, besides be seen at a slightly different wavenumber position, does not appear as an enhanced mode and also as a combination, such as for the natural carotenoids. Theoretical molecular orbital analysis of polyenal-11 and lycopene has shown the structural differences which are also responsible for the resonance Raman data, based on the appearance of the (CH3) vibrational mode in the resonant transition only for lycopene. At last, the Raman band at ca. 1010 cm(-1), assigned to the (CH₃) vibrational mode, can be used for attributing the presence of each one of the conjugated polyenes: the resonance Raman spectrum containing the band at ca. 1010 cm(-1) refers to the carotenoid (in this case lycopene), and the absence of such band in resonance conditions refers to the polyenal (in this case the polyenal-11).
authors.affiliation: NEEM - Núcleo de Espectroscopia e Estrutura Molecular, Departamento de Química, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, MG, Brazil.
authors.forename: Rafaella F
authors.initials: RF
authors.lastname: Fernandes
authors.affiliation: NEEM - Núcleo de Espectroscopia e Estrutura Molecular, Departamento de Química, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, MG, Brazil.
authors.forename: Lenize F
authors.initials: LF
authors.lastname: Maia
authors.affiliation: NEEM - Núcleo de Espectroscopia e Estrutura Molecular, Departamento de Química, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, MG, Brazil.
authors.forename: Mara R C
authors.initials: MR
authors.lastname: Couri
authors.affiliation: NEQC - Núcleo de Estudos em Química Computacional, Departamento de Química, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, MG, Brazil.
authors.forename: Luiz Antonio S
authors.initials: LA
authors.lastname: Costa
authors.affiliation: NEEM - Núcleo de Espectroscopia e Estrutura Molecular, Departamento de Química, Universidade Federal de Juiz de Fora, 36036-330 Juiz de Fora, MG, Brazil. Electronic address: luiz.oliveira@ufjf.edu.br.
authors.forename: Luiz Fernando C
authors.initials: LF
authors.lastname: de Oliveira
mesh_terms: D000818:Animals; D037421:Anthozoa / Q000737:chemistry*; D002338:Carotenoids / Q000032:analysis*; D011090:Polyenes / Q000032:analysis*; D013059:Spectrum Analysis, Raman / Q000379:methods
chemical_list: D011090:Polyenes; D002338:Carotenoids
keywords: Carotenoids; Corals; DFT calculations; Lycopene; Polyenal; Raman effect