WorldWideScience

Sample records for carotenoid radical cations

  1. Excited states and electrochromism of radical cation of the carotenoid astaxanthin

    Science.gov (United States)

    Krawczyk, Stanisław

    1998-09-01

    Radical cations of the carotenoid astaxanthin were generated by chemical oxidation with Fe(Cl) 3, and their absorption and electroabsorption (Stark) spectra at temperatures about 150 K were recorded in the spectral range from 5900 to 26000 cm -1 (380 to 1700 nm), covering two absorptive electronic transitions from D 0 (ground) to D 1 and D 2 excited states. The changes in static polarizability are negative and equal -40±10 A 3 for D 0→D 1 and -105±15 A 3 for D 0→D 2, pointing that dominant contribution to polarizabilities results from the coupling of D 1 and D 2 with the ground state. An approximate localization of the next excited state with ground-state parity is estimated based on arguments from perturbation theory.

  2. Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor.

    Science.gov (United States)

    El-Agamey, Ali; McGarvey, David J

    2016-01-01

    The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

  3. Adaptive Neuro-Fuzzy Inference System Applied QSAR with Quantum Chemical Descriptors for Predicting Radical Scavenging Activities of Carotenoids.

    Science.gov (United States)

    Jhin, Changho; Hwang, Keum Taek

    2015-01-01

    One of the physiological characteristics of carotenoids is their radical scavenging activity. In this study, the relationship between radical scavenging activities and quantum chemical descriptors of carotenoids was determined. Adaptive neuro-fuzzy inference system (ANFIS) applied quantitative structure-activity relationship models (QSAR) were also developed for predicting and comparing radical scavenging activities of carotenoids. Semi-empirical PM6 and PM7 quantum chemical calculations were done by MOPAC. Ionisation energies of neutral and monovalent cationic carotenoids and the product of chemical potentials of neutral and monovalent cationic carotenoids were significantly correlated with the radical scavenging activities, and consequently these descriptors were used as independent variables for the QSAR study. The ANFIS applied QSAR models were developed with two triangular-shaped input membership functions made for each of the independent variables and optimised by a backpropagation method. High prediction efficiencies were achieved by the ANFIS applied QSAR. The R-square values of the developed QSAR models with the variables calculated by PM6 and PM7 methods were 0.921 and 0.902, respectively. The results of this study demonstrated reliabilities of the selected quantum chemical descriptors and the significance of QSAR models. PMID:26474167

  4. Adaptive Neuro-Fuzzy Inference System Applied QSAR with Quantum Chemical Descriptors for Predicting Radical Scavenging Activities of Carotenoids.

    Directory of Open Access Journals (Sweden)

    Changho Jhin

    Full Text Available One of the physiological characteristics of carotenoids is their radical scavenging activity. In this study, the relationship between radical scavenging activities and quantum chemical descriptors of carotenoids was determined. Adaptive neuro-fuzzy inference system (ANFIS applied quantitative structure-activity relationship models (QSAR were also developed for predicting and comparing radical scavenging activities of carotenoids. Semi-empirical PM6 and PM7 quantum chemical calculations were done by MOPAC. Ionisation energies of neutral and monovalent cationic carotenoids and the product of chemical potentials of neutral and monovalent cationic carotenoids were significantly correlated with the radical scavenging activities, and consequently these descriptors were used as independent variables for the QSAR study. The ANFIS applied QSAR models were developed with two triangular-shaped input membership functions made for each of the independent variables and optimised by a backpropagation method. High prediction efficiencies were achieved by the ANFIS applied QSAR. The R-square values of the developed QSAR models with the variables calculated by PM6 and PM7 methods were 0.921 and 0.902, respectively. The results of this study demonstrated reliabilities of the selected quantum chemical descriptors and the significance of QSAR models.

  5. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  6. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    DEFF Research Database (Denmark)

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.; Wilbrandt, R.

    1998-01-01

    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...... the Raman spectrum excited in resonance with the absorption band at 425 nm. The spectrum was interpreted with the help of density functional theory calculations. (C) 1998 Elsevier Science B.V.......The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution and...

  7. Adaptive Neuro-Fuzzy Inference System Applied QSAR with Quantum Chemical Descriptors for Predicting Radical Scavenging Activities of Carotenoids

    OpenAIRE

    Changho Jhin; Keum Taek Hwang

    2015-01-01

    One of the physiological characteristics of carotenoids is their radical scavenging activity. In this study, the relationship between radical scavenging activities and quantum chemical descriptors of carotenoids was determined. Adaptive neuro-fuzzy inference system (ANFIS) applied quantitative structure-activity relationship models (QSAR) were also developed for predicting and comparing radical scavenging activities of carotenoids. Semi-empirical PM6 and PM7 quantum chemical calculations were...

  8. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    Energy Technology Data Exchange (ETDEWEB)

    Bors, W.; Saran, M.; Michel, C. (Gesellschaft fuer Strahlen- und Umweltforschung m.b.H. Muenchen, Neuherberg (Germany, F.R.). Abt. Strahlenbiologie)

    1982-05-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e/sup -/sub(aq)), while superoxide anions (O/sub 2//sup -/) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation.

  9. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e-sub(aq)), while superoxide anions (O2-) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  10. Investigation of Fragmentation of Tryptophan Nitrogen Radical Cation

    Science.gov (United States)

    Piatkivskyi, Andrii; Happ, Marshall; Lau, Justin Kai-Chi; Siu, K. W. Michael; Hopkinson, Alan C.; Ryzhov, Victor

    2015-08-01

    This work describes investigation of the fragmentation mechanism of tryptophan N-indolyl radical cation, H3N+-TrpN• ( m/ z 204) studied via DFT calculations and several gas-phase experimental techniques. The main fragment ion at m/ z 131, shown to be a mixture of up to four isomers including 3-methylindole (3MI) π-radical cation, was found to undergo further loss of an H atom to yield one of the two isomeric m/ z 130 ions. 3-Methylindole radical cation generated independently (via CID of [CuII(terpy)3MI]•2+) displayed gas-phase reactivity partially similar to that of the m/ z 131 fragment, further confirming our proposed mechanism. CID of deuterated tryptophan N-indolyl radical cation ( m/ z 208) suggested that up to six H atoms are involved in the pathway to formation of the m/ z 131 ion, consistent with hydrogen atom scrambling during CID of protonated Trp.

  11. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    DEFF Research Database (Denmark)

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.;

    1998-01-01

    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...... the Raman spectrum excited in resonance with the absorption band at 425 nm. The spectrum was interpreted with the help of density functional theory calculations. (C) 1998 Elsevier Science B.V....

  12. Radiolytically generated cation radicals and their intramolecular transformations

    International Nuclear Information System (INIS)

    Recent theoretical and experimental results indicate that conventional cation radicals derived directly from their neutral precursors are often less stable than their nonconventional isomers with no stable counterparts. Many organic cation radicals may spontaneously isomerise, often by a single intramolecular hydrogen transfer, to more stable distonic forms characterised by spatially separated charge and radical side. Cation radicals radiolytically generated in Freon matrices were investigated using low temperature EPR spectroscopy and DFT quantum chemical calculations, which helped to assign the observed transients and to explain the underlying transformations. Different types of transformations of the cation radicals were comprehensively studied. The primary cation radicals of the 2,5-dihydrofuran (2,5-DHF) and 2,5-dihydropyrrol (2,5-DHP) are not stable and undergo irreversible transformation to 2,4-DHF.+ or 2,4-DHP.+, respectively, by intramolecular H-shift within the molecular ring to the former double bond. The 2,4-DHF.+ and 2,4-DHP.+ are stable only at a small temperature range and undergo further intramolecular rearrangements through 2→3 and 3→4 H-shifts, which can be induced by illumination with visible light. In case of lactone cation radicals intramolecular H-transfer occurs from the methylene group in α-position to the primary radical centre localized on carbonyl oxygen. The stability of the primary species depends on geometrical parameters of the lactones studied. The cation radicals of 5-membered ring lactones are most stable, due to the largest separation between the H-atom on the ring and the carbonyl oxygen and, as follows, the largest activation energy. The formation of two new cyclic species was observed in the case of the cation radical of ethyl acrylate (EA), in a reaction sequence of hydrogen transfer from the ester group to the carbonyl oxygen and subsequent intramolecular cycloaddition of the terminal radical to the vinyl double bond

  13. Formation and Dissociation of Phosphorylated Peptide Radical Cations

    OpenAIRE

    Kong, Ricky P. W.; Quan, Quan; Hao, Qiang; Lai, Cheuk-kuen; Siu, Chi-Kit; Chu, Ivan K.

    2012-01-01

    In this study, we generated phosphoserine- and phosphothreonine-containing peptide radical cations through low-energy collision-induced dissociation (CID) of the ternary metal–ligand phosphorylated peptide complexes [CuII(terpy) p M]·2+ and [CoIII(salen) p M]·+ [ p M: phosphorylated angiotensin III derivative; terpy: 2,2':6',2''-terpyridine; salen: N,N '-ethylenebis(salicylideneiminato)]. Subsequent CID of the phosphorylated peptide radical cations ( p M·+) revealed fascinating gas-phase radi...

  14. Surface hopping investigation of the relaxation dynamics in radical cations

    Energy Technology Data Exchange (ETDEWEB)

    Assmann, Mariana; Matsika, Spiridoula, E-mail: smatsika@temple.edu [Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122 (United States); Weinacht, Thomas [Department of Physics, Stony Brook University, Stony Brook, New York 11794 (United States)

    2016-01-21

    Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in these systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.

  15. Radical Addition to Iminium Ions and Cationic Heterocycles

    Directory of Open Access Journals (Sweden)

    Johannes Tauber

    2014-10-01

    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

  16. Formation and Dissociation of Phosphorylated Peptide Radical Cations

    Science.gov (United States)

    Kong, Ricky P. W.; Quan, Quan; Hao, Qiang; Lai, Cheuk-Kuen; Siu, Chi-Kit; Chu, Ivan K.

    2012-12-01

    In this study, we generated phosphoserine- and phosphothreonine-containing peptide radical cations through low-energy collision-induced dissociation (CID) of the ternary metal-ligand phosphorylated peptide complexes [CuII(terpy) p M]·2+ and [CoIII(salen) p M]·+ [ p M: phosphorylated angiotensin III derivative; terpy: 2,2':6',2''-terpyridine; salen: N, N '-ethylenebis(salicylideneiminato)]. Subsequent CID of the phosphorylated peptide radical cations ( p M·+) revealed fascinating gas-phase radical chemistry, yielding (1) charge-directed b- and y-type product ions, (2) radical-driven product ions through cleavages of peptide backbones and side chains, and (3) different degrees of formation of [M - H3PO4]·+ species through phosphate ester bond cleavage. The CID spectra of the p M·+ species and their non-phosphorylated analogues featured fragment ions of similar sequence, suggesting that the phosphoryl group did not play a significant role in the fragmentation of the peptide backbone or side chain. The extent of neutral H3PO4 loss was influenced by the peptide sequence and the initial sites of the charge and radical. A preliminary density functional theory study, at the B3LYP 6-311++G(d,p) level of theory, of the neutral loss of H3PO4 from a prototypical model— N-acetylphosphorylserine methylamide—revealed several factors governing the elimination of neutral phosphoryl groups through charge- and radical-induced mechanisms.

  17. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    Science.gov (United States)

    Dreuw, Andreas; Starcke, Jan Hendrik; Wachtveitl, Josef

    2010-07-01

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT rad + ) are investigated. While the optically allowed excited D 1 and D 3 states are typical ππ∗ excited states, the D 2 and D 4 states are nπ∗ states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ∗ states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  18. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    Energy Technology Data Exchange (ETDEWEB)

    Dreuw, Andreas, E-mail: andreas.dreuw@theochem.uni-frankfurt.de [Institute of Physical and Theoretical Chemistry, Goethe-University Frankfurt, Max von Laue-Str. 7, 60438 Frankfurt am Main (Germany); Starcke, Jan Hendrik; Wachtveitl, Josef [Institute of Physical and Theoretical Chemistry, Goethe-University Frankfurt, Max von Laue-Str. 7, 60438 Frankfurt am Main (Germany)

    2010-07-19

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT{sup {center_dot}+}) are investigated. While the optically allowed excited D{sub 1} and D{sub 3} states are typical {pi}{pi}* excited states, the D{sub 2} and D{sub 4} states are n{pi}* states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed {pi}{pi}* states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  19. Excited state properties of the astaxanthin radical cation: A quantum chemical study

    International Nuclear Information System (INIS)

    Using time-dependent density functional theory, the excited electronic states of the astaxanthin radical cation (AXT·+) are investigated. While the optically allowed excited D1 and D3 states are typical ππ* excited states, the D2 and D4 states are nπ* states. Special emphasis is put onto the influence of the carbonyl groups onto the excited states. For this objective, the excited states of four hypothetical carotenoids and zeaxanthin have been computed. Addition of a carbonyl group to a conjugated carbon double bond system does essentially not change the vertical excitation energies of the optically allowed ππ* states due to two counter-acting effects: the excitation energy should increase due to the -M-effect of the carbonyl group and at the same time decrease owing to the elongation of the conjugated double bond system by the carbonyl group itself.

  20. Zeaxanthin Radical Cation Formation in Minor Light-Harvesting Complexes of Higher Plant Antenna

    Energy Technology Data Exchange (ETDEWEB)

    Avenson, Thomas H.; Ahn, Tae Kyu; Zigmantas, Donatas; Niyogi, Krishna K.; Li, Zhirong; Ballottari, Matteo; Bassi, Roberto; Fleming, Graham R.

    2008-01-31

    Previous work on intact thylakoid membranes showed that transient formation of a zeaxanthin radical cation was correlated with regulation of photosynthetic light-harvesting via energy-dependent quenching. A molecular mechanism for such quenching was proposed to involve charge transfer within a chlorophyll-zeaxanthin heterodimer. Using near infrared (880-1100 nm) transient absorption spectroscopy, we demonstrate that carotenoid (mainly zeaxanthin) radical cation generation occurs solely in isolated minor light-harvesting complexes that bind zeaxanthin, consistent with the engagement of charge transfer quenching therein. We estimated that less than 0.5percent of the isolated minor complexes undergo charge transfer quenching in vitro, whereas the fraction of minor complexes estimated to be engaged in charge transfer quenching in isolated thylakoids was more than 80 times higher. We conclude that minor complexes which bind zeaxanthin are sites of charge transfer quenching in vivo and that they can assume Non-quenching and Quenching conformations, the equilibrium LHC(N)<--> LHC(Q) of which is modulated by the transthylakoid pH gradient, the PsbS protein, and protein-protein interactions.

  1. Electron exchange involving a sulfur-stabilized ruthenium radical cation.

    Science.gov (United States)

    Shaw, Anthony P; Ryland, Bradford L; Norton, Jack R; Buccella, Daniela; Moscatelli, Alberto

    2007-07-01

    Half-sandwich Ru(II) amine, thiol, and thiolate complexes were prepared and characterized by X-ray crystallography. The thiol and amine complexes react slowly with acetonitrile to give free thiol or amine and the acetonitrile complex. With the thiol complex, the reaction is dissociative. The thiolate complex has been oxidized to its Ru(III) radical cation and the solution EPR spectrum of that radical cation recorded. Cobaltocene reduces the thiol complex to the thiolate complex. The 1H and 31P NMR signals of the thiolate complex in acetonitrile become very broad whenever the thiolate and thiol complexes are present simultaneously. The line broadening is primarily due to electron exchange between the thiolate complex and its radical cation; the latter is generated by an unfavorable redox equilibrium between the thiol and thiolate complexes. Pyramidal inversion of sulfur in the thiol complex is fast at room temperature but slow at lower temperatures; major and minor conformers of the thiol complex were observed by 31P NMR at -98 degrees C in CD2Cl2. PMID:17569530

  2. Polyenyl cations and radical cations – synthesis, spectroscopic properties and reactions

    OpenAIRE

    Kildahl-Andersen, Geir

    2007-01-01

    In the present work, polyene precursors for the formation of charged polyenyl species were synthesised. Their conversion to charge delocalised radical cations and diamagnetic mono- and dications was carried out by treatment with Brønsted and Lewis acids. Reaction conditions were optimised to achieve sufficient stability of the charged polyenes for characterisation by modern spectroscopic methods; in particular nearinfrared absorption spectroscopy (NIR), two-dimensional nuclear magnetic resona...

  3. Structure and Reactivity of the N-Acetyl-Cysteine Radical Cation and Anion: Does Radical Migration Occur?

    NARCIS (Netherlands)

    Osburn, S.; G. Berden,; Oomens, J.; O' Hair, R. A. J.; Ryzhov, V.

    2011-01-01

    The structure and reactivity of the N-acetyl-cysteine radical cation and anion were studied using ion-molecule reactions, infrared multi-photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The radical cation was generated by first nitrosylating the thiol of N-

  4. Excited state dynamics of the astaxanthin radical cation

    Science.gov (United States)

    Amarie, Sergiu; Förster, Ute; Gildenhoff, Nina; Dreuw, Andreas; Wachtveitl, Josef

    2010-07-01

    Femtosecond transient absorption spectroscopy in the visible and NIR and ultrafast fluorescence spectroscopy were used to examine the excited state dynamics of astaxanthin and its radical cation. For neutral astaxanthin, two kinetic components corresponding to time constants of 130 fs (decay of the S 2 excited state) and 5.2 ps (nonradiative decay of the S 1 excited state) were sufficient to describe the data. The dynamics of the radical cation proved to be more complex. The main absorption band was shifted to 880 nm (D 0 → D 3 transition), showing a weak additional band at 1320 nm (D 0 → D 1 transition). We found, that D 3 decays to the lower-lying D 2 within 100 fs, followed by a decay to D 1 with a time constant of 0.9 ps. The D 1 state itself exhibited a dual behavior, the majority of the population is transferred to the ground state in 4.9 ps, while a small population decays on a longer timescale of 40 ps. Both transitions from D 1 were found to be fluorescent.

  5. Perturbing peptide cation-radical electronic states by thioxoamide groups: formation, dissociations, and energetics of thioxopeptide cation-radicals.

    Science.gov (United States)

    Zimnicka, Magdalena; Chung, Thomas W; Moss, Christopher L; Tureček, František

    2013-02-14

    Thioxodipeptides Gly-thio-Lys (GtK), Ala-thio-Lys (AtK), and Ala-thio-Arg (AtR) in which the amide group has been modified to a thioxoamide were made into dications by electrospray ionization and converted to cation-radicals, (GtK + 2H)(+•), (AtK + 2H)(+•), and (AtR + 2H)(+•), by electron transfer dissociation (ETD) tandem mass spectrometry using fluoranthene anion-radical as an electron donor. The common and dominant dissociation of these cation-radicals was the loss of a hydrogen atom. The dissociation products were characterized by collision-induced dissociation (CID) multistage tandem mass spectrometry up to CID-MS(5). The ground electronic states of several (GtK + 2H)(+•), (AtK + 2H)(+•), and (AtR + 2H)(+•) conformers were explored by extensive ab initio and density functional theory calculations of the potential energy surface. In silico electron transfer to the precursor dications, (GtK + 2H)(2+), (AtK + 2H)(2+), and (AtR + 2H)(2+), formed zwitterionic intermediates containing thioenol anion-radical and ammonium cation groups that were local energy minima on the potential energy surface of the ground electronic state. The zwitterions underwent facile isomerization by N-terminal ammonium proton migration to the thioenol anion-radical group forming aminothioketyl intermediates. Combined potential energy mapping and RRKM calculations of dissociation rate constants identified N-C(α) bond cleavages as the most favorable dissociation pathways, in a stark contrast to the experimental results. This discrepancy is interpreted as being due to the population upon electron transfer of low-lying excited electronic states that promote loss of hydrogen atoms. For (GtK + 2H)(+•), these excited states were characterized by time-dependent density functional theory as A-C states that had large components of Rydberg-like 3s molecular orbitals at the N-terminal and lysine ammonium groups that are conducive to hydrogen atom loss. PMID:22765351

  6. Early events following radiolytic and photogeneration of radical cations in hydrocarbons

    International Nuclear Information System (INIS)

    Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials

  7. Novel Cationic Carotenoid Lipids as Delivery Vectors of Antisense Oligonucleotides for Exon Skipping in Duchenne Muscular Dystrophy

    Directory of Open Access Journals (Sweden)

    Vassilia Partali

    2012-01-01

    Full Text Available Duchenne Muscular Dystrophy (DMD is a common, inherited, incurable, fatal muscle wasting disease caused by deletions that disrupt the reading frame of the DMD gene such that no functional dystrophin protein is produced. Antisense oligonucleotide (AO-directed exon skipping restores the reading frame of the DMD gene, and truncated, yet functional dystrophin protein is expressed. The aim of this study was to assess the efficiency of two novel rigid, cationic carotenoid lipids, C30-20 and C20-20, in the delivery of a phosphorodiamidate morpholino (PMO AO, specifically designed for the targeted skipping of exon 45 of DMD mRNA in normal human skeletal muscle primary cells (hSkMCs. The cationic carotenoid lipid/PMO-AO lipoplexes yielded significant exon 45 skipping relative to a known commercial lipid, 1,2-dimyristoyl-sn-glycero-3-ethylphosphocholine (EPC.

  8. Understanding electrochromic processes initiated by dithienylcyclopentene cation-radicals.

    Science.gov (United States)

    Guirado, Gonzalo; Coudret, Christophe; Hliwa, Mohamed; Launay, Jean-Pierre

    2005-09-22

    Simple photochromic dithienylethylenes with either a perfluoro or a perhydro cyclopentene ring, and a variety of substituents (chlorine, iodine, trimethylsilyl, phenylthio, aldehyde, carboxylic acid, and ethynylanisyl), have been prepared and their electrochemical behavior was explored by cyclic voltammetry. All dithienylethylenes present two-electron irreversible oxidation waves in their open form, but the cation-radical of the open isomers can follow two different reaction pathways: dimerization or ring closure, whereas the halogen derivatives follow a dimerization mechanism, the presence of donor groups, such as the phenylthio-substituted compound, promote an efficient oxidative ring closure following an ECE/DISP mechanism. Electrochromic properties are also found in the corresponding ring-closed isomers. Depending on the substituents on the thiophene ring, and the perfluro or perhydro cyclopentene ring, open isomers can be obtained from oxidation (chemical or electrochemical) of the corresponding ring-closed isomers via an EC mechanism. This reaction pathway is favored by the presence of electron-withdrawing groups in the molecule. For all these compounds, closed or open, the oxidation lies between 0.8 and 1.5 V vs SCE, and provokes a permanent modification of the color, even after an oxidation-reduction cycle. This could be qualified as "electrochromism with memory". On the other hand, the ring-closed electron-rich isomers (E degrees electrochromism", for which no structural changes are observed. The experimental study was completed by theoretical calculations at the DFT level, using B3LYP density functional, which gave information on the total energy, the geometry, and the electronic structures of several representative compounds, either in the neutral form or in the cation-radical state. These results are important for the potential design of photochromic systems, such as three-state conjugated systems and photoelectrical molecular switching devices. PMID

  9. Spectroscopy of free-base N-confused tetraphenylporphyrin radical anion and radical cation.

    Science.gov (United States)

    Alemán, Elvin A; Manríquez Rocha, Juan; Wongwitwichote, Wongwit; Godínez Mora-Tovar, Luis Arturo; Modarelli, David A

    2011-06-23

    The radical anions and radical cations of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin have been studied using a combination of cyclic voltammetry, steady state absorption spectroscopy, and computational chemistry. N-Confused porphyrins (NCPs), alternatively called 2-aza-21-carba-5,10,15,20-tetraphenylporphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding the absorption spectra of the corresponding radical ions is paramount to future studies in multicomponent arrays where electron-transfer reactions are involved. NCP 1e was shown to oxidize at a potential of E(ox) 0.65 V vs Fc(+)|Fc in DMF and reduce at E(red) -1.42 V, while the corresponding values for 1i in toluene were E(ox) 0.60 V and E(red) -1.64 V. The geometries of these radical ions were computed at the B3LYP/6-31+G(d)//B3LYP/6-31G(d) level in the gas phase and in solution using the polarizable continuum model (PCM). From these structures and that of H(2)TPP and its corresponding radical ions, the computed redox potentials for 1e and 1i were calculated using the Born-Haber cycle. While the computed reduction potentials and electron affinities were in excellent agreement with the experimental reduction potentials, the calculated oxidation potentials displayed a somewhat less ideal relationship with experiment. The absorption spectra of the four radical ions were also measured experimentally, with radical cations 1e(•+) and 1i(•+) displaying significant changes in the Soret and Q-band regions as well as new low energy absorption bands in the near-IR region. The changes in the absorption spectra of radical anions 1e(•-) and 1i(•-) were not as dramatic, with the changes occurring only in the Soret and Q-band regions. These results were favorably modeled using time-dependent density functional calculations at the TD-B3LYP/6-31+G(d)//B3LYP/6-31G

  10. Radical cations of some water-soluble organoselenium compounds: Insights from pulse radiolysis studies

    Energy Technology Data Exchange (ETDEWEB)

    Priyadarsini, K. Indira [Radiation and Photochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400085 (India)], E-mail: kindira@barc.gov.in; Mishra, B. [Radiation and Photochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400085 (India)

    2008-10-15

    Radical cations of three water-soluble organoselenium compounds, viz., selenourea, selenomethionine, and selenocystine, were produced and their reactions in the pH range 1-7 were studied using nanosecond pulse radiolysis technique. The radical cations, centered on the selenium atom, were generated by one-electron oxidation using hydroxyl ({sup {center_dot}}OH) radicals and Cl{sub 2}{sup {center_dot}}{sup -} and Br{sub 2}{sup {center_dot}}{sup -} radicals. The radical cations of selenourea were converted to dimer radical cations in the entire pH range, which in presence of oxygen released elemental selenium as one of the products. The monomer radical cations of selenomethionine are stabilized at neutral pH by the lone pair of electrons on the N atom of the amino group and undergo partial decarboxylation to produce {alpha}-amino selenyl radicals, which are reducing in nature. At highly acidic conditions, when the lone pair is not available due to protonation, they were converted to dimer radical cations. Selenocystine, being a diselenide, produced monomer radical cations on one-electron oxidation in the entire pH range and acquires stability by sharing the electrons between the two adjacent selenium atoms.

  11. Application of ABTS radical cation for selective on-line detection of radical scavengers in HPLC eluates

    NARCIS (Netherlands)

    Koleva, [No Value; Niederlander, HAG; van Beek, TA

    2001-01-01

    The radical cation 2,2 ' -azinobis-(3 -ethylbenzothiazoline-6-sulfonate), (ABTS(.+)) was utilized in an on-line HPLC method for the detection of radical scavengers in complex matrixes. The HPLC-separated analytes react postcolumn with the preformed ABTS(.+), and the induced bleaching is detected as

  12. An electron spin resonance investigation of ester cation radicals at low temperatures

    International Nuclear Information System (INIS)

    The cation radicals of a series of esters have been produced by γ-irradiation of CFCl3 matrices containing the ester at 77 K. In previous work cations of methyl and ethyl esters were investigated. In this work we report results for larger esters. The cations of these esters are found to undergo immediate internal proton-transfer reactions involving specific sites on one of the alkyl substituents. For example, deuteration studies show that proton transfer occurs from the terminal methyl group in propyl formate to produce -OCH2CH2CH2; whereas in propyl acetate -OCH2CHCH3 is produced. The proton lost from these groups is assumed to add to an oxygen on the ester functional group. In the case of propyl acetate and esters with branched side chains we find that fragmentation reactions follow the proton transfer. In the cases of t-butyl acetate and isobutyl formate the fragmentation process occurs at 77 K and results in the isobutylene cation. Neopentyl formate gives evidence for the cation radical, an RCH2 radical and the fragmentation radical cation as the sample is annealed. These results show that ester cation radicals are highly reactive even at low temperatures where proton-transfer and fragmentation reactions are found. (author)

  13. Radical cation of hydrogen sulfide and reactions of cyclization of 1,5-diketones with its participation

    International Nuclear Information System (INIS)

    Hydrogen sulfide radical cation was generated by electrochemical method during γ-radiation in freon matrix induced by one-electron oxidants (spatially hindered o-benzoquinones). According to ESR spectroscopy data H2S+. radical cation is extremely unstable, even ata temperature of 77 K in freon matrix it exists for 15 min at most. It is shown that hydrogen sulfide radical cation has the properties of a superacid

  14. Molecular design of high performance fused heteroacene radical cations: A DFT study

    International Nuclear Information System (INIS)

    Hybrid density functional theory (DFT) calculations have been carried out for neutral and radical cation of fused furan oligomer, denoted by F(n) where n means number of furan rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused furan was also investigated using one-dimensional periodic boundary condition (PBC) for comparison. It was found that the reorganization energy of radical cation of F(n) from vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that F(n) has an effective hole transport property. It was found that the cation radical of F(n) has a low energy band at near IR region, which is strongly correlated to hole conductivity. The relation between the electronic states and hole conductivity was discussed on the basis of theoretical calculations

  15. Stability of phenol and thiophenol radical cations - interpretation by comparative quantum chemical approaches

    Science.gov (United States)

    Hermann, R.; Naumov, S.; Mahalaxmi, G. R.; Brede, O.

    2000-07-01

    The deprotonation kinetics of phenol-type radical cations, formed via a very efficient electron transfer in the pulse radiolysis of non-polar solutions, for example n-chlorobutane, is governed mainly by electronic effects due to the nature of the phenol substituents, whereas steric effects are of minor importance; thiophenols, which are sulphur analogues of phenols, exhibit a similar behavior. Comparative quantum chemical calculations show that the calculated spin densities at the hetero atoms correlate well with the experimentally determined radical cation lifetimes. Not only the Density Functional Theory (DTF) B3LYP but also the semiempirical quantum chemical model PM3 can be applied for the open shell systems mentioned.

  16. The First Example of Cation Radical Induced Ether Cleavage of Benzyl Phenyl Ether

    International Nuclear Information System (INIS)

    A thermally stable benzyl phenyl ether has been shown to cleavage under mild conditions. The new reaction described herein further expands the chemistry of the ether cleavage by cation radicals. Over the last several years, our lab has discovered cation radical-induced oxidative C-O bond cleavages such as carbonates (eq 1), carbamates (eq 2), peroxides (eq 3), and alcohols (eq 4), where R is either tert-butyl or benzyl. It was recognized from those reactions that carbocationic chemistry with C-O bond cleavages was predominant, with a 2:1 stoichiometry of Th+·:oxidized molecules

  17. A cation binding motif stabilizes the compound I radical of cytochrome c peroxidase.

    Science.gov (United States)

    Miller, M A; Han, G W; Kraut, J

    1994-11-01

    Cytochrome c peroxidase reacts with peroxide to form compound I, which contains an oxyferryl heme and an indolyl radical at Trp-191. The indolyl free radical has a half-life of several hours at room temperature, and this remarkable stability is essential for the catalytic function of cytochrome c peroxidase. To probe the protein environment that stabilizes the compound I radical, we used site-directed mutagenesis to replace Trp-191 with Gly or Gln. Crystal structures of these mutants revealed a monovalent cation binding site in the cavity formerly occupied by the side chain of Trp-191. Comparison of this site with those found in other known cation binding enzymes shows that the Trp-191 side chain resides in a consensus K+ binding site. Electrostatic potential calculations indicate that the cation binding site is created by partial negative charges at the backbone carbonyl oxygen atoms of residues 175 and 177, the carboxyl end of a long alpha-helix (residues 165-175), the heme propionates, and the carboxylate side chain of Asp-235. These features create a negative potential that envelops the side chain of Trp-191; the calculated free energy change for cation binding in this site is -27 kcal/mol (1 cal = 4.184J). This is more than sufficient to account for the stability of the Trp-191 radical, which our estimates suggest is stabilized by 7.8 kcal/mol relative to a Trp radical in solution. PMID:7972020

  18. Pulse radiolysis study of salt effects on reactions of aromatic radical cations with Cl-

    International Nuclear Information System (INIS)

    The effect of quaternary ammonium salts on the decays of the radical cations of biphenyl, trans-stilbene, anthracene and pyrene generated by pulse radiolysis in chlorohydrocarbons has been investigated. The decays, which are due to neutralization reactions with Cl-, are retarded by the addition of salts having non-nucleophilic PF6-, BF4- and ClO4-, whereas the radical cations are rapidly quenched by salts having I- and BPh4-. The retarding effect of the salts is attributed to the formation of ion pairs between the reacting ions and the counter-ions from the salts. The rate constants for the neutralization reactions in 1,2-dichloroethane have been determined for the free-ion and ion-paired states; the latter state is attained by the addition of Bu4NPF6. The rate constant determined in the absence of the salt for Pysup(radical)+ is one order of magnitude smaller than those for the others. The salt effect is also smallest on the reaction of Pysup(radical)+. The charge delocalisation of the large aromatic radical cation may be responsible for the exceptional results for Pysup(radical)+. The largest salt effect was observed on the reaction of Ph2CH+, a charge-localized carbenium ion investigated for comparison. The solvent effect on the neutralization reactions is also discussed. (author)

  19. Through-bond interaction in the radical cation of N,N-dimethylpiperazine

    DEFF Research Database (Denmark)

    Brouwer, A.M.; Langkilde, F.W.; Bajdor, K.;

    1994-01-01

    The radical cation of N,N-dimethylpiperazine is investigated by resonance Raman spectroscopy and ab initio calculations. The calculations strongly support the assignment of the vibrational spectrum to a chair conformation. It is shown that a dramatic geometry relaxation following ionization allow...

  20. Gas phase regioselectivity in the deprotonation of p-cresol radical cation

    Science.gov (United States)

    Chiavarino, B.; Crestoni, M. E.; Fornarini, S.

    2003-04-01

    The deprotonation of the radical cation of p-cresol, a model of tyrosine residues, has been studied kinetically in the gas phase. The reaction has revealed the operation of competitive deprotonation sites depending on the strength of the base, as shown by an FT-ICR study using d-labelling.

  1. Pulse radiolysis study of salt effects on reactions of aromatic radical cations with Cl-

    International Nuclear Information System (INIS)

    Pulse radiolysis of all-trans diphenyl-substituted polyenes, such as 1,4-diphenylbuta-1,3-diene, 1,6-diphenylhexa-1,3,5-triene and 1,8-diphenyl-octa-1,3,5,7-tetraene, in 1,2-dichloroethane solution has been undertaken in the absence and presence of Bu4NPF6. The absorption maxima of the diphenylpolyene radical cations are shifted to shorter wavelengths in the presence of the salt. This is evidence for the formation of the contact ion pairs between the radical cations and PF6-. The decays of the radical cations, which are due to neutralization reactions with Cl-, are retarded by the addition of the salt. The rate constants for the neutralization reactions have been determined for the free-ion and ion-paired states. The pulse radiolysis results are compared with those for other aromatic compounds such as triphenylethylene, tetraphenylethylene and perylene. The appreciable spectral shift is characteristic of the diphenylpolyene radical cations. (author)

  2. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    International Nuclear Information System (INIS)

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl4 and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN+radical) and the former to the known carbonium ion of malachite green dye (MG+). Observation of the consecutive charge transfer via the schemes: DCE+radical → BPh+radical → MGCN+radical and DCE+radical → MGCN+radical → TMPD+radical, allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV MGCN +radical radical cation is located in the ''aniline'' part of the molecule. (author)

  3. Kinetics and energetics of one-electron-transfer reactions involving tryptophan neutral and cation radicals

    International Nuclear Information System (INIS)

    Reversible one-electron-transfer reactions involving the tryptophan cation and neutral radicals were investigated by pulse radiolysis. The one-electron-reduction potential of the neutral tryptophan radical at pH 7 was determined to be E7 = 1.01 ± 0.03 V by using the bis(1,4,7-triazacyclononane)nickel(III/II) redox couple with E = 0.95 V as a standard. The value obtained with promethazine (E = 0.89 V) as a standard at pH 6 was E6 = 1.11 V. From these measurements, a mean value E7 = 1.03 V results, in agreement with some earlier determinations (1.05 and 1.08 V) obtained in experiments with inorganic redox standards. The kinetics and energetics of the reactions of the tryptophan neutral and cation radicals with selected electron donors were also investigated

  4. Electron spin resonance study of lactone radical cations formed in -irradiated freon matrices

    Energy Technology Data Exchange (ETDEWEB)

    Rideout, J.; Symons, M.C.R.; Swarts, S.; Besler, B.; Sevilla, M.D.

    1985-11-21

    Exposure of dilute solutions of a number of lactones in trichlorofluoromethane at 77 K to Co-60 -rays resulted in electron loss centers which underwent fragmentation, or complex formation with the solvent, but gave no evidence for uncomplexed primary cations. For propiolactone the authors suggest that ring opening occurs to give the .CH2CH2OCO radical cation. For US -butyrolactone fragmentation of the ring is suggested to occur. Although the cyclic four-membered rings are suggested to open or fragment their results show that the larger five-, six-, and seven-membered rings form complex cations with the freon solvent. The complexes have large chlorine couplings (A/sub max/(Cl-35) = 62-73 G) which are in accord with sigma*-bonding between an oxygen lone pair and a chlorine atom on a CFCl3 molecule. Photobleaching or annealing the complexes results in new species in which H transfer has occurred. For -butyrolactone hydrogen atom migration from one of the methylene groups to the carbonyl oxygen of the primary cation is inferred. In the case of -valerolactone the results suggest that it is the unique tertiary hydrogen atom that migrates. Similar reactions are proposed for the cations of delta-valerolactones and epsilon-caprolactone. Molecular orbital calculations at the MINDO/2 level with full geometry optimization for several lactone cation radicals and propiolactone cation's likely ring-opened product were performed and clarify the nature and identity of the radicals. The experimental results are discussed in relation to recent work on esters and other carbonyl compounds. 24 references, 5 figures, 1 table.

  5. Electron spin resonance study of lactone radical cations formed in Σ-irradiated freon matrices

    International Nuclear Information System (INIS)

    Exposure of dilute solutions of a number of lactones in trichlorofluoromethane at 77 K to Co-60 Σ-rays resulted in electron loss centers which underwent fragmentation, or complex formation with the solvent, but gave no evidence for uncomplexed primary cations. For propiolactone the authors suggest that ring opening occurs to give the .CH2CH2OCO+ radical cation. For β-butyrolactone fragmentation of the ring is suggested to occur. Although the cyclic four-membered rings are suggested to open or fragment their results show that the larger five-, six-, and seven-membered rings form complex cations with the freon solvent. The complexes have large chlorine couplings (A/sub max/(Cl-35) = 62-73 G) which are in accord with sigma*-bonding between an oxygen lone pair and a chlorine atom on a CFCl3 molecule. Photobleaching or annealing the complexes results in new species in which H transfer has occurred. For Σ-butyrolactone hydrogen atom migration from one of the methylene groups to the carbonyl oxygen of the primary cation is inferred. In the case of Σ-valerolactone the results suggest that it is the unique tertiary hydrogen atom that migrates. Similar reactions are proposed for the cations of delta-valerolactones and epsilon-caprolactone. Molecular orbital calculations at the MINDO/2 level with full geometry optimization for several lactone cation radicals and propiolactone cation's likely ring-opened product were performed and clarify the nature and identity of the radicals. The experimental results are discussed in relation to recent work on esters and other carbonyl compounds. 24 references, 5 figures, 1 table

  6. Formation of OH radicals from radical cations of some substituted benzenes in aqueous solutions at 800 C and at room temperature: effect of oxygen

    International Nuclear Information System (INIS)

    The reactions of a number of simple substituted-benzene radical cations with water at 800 C and at room temperature have been investigated. The radical cations were produced by thermal decomposition of Na2S2O8. The authors searched for the formation of OH radicals, which they identified by their reaction with nitrobenzene to give nitrophenols. The thermal decomposition of peroxydisulfate in deoxygenated, nitrobenzene-saturated aqueous solutions of chlorobenzene, bromobenzene, and tert-butylbenzene gave o- and p-nitrophenols, whereas fluorobenzene, iodobenzene, phenol, and chlorophenols gave no nitrophenols. With nitrobenzene alone, no nitrophenols were obtained. The structural requirements for the reaction of aromatic radical cations with water to produce OH radicals are discussed. In the presence of oxygen, the yield of chlorophenols and bromophenols increased dramatically, producing mainly the para isomer, but in the bromobenzene case also significant amounts of m-bromophenol. The mechanism of this oxidation is discussed. 3 tables

  7. The role of organic solvent radical cations in separations ligand degradation

    International Nuclear Information System (INIS)

    The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/ absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M-1s-1 in dodecane/0.10 M CH2Cl2 solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre-contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO·HNO3 complex formed in the acid contacted solvent. (author)

  8. Efficient scavenging of β-carotene radical cations by antiinflammatory salicylates

    DEFF Research Database (Denmark)

    Cheng, Hong; Liang, Ran; Han, Rui-Min;

    2014-01-01

    by the anion of salicylic acid with 2.2 × 10 L mol s, but still of possible importance for light-exposed tissue. Surprisingly, acetylsalicylate, the aspirin anion, reacts with an intermediate rate in a reaction assigned to the anion of the mixed acetic-salicylic acid anhydride formed through base induced......The radical cation generated during photobleaching of β-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k = 3.2 × 10 L mol s in 9:1 v/v chloroform-methanol at 23 °C, less efficiently...... rearrangements. The relative scavenging rate of the β-carotene radical cation by the three salicylates is supported by DFT-calculations. © 2014 The Royal Society of Chemistry....

  9. Electronic structures, vibrational spectra, and revised assignment of aniline and its radical cation: Theoretical study

    Science.gov (United States)

    Wojciechowski, Piotr M.; Zierkiewicz, Wiktor; Michalska, Danuta; Hobza, Pavel

    2003-06-01

    Comprehensive studies of the molecular and electronic structures, vibrational frequencies, and infrared and Raman intensities of the aniline radical cation, C6H5NH2+ have been performed by using the unrestricted density functional (UB3LYP) and second-order Møller-Plesset (UMP2) methods with the extended 6-311++G(df,pd) basis set. For comparison, analogous calculations were carried out for the closed-shell neutral aniline. The studies provided detailed insight into the bonding changes that take place in aniline upon ionization. The natural bond orbital (NBO) analysis has revealed that the pπ-radical conjugative interactions are of prime importance in stabilizing the planar, quinoid-type structure of the aniline radical cation. It is shown that the natural charges calculated for aniline are consistent with the chemical properties of this molecule (an ortho- and para-directing power of the NH2 group in electrophilic substitutions), whereas Mulliken charges are not reliable. The theoretical vibrational frequencies of aniline, calculated by the B3LYP method, show excellent agreement with the available experimental data. In contrast, the MP2 method is deficient in predicting the frequencies of several modes in aniline, despite the use of the extended basis set in calculations. The frequencies of aniline radical cation, calculated at the UB3LYP/6-311++G(df,pd) level, are in very good agreement with the recently reported experimental data from zero kinetic energy photoelectron and infrared depletion spectroscopic studies. The clear- cut assignment of the IR and Raman spectra of the investigated molecules has been made on the basis of the calculated potential energy distributions. Several bands in the spectra have been reassigned. It is shown that ionization of aniline can be easily identified by the appearance of the very strong band at about 1490 cm-1, in the Raman spectrum. The redshift of the N-H stretching frequencies and the blueshift of the C-H stretching

  10. The lightest organic radical cation for charge storage in redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jinhua; Pan, Baofei; Duan, Wentao; Wei, Xiaoliang; Assary, Rajeev S.; Su, Liang; Brushett, Fikile; Cheng, Lei; Liao, Chen; Ferrandon, Magali S.; Wang, Wei; Zhang, Zhengcheng; Burrell, Anthony K.; Curtiss, Larry A.; Shkrob, Ilya A.; Moore, Jeffrey S.; Zhang, Lu

    2016-08-25

    Electrochemically reversible fluids of high energy density are promising materials for capturing the electrical energy generated from intermittent sources like solar and wind. To meet this technological challenge there is a need to understand the fundamental limits and interplay of electrochemical potential, stability and solubility in “lean” derivatives of redox-active molecules. Here we describe the process of molecular pruning, illustrated for 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene, a molecule known to produce a persistently stable, high-potential radical cation. By systematically shedding molecular fragments considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form. Interestingly, we find the tert-butyl groups are unnecessary; high stability of the radical cation and high solubility are both realized in derivatives having appropriately positioned arene methyl groups. These stability trends are rationalized by mechanistic considerations of the postulated decomposition pathways. We suggest that the molecular pruning approach will uncover lean redox active derivatives for electrochemical energy storage leading to materials with long-term stability and high intrinsic capacity.

  11. Electronic structures of one-dimensional poly-fused selenophene radical cations: density functional theory study

    Directory of Open Access Journals (Sweden)

    Hiroshi Kawabata et al

    2008-01-01

    Full Text Available Hybrid density functional theory (DFT calculations have been carried out for neutral and radical cation species of a fused selenophene oligomer, denoted by Se(n, where n represents the number of selenophene rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused selenophene was also investigated using one-dimensional periodic boundary conditions (PBC for comparison. It was found that the reorganization energy of a radical cation of Se(n from a vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that Se(n has an effective intramolecular hole transport property. It was found that the radical cation species of Se(n has a low-energy band in the near-IR region, which is strongly correlated to hole conductivity. The relationship between the electronic states and intramolecular hole conductivity was discussed on the basis of theoretical calculations.

  12. Influence of orally taken carotenoids on the antioxidative status of the skin, the radical protection function of the skin and the skin lipids

    OpenAIRE

    Friedrich, Annette

    2015-01-01

    In this work, the bioavailability and the antioxidant effect of orally administered carotenoids on the skin were examined. For this purpose different spectroscopic methods were used. A double-blind placebo-controlled study was conducted in 22 subjects over a time period of 20 weeks. The aim of this work was to develop an in vivo method to enable studying the antioxidative and protective effects of naturally occurring antioxidants against radical formation by visible and near infrared (Vi...

  13. ESR studies of ion-molecule reactions of ether, thioether, and olefin radical cations in the CF2ClCFCl2 matrix

    International Nuclear Information System (INIS)

    Several ion-molecule reactions of radical cations with their corresponding neutral molecules have been studied by ESR spectroscopy. These reactions were observed at low temperatures (80-130 K) in a mobile halocarbon matrix following the radiolytic generation of the radical cations from dilute solutions of the parent compound at 77 K. Ether and thioether radical cations react to produce neutral carbon-centered radicals with high regiospecificity, only the oxetan-2-yl radical being detected in the oxetane (trimethylene oxide) system, while the THF-2-yl species is produced in greater abundance than the THF-3-yl species from tetrahydrofuran (THF). The mechanism of these reactions is discussed in terms of either proton transfer from the radical cation or hydrogen atom transfer from the neutral molecule. For dimethyl sulfide, the dimer radical cation is observed prior to the formation of the sup(·)CH2SMe radical. Similarly, the tetramethylethylene radical cation first forms the dimer radical cation which then undergoes a unimolecular reaction to give the 1,1,2-trimethylallyl radical. This is demonstrated by the fact that these two consecutive reactions can be observed separately rather than simultaneously by carefully controlled annealing, the dimer radical cation of tetramethylethylene being formed in high yield from the monomer cation before decomposing to the 1,1,2-trimethylallyl radical. (author)

  14. Charge transfer from the n-hexadecane radical cation to cycloalkanes, alkenes and aromatics

    International Nuclear Information System (INIS)

    Charge transfer from n-hexadecane radical cations C16H34+ to solutes as cycloalkanes, alkenes and aromatics was studied by pulse radiolysis. Using ion-pair kinetics the rate constants ksub(s) of the electron transfer reactions C16H34+ + S ->sup(ks) S+ + C16H34 were determined. The electron transfer rate constants ksub(s) increase from low values for slightly exothermic reactions to a limiting value of 9 . 109 dm3 mol-1 s-1 when the electron transfer reaction is more exothermic than -0.4 eV. (orig.)

  15. Enantiopure Radical Cation Salt Based on Tetramethyl-Bis(ethylenedithio-Tetrathiafulvalene and Hexanuclear Rhenium Cluster

    Directory of Open Access Journals (Sweden)

    Flavia Pop

    2016-01-01

    Full Text Available Electrocrystallization of the (S,S,S,S enantiomer of tetramethyl-bis(ethylenedithio-tetrathiafulvalene donor 1 in the presence of the dianionic hexanuclear rhenium (III cluster [Re6S6Cl8]2− affords a crystalline radical cation salt formulated as [(S-1]2·Re6S6Cl8, in which the methyl substituents of the donors adopt an unprecedented all-axial conformation. A complex set of intermolecular TTF···TTF and cluster···TTF interactions sustain an original tridimensional architecture.

  16. Spin-coupling in ferric metalloporphyrin radical cation complexes: Mössbauer and susceptibility studies

    Science.gov (United States)

    Lang, George; Boso, Brian; Erler, Brian S.; Reed, Christopher A.

    1986-03-01

    The ferric metalloporphyrin π-radical cation complexes Fe(III) (OClO3)2 (TPP.) and [Fe(III) Cl (TPP.)] [SbCl6] were examined in microcrystalline form by Mössbauer spectroscopy and magnetic susceptometry over a range of temperatures and applied fields. All measurements on the six-coordinate Fe(OClO3)2 (TPP.) were consistent with isolated molecules having an S=5/2 iron site with zero field splitting (12 cm-1) S2z that is ferromagnetically coupled to the S=1/2 porphyrin radical by an energy term (-110 cm-1) Sṡs. Thus the ground state is overall spin-3. In the five-coordinate [FeCl (TPP.)] [SbCl6] the susceptibility is in reasonable agreement with the results of a calculation based on zero field splitting (12 cm-1) S2z for the S=5/2 iron and antiferromagnetic coupling (200 cm-1) Sṡs with the radical to give an overall spin-2 ground state. However, the Mössbauer measurements require a more complicated model having the same large intramolecular iron-radical coupling, a smaller zero field splitting (3 cm-1) S2z, and weak intermolecular antiferromagnetic coupling between heme pairs given by (32 cm-1) s1ṡs2 or, equivalently, (0.65 cm-1) S1ṡS2. A slightly improved correspondence with the measured susceptibility results. The intermolecular antiferromagnetic coupling probably results from crystallization of the [FeCl (TPP.)]+ cations in face-to-face dimers as observed in other closely related five-coordinate iron (III) porphyrins.

  17. A DFT study on the deprotonation antioxidant mechanistic step of ortho-substituted phenolic cation radicals

    International Nuclear Information System (INIS)

    The conformers of the 2-, 3- and 4-substituted phenolic cation radicals, 2-X-, 3-X- and 4-X-ArOH ·+, and the respective phenoxyl radicals, ArO ·, the intramolecular hydrogen bond strength (ΔH intra) estimate along with the electronic effects of five electron withdrawing (EWG) and eight electron donating groups (EDG) on the gas-phase O-H proton dissociation enthalpies, (PDEs), of the short-lived, 2-X-ArOH ·+, (involved in the single-electron transfer antioxidant mechanism), are studied at the DFT/B3LYP level of theory. EWG result to smaller PDEs, hence to stronger acidity; EDG to weaker acidity. The deprotonation antioxidant mechanistic step is not a rate-controlling step for 2-X-ArOH to scavenge free radicals. Approximate estimations of the ΔPDEs (hence acidities as well) can be derived from calculated structural and/or vibrational frequency values. ΔH intras correlate reasonably with geometrical parameters for the closed-shell, neutral counterparts, in contrast with previous estimates

  18. Single-Crystal X-ray Structures of conductive π-Stacking Dimers of Tetrakis(alkylthio)benzene Radical Cations

    Science.gov (United States)

    Chen, Xiaoyu; Gao, Feng; Yang, Wuqin

    2016-07-01

    Salts containing radical cations of 1,2,4,5-tetrakis(isopropylthio)benzene (TPB) and 1,2,4,5-tetrakis(ethylthio) benzene (TEB) have been successfully synthesized with . These newly synthesized salts have been characterized by UV-Vis absorption, EPR spectroscopy, conductivity measurement, single crystal X-ray diffraction analysis as well as DFT calculation. This study raises the first crystal structure of conductive π-stacking radical cation with single phenyl ring and reveals their conductivity has relationship with the stack structure which affected by the substituent.

  19. l-Tryptophan Radical Cation Electron Spin Resonance Studies: Connecting Solution-derived Hyperfine Coupling Constants with Protein Spectral Interpretations

    OpenAIRE

    Connor, Henry D.; Sturgeon, Bradley E.; Mottley, Carolyn; Sipe, Herbert J.; Mason, Ronald P.

    2008-01-01

    Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce4+ in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support expe...

  20. NF3+ radical cation. Electron spin resonance studies of radiation effects in NF4+ salts

    International Nuclear Information System (INIS)

    Exposure of NF4+AsF6- and NF4+ SbF6- . 0.8SbF5 to 60Co γ rays at 770K gave two paramagnetic centers, one of which is shown by ESR spectroscopy to contain one nitrogen atom and three equivalent fluorine atoms. Based on its magnetic properties it is identified as pyramidal NF3+, a novel radical cation. The other center exhibits strong interaction of the electron with two fluorine atoms, weaker interaction with the antimony or arsenic central atom, and small interaction with several other fluorine atoms. It is tentatively assigned to the electron-loss species AsF6, SbF6, or Sb2F11 with the unpaired electron largely confined to two fluorine ligands. Irradiation of NF4+BF4- did not result in well-defined magnetic centers. An improved synthesis of NF4+BF4- is reported. (U.S.)

  1. Photochemical Production of Interpenetrating Polymer Networks; Simultaneous Initiation of Radical and Cationic Polymerization Reactions

    Directory of Open Access Journals (Sweden)

    Jean Pierre Fouassier

    2014-10-01

    Full Text Available In this paper, we propose to review the ways to produce, through photopolymerization, interpenetrating polymer networks (IPN based, e.g., on acrylate/epoxide or acrylate/vinylether blends and to outline the recent developments that allows a one-step procedure (concomitant radical/cationic polymerization, under air or in laminate, under various irradiation conditions (UV/visible/near IR; high/low intensity sources; monochromatic/polychromatic sources; household lamps/laser diodes/Light Emitting Diodes (LEDs. The paper illustrates the encountered mechanisms and the polymerization profiles. A short survey on the available monomer systems and some brief examples of the attained final properties of the IPNs is also provided.

  2. Aqueous oxidation of sulfonamide antibiotics: aromatic nucleophilic substitution of an aniline radical cation.

    Science.gov (United States)

    Tentscher, Peter R; Eustis, Soren N; McNeill, Kristopher; Arey, J Samuel

    2013-08-19

    Sulfonamide antibiotics are an important class of organic micropollutants in the aquatic environment. For several, sulfur dioxide extrusion products have been previously reported upon photochemical or dark oxidation. Using quantum chemical modeling calculations and transient absorption spectroscopy, it is shown that single-electron oxidation from sulfadiazine produces the corresponding aniline radical cation. Density functional theory calculations indicate that this intermediate can exist in four protonation states. One species exhibits a low barrier for an intramolecular nucleophilic attack at the para position of the oxidized aniline ring, in which a pyrimidine nitrogen acts as a nucleophile. This attack can lead to a rearranged structure, which exhibits the same connectivity as the SO2 -extruded oxidation product that was previously observed in the aquatic environment and characterized by NMR spectroscopy. We report a detailed reaction mechanism for this intramolecular aromatic nucleophilic substitution, and we discuss the possibility of this reaction pathway for other sulfonamide drugs. PMID:23828254

  3. The first BETS radical cation salts with dicyanamide anion: Crystal growth, structure and conductivity study

    International Nuclear Information System (INIS)

    Electrochemical oxidation of bis(ethylenedithio)tetraselenafulvalene (BETS) has been investigated. Simple and complex dicyanamides of transition metals (Mn2+, Ni2+ and Fe2+) were used as electrolytes. The correlation between composition of prepared radical cation salts and metal nature in electrolytes was established. Manganese dicyanamides provide the formation of BETS salts with the {Mn[N(CN)2]3}- and [N(CN)2]-XH2O anions. When Ni- or Fe-containing electrolytes were used only metalless BETS salts, α''-BETS2[N(CN)2].2H2O (I) and θ-BETS2[N(CN)2].3.6H2O (II), formed. Structures and conducting properties of these salts were analyzed. Both salts exhibit layered structure. Conducting radical cation layers have α'' (I)- or θ-type (II). Anion sheets appear as two-dimensional polymer networks of different types. These networks are formed by [N(CN)]2- anions and water molecules interlinked by hydrogen bonds. Salt I is a semiconductor and II demonstrates resistance drop down to150 K at normal pressure and down to 72 K at ∼0.4 kbar pressure. - Graphical abstract: We studied electrochemical oxidation of BETS donor in the presence of simple and/or complex dicyanamides of transition metals (Ni, Fe, Mn) as electrolytes. New conducting salts α''-BETS2[N(CN)2].2H2O and θ-BETS2[N(CN)2].3.8H2O have been synthesized and characterized. Highlights: → We studied electrochemical oxidation of BETS donor. → Dicyanamides of transition metals (Ni, Fe, Mn) were used as electrolytes. → We found a well-reproducible synthesis of magnetic superconductor BETS2Mn[N(CN)2]3. → Two new metalless BETS salts form when Ni and Fe electrolytes were used. → Their structure and conductivity were investigated.

  4. Efficient production of aromatic cation radicals by irradiation with visible light. Utilization of 60C as photocatalyst

    International Nuclear Information System (INIS)

    Complete text of publication follows. Photoinduced electron transfer reactions of fullerenes have of widespread interest because of their potential application in the initiation of chemical processes. The high stability, broad range of visible absorption of 60C as well as the efficient formation and long lifetime of the triplet excited state facilitate its implementation as light harvester. The remarkable ability of the 60C to accept electron have stimulated a number of studies, however, the data concerning the participation of the triplet 60C as electron donor are scarce and formation of 60C+ cation radical has not been detected in photoinduced reactions with strong electron acceptors such as tetracyanoethylene tetracyanoquinodimethane or chloranil. We now report a laser flash photolysis study of triplet 60C quenching by chloranil and demonstrate that addition of trifluoroacetic acid (TFA) results in several orders of magnitude increase in reaction rate. The large rate enhancement is attributed to development of a local polar environment by the preferential solvation of chloranil with TFA. 60C+ cation radical and semiquinone radical are clearly identified as reaction products. The quantum yield of radical formation is found to be as high as 0.80 in the presence of 0.5 M TFA indicating that the efficient protonation of the chloranil radical anion, formed in the primary electron transfer, competes effectively with the back electron transfer process. Because of its high oxidation potential (1.76 V vs. SCE in benzonitrile) 60C+ cation radical readily oxidizes aromatic compounds e.g. fluoranthene, naphthalene derivatives in secondary electron transfer process. Therefore, 60C is a very efficient photocatalyst for production of aromatic cation radicals by irradiation with visible light

  5. Sequential synthesis of methyl methacrylate, styrene and isobutylene pentablock copolymers by atom transfer radical and cationic polymerization

    Czech Academy of Sciences Publication Activity Database

    Janata, Miroslav; Toman, Luděk; Vlček, Petr; Spěváček, Jiří; Látalová, Petra; Masař, Bohumil; Sikora, Antonín

    Goa : International Union of Pure and Applied Chemistry, 2005. s. 101. [International Symposium on Ionic Polymerization. 23.10.2005-28.10.2005, Goa ] R&D Projects: GA ČR GA203/04/1050 Keywords : block copolymers * atom transfer radical polymerization * cationic polymerization Subject RIV: CD - Macromolecular Chemistry

  6. Direct observation of hexamethylbenzenium radical cations generated during zeolite methanol-to-olefin catalysis: an ESR study.

    Science.gov (United States)

    Kim, Sun Jung; Jang, Hoi-Gu; Lee, Jun Kyu; Min, Hyung-Ki; Hong, Suk Bong; Seo, Gon

    2011-09-01

    The generation of hexamethylbenzenium radical cations as the key reaction intermediate in chabazite-type molecular sieve acids (i.e., H-SAPO-34 and H-SSZ-13) during the methanol-to-olefin process has been directly evidenced by ESR spectroscopy. PMID:21766115

  7. Kinetics of ABTS derived radical cation scavenging by bucillamine, cysteine, and glutathione. Catalytic effect of Cu(2+) ions.

    Science.gov (United States)

    Valent, Ivan; Topoľská, Dominika; Valachová, Katarína; Bujdák, Juraj; Šoltés, Ladislav

    2016-05-01

    Kinetics of reduction of the stable radical cation derived from 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) in reaction with the anti-rheumatic drug bucillamine (BUC) and two reference thiols - cysteine (Cys) and glutathione (GSH) was followed spectrophotometrically in acidic medium with 10-fold molar excess of the reductant. Decay of the radical is governed by pseudo-first order kinetics with small deviation in the case of GSH. H(+) ions displayed second order inhibition of the reaction with all the studied compounds. The reaction of BUC exhibits zero order kinetics to the radical at lower acidities with a moderate acceleration of the reaction rate by H(+) ions. A significant catalytic effect of Cu(2+) ions on the reactions with all the reductants was observed. The most sensitive to Cu(2+)-catalysis was the reaction of BUC with the radical cation, while Cu(2+) ions showed much lower effect on the reaction with GSH. The presence of EDTA strongly inhibited the reactions and equalized the reaction rates for all the reductants. A Cu(I) selective chelator bathocuproine disulfonate reduced the reaction rate with Cys, but accelerated the reaction with BUC at the lower acidities. The experimental results were rationalized in the framework of the mechanism of reductive chelation. The conclusions may have important consequences for interpretation of antioxidant capacity assays, such as TEAC, utilizing the ABTS derived radical cation. PMID:26978549

  8. Reaction of carotenoids with CCl3OO· by using pulse radiolysis

    Institute of Scientific and Technical Information of China (English)

    赵文恩; 姚思德; 王强; 钱素平; 王文峰; 韩雅珊

    2003-01-01

    The interactions of carotenoids (bixin, β-carotene and lycopene) with CCl3OO@ in aqueous and i-propylalcohol solution saturated with air have been studied by pulse radiolysis. For bixin and β-carotene reaction products from forming process, absorbing in the region of 650 nm, is observed with concomitant carotenoid bleaching (bixin at 500 nm, β-carotene at 450 nm). Their rate constants from forming process are 1.78×108 and 7.8×107 mol-1@L@s-1 respectively. However, in the case of lycopene, no such a forming process of reaction as bixin and β-carotene can be observed although there is the bleaching reaction (rate constant 4×107 mol-1@L@s-1). The results suggest that the carotenoid radical cationand an additional radical are produced in the case of bixin and β-carotene, whereas lycopene undergoes electron transfer with CCl3OO@, forming cation radical.

  9. EPR at 24 T of the primary donor radical cation from Blastochloris viridis

    International Nuclear Information System (INIS)

    The g-matrix of photosynthetic pigments has been studied in the last decade due to the advent of high-field EPR techniques. It can be observed when the spectral splitting of the principal g-factor components is larger than the linewidth due to unresolved hyperfine splitting and if there is no g-strain obscuring it. For large organic molecules such as the primary electron donor in photosynthetic reaction centers (RC) this usually requires fields above 11 T, or, for fields between 3 and 11 T, full deuteration and/or single crystal work. Here we present for the first time the fully resolved rhombic EPR spectrum of the primary donor of Blastochloris viridis (formerly called Rhodopseudomonas viridis), a purple photosynthetic bacterium containing bacteriochlorophyll b. As was the case for Rhodobacter sphaeroides, g-strain is negligible for this radical up to a field of 24 T. The temperature dependence of the g-anisotropy is presented and compared with that of the bacteriochlorophyll a-containing Rb. sphaeroides and plant photosystem I. A slight shift in the principal components of the g-matrix is observed at temperatures below 70 K, where it becomes more axial. The experimental work is complemented with theoretical calculations for g using the semi-empirical INDO/S method as implemented in the program ZINDO. The theoretical results generally agree well with the experiment. This indicates that a satisfactory description of the anisotropic g-tensor for radical cations of large planar molecules like the chlorophylls as well as their aggregates, e.g., reaction center primary donor special pairs, is possible with this relatively cheap semi-empirical approach

  10. Electron-transfer reactions between viologen radical cations and quinones in AOT reverse micelles studied by electron pulse radiolysis

    International Nuclear Information System (INIS)

    Electron-transfer reactions between viologen radical cations (CnVsm-bullet+, n = 1-18) and various quinones have been studied in aqueous and reverse micellar (AOT/isooctane/H2O) solution by use of the electron pulse radiolysis technique. By use of dynamic light scattering measurements, the concentration of water pools was determined and the number of electron-transfer reactants per water pool could be calculated. Rate constants measured for the reaction between CnVsm-bullet+ radicals and anthraquinonesulfonate ions (AQS-) decreased with increasing length of the aliphatic chain of the viologens, caused by association of the viologen with the surfactant interface

  11. One-electron oxidation of chlorophyll a and (tetraphenylporphyrinato)cobalt(II) by various metalloporphyrin cation radicals. Kinetic spectrophotometric studies

    International Nuclear Information System (INIS)

    One-electron oxidations of various metalloporphyrins in dichloroethane solutions were studied by kinetic spectrophotometric pulse radiolysis. Co/sup II/TPP (TPP = tetraphenylporphyrin) was found to produce Co/sup III/TPP while the Cd(II), Cu(II), Pb(II), and VO complexes, like the ZnTPP and MgTPP, yield the cation radicals. Ni/sup II/TPP is oxidized at the metal center in the presence of pyridine but at the ligand in its absence. The subsequent one-electron oxidation of chlorophyll a and Co/sup II/TPP by the above cation radicals was also followed. The rate constants for these reactions were found to be mostly in the range of 3 x 108-5 x 108 M-1 s-1, much lower than the expected diffusion-controlled rates

  12. Formation of radical cations and dose response of alpha-terthiophene-cellulose triacetate films irradiated by electrons and gamma rays

    CERN Document Server

    Emmi, S S; Ceroni, P; D'Angelantonio, M; Lavalle, M; Fuochi, P G; Kovács, A

    2002-01-01

    The radiation-induced UV-vis spectrum of alpha-terthiophene radical cation in solid is reported. The radical cation initiates an oligomerization in the CTA matrix producing permanently coloured conjugated polarons. The specific net absorbance at 465 nm is linearly related with dose up to 2x10 sup sup 6 sup sup G y, for electrons and gamma irradiation. The decrease of the UV typical absorption (355 nm) and of four IR bands of alpha-terthiophene is linear with dose, as well. Although sensitivity is influenced by dose rate, it turned out that a linear relationship holds between sensitivity and log dose rate, in the range from 2 to 10 sup sup 5 Gy, min. These findings suggest a potential application of the system for dosimetric purposes over a wide range of dose and dose rate.

  13. Multistep π dimerization of tetrakis(n-decyl)heptathienoacene radical cations: a combined experimental and theoretical study.

    Science.gov (United States)

    Ferrón, Cristina Capel; Capdevila-Cortada, Marçal; Balster, Russell; Hartl, František; Niu, Weijun; He, Mingqian; Novoa, Juan J; López Navarrete, Juan T; Hernández, Víctor; Ruiz Delgado, M Carmen

    2014-08-11

    Radical cations of a heptathienoacene α,β-substituted with four n-decyl side groups (D4T7(.) (+) ) form exceptionally stable π-dimer dications already at ambient temperature (Chem. Comm. 2011, 47, 12622). This extraordinary π-dimerization process is investigated here with a focus on the ultimate [D4T7(.) (+) ]2 π-dimer dication and yet-unreported transitory species formed during and after the oxidation. To this end, we use a joint experimental and theoretical approach that combines cyclic voltammetry, in situ spectrochemistry and spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The impact of temperature, thienoacene concentration, and the nature and concentration of counteranions on the π-dimerization process is also investigated in detail. Two different transitory species were detected in the course of the one-electron oxidation: 1) a different transient conformation of the ultimate [D4T7(.) (+) ]2 π-dimer dications, the stability of which is strongly affected by the applied experimental conditions, and 2) intermediate [D4T7]2 (.) (+) π-dimer radical cations formed prior to the fully oxidized [D4T7]2 (.) (+) π-dimer dications. Thus, this comprehensive work demonstrates the formation of peculiar supramolecular species of heptathienoacene radical cations, the stability, nature, and structure of which have been successfully analyzed. We therefore believe that this study leads to a deeper fundamental understanding of the mechanism of dimer formation between conjugated aromatic systems. PMID:25043826

  14. Carotenoid Distribution in Nature.

    Science.gov (United States)

    Alcaíno, Jennifer; Baeza, Marcelo; Cifuentes, Víctor

    2016-01-01

    Carotenoids are naturally occurring red, orange and yellow pigments that are synthesized by plants and some microorganisms and fulfill many important physiological functions. This chapter describes the distribution of carotenoid in microorganisms, including bacteria, archaea, microalgae, filamentous fungi and yeasts. We will also focus on their functional aspects and applications, such as their nutritional value, their benefits for human and animal health and their potential protection against free radicals. The central metabolic pathway leading to the synthesis of carotenoids is described as the three following principal steps: (i) the synthesis of isopentenyl pyrophosphate and the formation of dimethylallyl pyrophosphate, (ii) the synthesis of geranylgeranyl pyrophosphate and (iii) the synthesis of carotenoids per se, highlighting the differences that have been found in several carotenogenic organisms and providing an evolutionary perspective. Finally, as an example, the synthesis of the xanthophyll astaxanthin is discussed. PMID:27485217

  15. On the time behaviour of the concentration of pyrazinium radical cations in the early stage of the Maillard reaction

    Science.gov (United States)

    Stoesser, Reinhard; Klein, Jeannette; Peschke, Simone; Zehl, Andrea; Cämmerer, Bettina; Kroh, Lothar W.

    2007-08-01

    During the early stage of the Maillard reaction pyrazinium radical cations were detected by ESR within the reaction system D-glucose/glycine. The spectra were characterized by completely resolved hyperfine structure. The partial pressure of oxygen and the radical concentrations were measured directly in the reaction mixture by ESR using solutions of the spin probe TEMPOL and of DPPH, respectively. There are quantitative and qualitative relations of the actual concentration of the radical ions to the partial pressure of oxygen, the temperature-time regime and the mechanical mixing of the reaction system. These macroscopic parameters significantly affect both the induction period and the velocity of the time-dependent formation of free radicals. From in situ variations of p(O 2) and p(Ar) including the connected mixing effects caused by the passing the gases through the reaction mixture, steric and chemical effects of the stabilization of the radical ions were established. The determination of suitable and relevant conditions for stabilization and subsequent radical reactions contributes to the elucidation of the macroscopically known antioxidant activity of Maillard products.

  16. A cation binding motif stabilizes the compound I radical of cytochrome c peroxidase.

    OpenAIRE

    Miller, M.A.; Han, G W; Kraut, J

    1994-01-01

    Cytochrome c peroxidase reacts with peroxide to form compound I, which contains an oxyferryl heme and an indolyl radical at Trp-191. The indolyl free radical has a half-life of several hours at room temperature, and this remarkable stability is essential for the catalytic function of cytochrome c peroxidase. To probe the protein environment that stabilizes the compound I radical, we used site-directed mutagenesis to replace Trp-191 with Gly or Gln. Crystal structures of these mutants revealed...

  17. The loss of NH2O from the N-hydroxyacetamide radical cation CH3C(O)NHOH+

    Science.gov (United States)

    Jobst, Karl J.; Burgers, Peter C.; Ruttink, Paul J. A.; Terlouw, Johan K.

    2006-08-01

    A previous study [Ch. Lifshitz, P.J.A. Ruttink, G. Schaftenaar, J.K. Terlouw, Rapid Commun. Mass Spectrom. 1 (1987) 61] shows that metastable N-hydroxyacetamide ions CH3C(O)NHOH+ (HA-1) do not dissociate into CH3CO+ + NHOH by direct bond cleavage but rather yield CH3CO+ + NH2OE The tandem mass spectrometry based experiments of the present study on the isotopologue CH3C(O)NDOD+ reveal that the majority of the metastable ions lose the NH2O radical as NHDO rather than ND2O. A mechanistic analysis using the CBS-QB3 model chemistry shows that the molecular ions HA-1 rearrange into hydrogen-bridged radical cations [OCC(H2)H...N(H)OH]+ whose acetyl cation component then catalyses the transformation NHOH --> NH2O prior to dissociation. The high barrier for the unassisted 1,2-H shift in the free radical, 43 kcal mol-1, is reduced to a mere 7 kcal mol-1 for the catalysed transformation which can be viewed as a quid-pro-quo reaction involving two proton transfers.

  18. Lycopene as A Carotenoid Provides Radioprotectant and Antioxidant Effects by Quenching Radiation-Induced Free Radical Singlet Oxygen: An Overview

    Directory of Open Access Journals (Sweden)

    Jalil Pirayesh Islamian

    2015-01-01

    Full Text Available Radio-protectors are agents that protect human cells and tissues from undesirable ef - fects of ionizing radiation by mainly scavenging radiation-induced free radicals. Although chemical radio-protectors diminish these deleterious side effects they induce a number of unwanted effects on humans such as blood pressure modifications, vomiting, nausea, and both local and generalized cutaneous reactions. These disadvantages have led to emphasis on the use of some botanical radio-protectants as alternatives. This review has collected and organized studies on a plant-derived radio-protector, lycopene. Lycopene protects normal tissues and cells by scavenging free radicals. Therefore, treatment of cells with lycopene prior to exposure to an oxidative stress, oxidative molecules or ion - izing radiation may be an effective approach in diminishing undesirable effects of radia - tion byproducts. Studies have designated lycopene to be an effective radio-protector with negligible side effects.

  19. Study of transitory forms of carotenoids

    International Nuclear Information System (INIS)

    In order to explain the biological role of the carotenoids their transitory forms were studied with an apparatus measuring the small (∼10-3) short-lived (100 ns to 1 ms) optical density variations obtained by excitation with a ruby laser. Two forms were studied: a) Triplet state 3Car. - This state (t1/2∼6 μs) is obtained not by direct excitation but by T-T energy transfer from chlorophyll, in different media (chloroplasts, pigments in solution or in micelle). Two arguments can be advanced to explain in terms of triplet energy transfer an essential biological role of carotenoids, protection against photodynamic effects: - the energy level of 3Car is lower than that of the singlet of oxygen; - in vivo the T-T transfer from chlorophyll to the carotenoids is very fast: 30 ns.. b) Radical cation Car+. - This form is obtained by electron transfer from carotene to the triplet of Toluidine Blue, in ethanol. Car+ (t1/2∼200 μs) shows a strong absorption band at 910 nm. The properties of Car+ are discussed in relation to other polyene derivatives and to hydrocarbon ions. Car+ could be involved in certain biological electron transfers. (author)

  20. ESR investigation of ester π-cation radicals in a freon matrix at low temperatures: evidence for unusual barriers to methyl group rotation and intramolecular bonding

    International Nuclear Information System (INIS)

    γ-Irradiation of dilute solutions of a number of esters in CFCl3 at 77 K is shown by ESR spectroscopy to produce the π-cation radicals of these molecules. The π-cations formed are those of the methyl and ethyl formates, acetates, and propionates. Larger esters containing propyl and butyl side chains are suggested to be unstable toward deprotonation at 77 K. Synthesis of deuterium-labeled compounds was employed to assign proton hyperfine couplings to specific sites in the π-cation radicals. The π-cations of the ethyl esters show unusually large couplings to the terminal methyl groups. In addition, large barriers to methyl group rotation are found for both the methyl and ethyl ester cation radicals. The large barriers suggest intermolecular bonding between the alkyl group and the carbonyl oxygen in the ester functional group. Such a hypothesis is supported by the finding of a torsional motion in the terminal methyl group of ethyl formate π-cation which has a ca. 1.7 kcal/mol activation energy barrier. It is suggested that a new intramolecular π*-bond is responsible for the formation of cyclic rings in the methyl- and ethyl-substituted ester cation radicals

  1. Electrochemical Behavior of meso-Substituted Porphyrins: The Role of Cation Radicals to the Half-Wave Oxidation Potential Splitting.

    Science.gov (United States)

    Tran, Thai T H; Chang, Yan-Ru; Hoang, Tuan K A; Kuo, Ming-Yu; Su, Yuhlong O

    2016-07-21

    In this study, the electrochemical behavior of free base and zinc meso-substituted porphyrins is examined by cyclic voltammetry (CV) and density functional theory (DFT). The results show that the half-wave oxidation potential splitting of the two oxidation states (ΔE= second E1/2 - first E1/2) of tetraphenylporphyrin (H2TPP) and its zinc complex (ZnTPP) are higher than those of porphyrins and their zinc complexes with meso-substituted five-membered heterocylic rings. The ΔE values follow the trend of TPP > T(3'-thienyl)P > T(3'-furyl)P > T(2'-thienyl)P for both meso-porphyrins and their respective zinc complexes. By employing DFT calculations, we have found that the trend of ΔE values is consistent with that of highest spin density (HSD) distribution and HOMO-LUMO energy gaps of cationic radicals as well as the π-conjugation between central porphyrin and meso-substituted rings. Also, they exhibit the better resonance between the porphyrin ring with meso-substituted rings as moving from porphyrins and their zinc complexes with phenyl rings to five-membered heterocyclic rings. A good agreement between calculated and experimental results indicates that cationic radicals, especially their spin density distribution, do play an important role in half-wave oxidation potential splitting of meso-porphyrins and their zinc complexes. PMID:27379447

  2. Xe-bearing hydrocarbon ions: Observation of Xe.acetylene+rad and Xe.benzene+rad radical cations and calculations of their ground state structures

    Science.gov (United States)

    Cui, Zhong-hua; Attah, Isaac K.; Platt, Sean P.; Aziz, Saadullah G.; Kertesz, Miklos; El-Shall, M. S.

    2016-04-01

    This work reports evidence for novel types of Xe-bearing hydrocarbon radical cations. The Xe.acetylene+rad radical cation adduct is observed at nearly room temperature using the mass-selected drift cell technique. The irreversible addition of the Xe atom and the lack of back dissociation to HCCH+rad + Xe is consistent with the calculated binding energy of 0.85 eV to be contrasted with the metastable nature of the neutral Xe.acetylene adduct. The observed Xe.benzene+rad radical cation appears to be a weakly bound complex stabilized mainly by ion-induced dipole interaction consistent with a calculated binding energy in the range of 0.14-0.17 eV.

  3. Density Functional Theory (DFT) studies on the ground state of NO3(2A '2) radical and the first triplet state of NO3+ cation

    Institute of Scientific and Technical Information of China (English)

    CAO, Xiao-Yan(曹晓燕); HONG, Gong-Yi(洪功义); WANG, Dian-Xun(王殿勋); LI, Le-Min(黎乐民); XU, Guang-Xian(徐光宪)

    2000-01-01

    Density Functional Theory (DFT) studies on the ground states (2A'2) of NO3 radical and on the ground state (1A'1) and the first triplet state (3E") of NO3+ cation provide an unambiguous prediction about their geometrical structure: the ground states of both NO3 radical and NO3+ cation have D3h symmetry and the geometrical configuration of the first triplet state 3E" of NO3+ cation has C2v symmetry. It is shown that s far as the ionization energy calculations on NO3 radical are concerned, the results are only slightly different, no mater that gradient corrections of the exchange-correlation energy are included during self-consistent iterations of they are included as perturbations after the self-consistent iterations.

  4. Actinide bis(porphyrinate) π-radical cations and dications, including the x-ray crystal structure of [(TPP)2Th][SbCl6

    International Nuclear Information System (INIS)

    The chemistry of actinide porphyrin complexes remains in large part undeveloped. The authors report here the first synthesis, isolation, and detailed characterization of several actinide bis-porphyrin sandwich complexes, including the neutral, π-radical monocation, and π-radical dication complexes, [(TPP)2M]/sup n+/, where M = Th(IV) or U(IV) and n = 0, 1, or 2. In addition, the x-ray crystal structure of both the neutral Th complex and its oxidized π-radical cation, [(TPP)2Th][SbCl60, have been solved. These complexes are among the very first π-radical cations where close interaction between two porphyrins occurs. Moreover, these complexes belong to an unusual class of actinide complexes where redox processes can occur in near proximity to the f-element

  5. Umbrella motion of the methyl cation, radical, and anion molecules. I. Potentials, energy levels and partition functions

    Science.gov (United States)

    Ragni, Mirco; Bitencourt, Ana Carla P.; Prudente, Frederico V.; Barreto, Patricia R. P.; Posati, Tamara

    2016-03-01

    A study of the umbrella motion of the methyl cation, radical, and anion molecules is presented. This is the floppiest mode of vibration of all three species and its characterization is of fundamental importance for understanding their reactivity. Minimum Energy Paths of the umbrella motions according to the hyperspherical treatment were obtained, by single point calculations, at the CCSD(T)/aug-cc-pVQT level of theory in the Born-Oppenheimer approximation. These energy profiles permit us to calculate the vibrational levels through the Hyperquantization algorithm, which is shown appropriated for the description of the umbrella motion of these three molecules. The adiabatic electron affinity and ionization potentials were estimated to good accuracy. Partition functions are also calculated in order to obtain information on the reaction rates involving these groups.

  6. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2C(O)OH2+

    Science.gov (United States)

    Lee, Richard; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    2006-09-01

    Previous studies have shown that the solitary ketene-water ion CH2C(O)OH2+ (1) does not isomerize into CH2C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2O loss from low-energy 1,3-dihydroxyacetone ions (HOCH2)2CO+. A mechanistic analysis using the CBS-QB3 model chemistry shows that such molecular ions rearrange into hydrogen-bridged radical cations [CH2C(O)O(H)-H...OCH2]+ in which the CH2O molecule catalyzes the transformation 1 --> 2 prior to dissociation. The barrier for the unassisted reaction, 29 kcal mol-1, is reduced to a mere 0.6 kcal mol-1 for the catalysed transformation. Formaldehyde is an efficient catalyst because its proton affinity meets the criterion for facile proton-transport catalysis.

  7. A 1,2,3-dithiazolyl-o-naphthoquinone: a neutral radical with isolable cation and anion oxidation states.

    Science.gov (United States)

    Smithson, Chad S; MacDonald, Daniel J; Matt Letvenuk, T; Carello, Christian E; Jennings, Michael; Lough, Alan J; Britten, James; Decken, Andreas; Preuss, Kathryn E

    2016-06-21

    Under aprotic conditions, the reaction of 4-amino-1,2-naphthoquinone with excess S2Cl2 generates 4,5-dioxo-naphtho[1,2-d][1,2,3]dithiazol-2-ium chloride in a typical Herz condensation. By contrast, prior literature reports an imine (NH) product, 4,5-dioxo-1H-naphtho[1,2-d][1,2,3]dithiazole, for the same reaction performed in acetic acid. Herein, the cation product is isolated with four different counter-anions (Cl(-), GaCl4(-), FeCl4(-) and OTf(-)). Reduction of the cation generates a neutral radical 1,2,3-dithiazolyl-o-naphthoquinone, with potential ligand properties. Further reduction generates a closed shell anion, isolated as a water-stable Li(+) complex and exhibiting O,O-bidentate chelation. The hydroxy (OH) isomer of the original imine (NH) product is reported, and this can be readily deprotonated and acylated (OAc). All species are structurally characterized. Solution redox behaviour and EPR are discussed where appropriate. PMID:27216412

  8. Reactions of aliphatic free radicals with copper cations in aqueous solutions

    International Nuclear Information System (INIS)

    Helium-saturated solutions containing copper sulphate and an aliphatic alcohol (methanol, ethanol or propan-2-ol) were pulse irradiated. The kinetics of the reactions thus initiated were followed by the spectrophotometric and conductometric techniques. The results indicate that all three radicals, CR1R2OH, react with Cu2+sub(aq) to yield Cu+sub(aq) + CR1R2O+H3O+. CH2OH radicals react with Cu+sub(aq) according to Cu+sub(aq) + CH2OH yields reversibly Cusup(II) -CH2OH+, K approximately 5 x 103 dm3 mol-1. (Note: In writing Cusup(II) - R+ or Cusup(III) - R2+ the accepted nomenclature is followed for organometallic compounds. This notation does not imply that the nature of the chemical bond is ionic. Furthermore, the results indicate that the Cu - C bond has at least partially a covalent nature.) The corresponding equilibrium constants for Cusup(II) - CH(CH3)OH+ and Cusup(II) - C(CH3)2OH+ are too low to be measured and the corresponding intermediates are not observed. Cu+sub(aq) reacts with the β radicals, CH2CH2OH and CH2CH(CH3)OH, according to Cu+sub(aq) + CH2CR1R2OH → Cusup(II) - CH2CR1R2OH+. The latter intermediates decompose via acid catalysed reactions to yield Cu2+sub(aq) + H2C = CR1R2 + H2O. (author)

  9. Time-dependent density functional study on the electronic excitation energies of polycyclic aromatic hydrocarbon radical cations of naphthalene, anthracene, pyrene, and perylene

    International Nuclear Information System (INIS)

    Time-dependent density functional theory (TDDFT) and its modification, the Tamm - Dancoff approximation to TDDFT, are employed to calculate the electronic excitation energies and oscillator strengths for a series of polycyclic aromatic hydrocarbon radical cations. For the radical cations of naphthalene and anthracene, TDDFT using the Becke - Lee - Yang - Parr functional and the 6-31G** basis set provides the excitation energies that are roughly within 0.3 eV of the experimental data. The assignments of the electron transitions proposed by TDDFT accord with the previous assignments made by accurate ab initio calculations, except that TDDFT indicates the existence of a few additional transitions of π*left-arrow σ character among the several low-lying transitions. The calculated energies for these π*left-arrow σ transitions are found to be consistent with the onset of a σ electron ionization manifold in the photoelectron spectra. For the pyrene radical cation, TDDFT supports the previous assignments made by semiempirical calculations, whereas for the perylene radical cation, TDDFT suggests the energy ordering of the three lowest-lying excited states be changed from those of the semiempirical results. copyright 1999 American Institute of Physics

  10. Formation of environmentally persistent free radical (EPFR) in iron(III) cation-exchanged smectite clay.

    Science.gov (United States)

    Nwosu, Ugwumsinachi G; Roy, Amitava; dela Cruz, Albert Leo N; Dellinger, Barry; Cook, Robert

    2016-01-01

    Environmentally persistent free radicals (EPFRs) have been found at a number of Superfund sites, with EPFRs being formed via a proposed redox process at ambient environmental conditions. The possibility of such a redox process taking place at ambient environmental conditions is studied utilizing a surrogate soil system of phenol and iron(III)-exchanged calcium montmorillonite clay, Fe(III)CaM. Sorption of phenol by the Fe(III)CaM is demonstrated by Fourier-transformed infra-red (FT-IR) spectroscopy, as evidenced by the peaks between 1345 cm(-1) and 1595 cm(-1), and at lower frequencies between 694 cm(-1) and 806 cm(-1), as well as X-ray diffraction (XRD) spectroscopy, as shown by an increase in interlayer spacing within Fe(III)CaM. The formation and characterization of the EPFRs is determined by electron paramagnetic resonance (EPR) spectroscopy, showing phenoxyl-type radical with a g-factor of 2.0034 and ΔHP-P of 6.1 G at an average concentration of 7.5 × 10(17) spins per g. EPFRs lifetime data are indicative of oxygen and water molecules being responsible for EPFR decay. The change in the oxidation state of the iron redox center is studied by X-ray absorption near-edge structure (XANES) spectroscopy, showing that 23% of the Fe(III) is reduced to Fe(II). X-ray photoemission spectroscopy (XPS) results confirm the XANES results. These findings, when combined with the EPFR concentration data, demonstrate that the stoichiometry of the EPFR formation under the conditions of this study is 1.5 × 10(-2) spins per Fe(II) atom. PMID:26647158

  11. Radicals

    Czech Academy of Sciences Publication Activity Database

    Jahn, Ullrich; Cornils, B.

    Weinheim: Wiley-VCH, 2013 - (Cornils, B.; Herrmann, W.; Wong, C.; Zanthoff, H.), s. 1897-1898 ISBN 978-3-527-33307-3 Institutional support: RVO:61388963 Keywords : radicals * enzymatic catalysis * coenzyme B12 * ribonucleotide reductase * mutases Subject RIV: CC - Organic Chemistry

  12. Ultrafast studies on the photophysics of matrix-isolated radical cations of polycyclic aromatic hydrocarbons: implications for the Diffuse Interstellar Bands (DIB) problem

    CERN Document Server

    Zhao, L; Shkrob, I A; Crowell, R A; Pommeret, S; Chronister, E L; Liu, A D; Trifunac, A D; Zhao, Liang; Lian, Rui; Shkrob, Ilya A.; Crowell, Robert A.; Pommeret, Stanislas; Chronister, Eric L.; Liu, An Dong; Trifunac, Alexander D.

    2004-01-01

    Rapid, efficient deactivation of the photoexcited PAH cations accounts for their remarkable photostability and have important implications for astrochemistry, as these cations are the leading candidates for the species responsible for the diffuse interstellar bands (DIB) observed throughout the Galaxy.Ultrafast relaxation dynamics for photoexcited PAH cations isolated in boric acid glass have been studied using femtosecond and picosecond transient grating spectroscopy. With the exception of perylene+, the recovery kinetics for the ground doublet (D0) states of these radical cations are biexponential, containing a fast (< 200 fs) and a slow (3-20 ps) components. No temperature dependence or isotope effect was observed for the fast component, whereas the slow component exhibits both the H/D isotope effect (1.1-1.3) and strong temperature dependence (15 to 300 K). We suggest that the fast component is due to internal Dn to D0 conversion and the slow component is due to vibrational energy transfer (VET) from a...

  13. Plastids and Carotenoid Accumulation.

    Science.gov (United States)

    Li, Li; Yuan, Hui; Zeng, Yunliu; Xu, Qiang

    2016-01-01

    Plastids are ubiquitously present in plants and are the organelles for carotenoid biosynthesis and storage. Based on their morphology and function, plastids are classified into various types, i.e. proplastids, etioplasts, chloroplasts, amyloplasts, and chromoplasts. All plastids, except proplastids, can synthesize carotenoids. However, plastid types have a profound effect on carotenoid accumulation and stability. In this chapter, we discuss carotenoid biosynthesis and regulation in various plastids with a focus on carotenoids in chromoplasts. Plastid transition related to carotenoid biosynthesis and the different capacity of various plastids to sequester carotenoids and the associated effect on carotenoid stability are described in light of carotenoid accumulation in plants. PMID:27485226

  14. Key to xenobiotic carotenoids

    OpenAIRE

    Hans-Richard Sliwka; Vassilia Partali

    2012-01-01

    A listing of carotenoids with heteroatoms (X = F, Cl, Br, I, Si, N, S, Se, Fe) directly attached to the carotenoid carbon skeleton has been compiled. The 178 listed carotenoids with C,H,X atoms demonstrate that the classical division of carotenoids into hydrocarbon carotenoids (C,H) and xanthophylls (C,H,O) has become obsolete.

  15. The Role of Carotenoids in Human Skin

    Directory of Open Access Journals (Sweden)

    Theognosia Vergou

    2011-12-01

    Full Text Available The human skin, as the boundary organ between the human body and the environment, is under the constant influence of free radicals (FR, both from the outside in and from the inside out. Carotenoids are known to be powerful antioxidant substances playing an essential role in the reactions of neutralization of FR (mainly reactive oxygen species ROS. Carotenoid molecules present in the tissue are capable of neutralizing several attacks of FR, especially ROS, and are then destroyed. Human skin contains carotenoids, such as α-, γ-, β-carotene, lutein, zeaxanthin, lycopene and their isomers, which serve the living cells as a protection against oxidation. Recent studies have reported the possibility to investigate carotenoids in human skin quickly and non-invasively by spectroscopic means. Results obtained from in-vivo studies on human skin have shown that carotenoids are vital components of the antioxidative protective system of the human skin and could serve as marker substances for the overall antioxidative status. Reflecting the nutritional and stress situation of volunteers, carotenoids must be administered by means of antioxidant-rich products, e.g., in the form of fruit and vegetables. Carotenoids are degraded by stress factors of any type, inter alia, sun radiation, contact with environmental hazards, illness, etc. The kinetics of the accumulation and degradation of carotenoids in the skin have been investigated.

  16. A search for blues brothers: X-ray crystallographic/spectroscopic characterization of the tetraarylbenzidine cation radical as a product of aging of solid magic blue.

    Science.gov (United States)

    Talipov, Marat R; Hossain, Mohammad M; Boddeda, Anitha; Thakur, Khushabu; Rathore, Rajendra

    2016-03-14

    Magic blue (MB+˙ SbCl6− salt), i.e. tris-4-bromophenylamminium cation radical, is a routinely employed one-electron oxidant that slowly decomposes in the solid state upon storage to form so called ‘blues brothers’, which often complicate the quantitative analyses of the oxidation processes. Herein, we disclose the identity of the main ‘blues brother’ as the cation radical and dication of tetrakis-(4-bromophenyl)benzidine (TAB) by a combined DFT and experimental approach, including isolation of TAB+˙ SbCl6− and its X-ray crystallography characterization. The formation of TAB in aged magic blue samples occurs by a Scholl-type coupling of a pair of MB followed by a loss of molecular bromine. The recognition of this fact led us to the rational design and synthesis of tris(2-bromo-4-tert-butylphenyl)amine, referred to as ‘blues cousin’ (BC: Eox1 = 0.78 V vs. Fc/Fc+, λmax(BC+˙) = 805 nm, εmax = 9930 cm−1 M−1), whose oxidative dimerization is significantly hampered by positioning the sterically demanding tert-butyl groups at the para-positions of the aryl rings. A ready two-step synthesis of BC from triphenylamine and the high stability of its cation radical (BC+˙) promise that BC will serve as a ready replacement for MB and an oxidant of choice for mechanistic investigations of one-electron transfer processes in organic, inorganic, and organometallic transformations. PMID:26878458

  17. Kinetics of electron transfer from cobalt(II) porphyrins to various metalloporphyrin pi-radical cations in irradiated carbon tetrachloride solutions

    International Nuclear Information System (INIS)

    One-electron oxidation of a series of metallotetraphenylporphyrins (M-TPP) was studied by pulse radiolysis in CCl4 solutions. The resultant pi-radical cations were found to oxidize Co/sup II/TPP to Co/sup III/TPP with rate constants of the order of 105 M-1 s-1, much slower than the diffusion-controlled rates despite the high free energies of these reactions. In the presence of pyridine these electron-transfer reactions were much faster (107-108 M-1 s-1), suggesting that pyridine, as an axial ligand, facilitates the electron transfer between metalloporphyrins. 20 references, 1 table

  18. Chemical and Spectroscopic Studies of Carotenoids and Related Compounds

    OpenAIRE

    Lutnæs, Bjart Frode

    2004-01-01

    Structure elucidation of charge delocalised carotenoid mono- and dications by NMR and VIS/NIR spectroscopy. Studies of the nucleophilic reactions of these cations. Studies of the β,β-carotene-iodine complex. Isolation and anmalysis of new carotenoid glucoside esters from extremophilic bacteria.

  19. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    Science.gov (United States)

    Solano, Eduardo A.; Mayer, Paul M.

    2015-09-01

    The fragmentation mechanisms of the naphthalene molecular ion to [M-C4H2]+•, [M-C2H2]+•, [M-H2]+•, and [M-H•]+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)'s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)'s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0-18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%-100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M-C2H2]+• structure is the phenylacetylene cation.

  20. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    International Nuclear Information System (INIS)

    The fragmentation mechanisms of the naphthalene molecular ion to [M–C4H2]+•, [M–C2H2]+•, [M–H2]+•, and [M–H•]+ were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H2 molecule in a two-step fragmentation. H• loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C4H2) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C2H2]+• structure is the phenylacetylene cation

  1. A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface

    Energy Technology Data Exchange (ETDEWEB)

    Solano, Eduardo A.; Mayer, Paul M., E-mail: pmmayer@uottawa.ca [Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5 (Canada)

    2015-09-14

    The fragmentation mechanisms of the naphthalene molecular ion to [M–C{sub 4}H{sub 2}]{sup +•}, [M–C{sub 2}H{sub 2}]{sup +•}, [M–H{sub 2}]{sup +•}, and [M–H{sup •}]{sup +} were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H{sub 2} molecule in a two-step fragmentation. H{sup •} loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C{sub 4}H{sub 2}) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C{sub 2}H{sub 2}]{sup +•} structure is the phenylacetylene cation.

  2. One-electron oxidation of nickel porphyrins. Effect of structure and medium on formation of nickel(III) porphyrin or nickel(II) porphyrin π-radical cation

    International Nuclear Information System (INIS)

    The oxidation of several nickel(II) porphyrins by various radicals has been studied by pulse radiolysis in different media (Cl2sm-bullet- and Br2sm-bullet- in aqueous systems, Br atoms in organic solvents, and peroxyl radicals in organic and aqueous/organic systems). Photochemical oxidation was also examined in some cases. The absorption spectrum of the oxidation product was monitored within several microseconds after the pulse. Two types of differential spectra were observed, a broad absorption at 640-700 nm ascribed to the π-radical cation, or a sharp absorption at 560-580 nm ascribed to nickel(III) porphyrin. NiIITPP (tetraphenylporphyrin) in several organic solvents, protic and aprotic, was oxidized to NiIIITPP. The addition of 10% water as cosolvent or 0.1 M of electrolyte changed the route of oxidation to give the radical cation NiIITPPsm-bullet+. On the other hand, NiIITSPP (tetrakis(4-sulfonatophenyl)porphyrin), which has four negative charges, was oxidized on the porphyrin ligand by all the radicals examined, in water and in several organic solvents. NiIIbis(N-methyl-4-pyridyl)diphenylporphyrin, with a charge of +2, and NiII tris(4-sulfonatophenyl)(N-methyl-4-pyridyl)porphyrin, with an overall charge of -2, were oxidized on the ligand in aqueous solution but on the metal in organic solvents. These and other results led to the conclusion that most radicals react with NiIIP by an inner-sphere mechanism to bind onto the metal and give the NiIIIP form. However, when the porphyrin is sufficiently charged to repel the axially bound anion, and/or when the medium enhances the separation of this anion from the metal, the result is oxidation of the porphyrin π-system. In all cases, however, the one-electron-oxidation products, whether NiIIPsm-bullet+ or NiIIIP, decay to yield two-electron ring oxidation products

  3. Phytochemical profile and ABTS cation radical scavenging, cupric reducing antioxidant capacity and anticholinesterase activities of endemic Ballota nigra L. subsp. anatolica P.H. Davis from Turkey

    Directory of Open Access Journals (Sweden)

    Abdulselam Ertaş

    2014-07-01

    Full Text Available Objective: To evaluate the chemical compositions and biological activities of an endemic Ballota nigra L. subsp. anatolica P.H. Davis. Methods: Essential oil and fatty acid composition were determined by GC/MS analysis. ABTS cation radical decolourisation and cupric reducing antioxidant capacity assays were carried out to indicate the antioxidant activity. The anticholinesterase potential of the extracts were determined by Ellman method. Results: The major compounds in the fatty acid composition of the petroleum ether extract were identified as palmitic (36.0% and linoleic acids (14.3%. The major components of essential oil were 1-hexacosanol (26.7%, germacrene-D (9.3% and caryophyllene oxide (9.3%. The water extract indicated higher ABTS cation radical scavenging activity than α-tocopherol and BHT, at 100 µg/ mL. The acetone extract showed 71.58 and 44.71% inhibitory activity against butyrylcholinesterase and acetylcholinesterase enzyme at 200 µg/mL, respectively. Conclusions: The water and acetone extracts of Ballota nigra subsp. anatolica can be investigated in terms of both phytochemical and biological aspects to find natural active compounds.

  4. Experimental study of the bridged and classical structures of the ethyl radical and cation by neutralized ion-beam spectroscopy

    International Nuclear Information System (INIS)

    The states of ethyl radicals formed in electron capture reactions of a fast beam of C2H5+ with a series of metal target atoms (K, Na, Ca, Mg, and Zn) have been investigated by neutral beam scattering techniques. Reactions of C2H5+ with Mg or Zn atoms lead to formation of ground state radicals and an excited state about 0.5 eV above the dissociation limit of C2H4+H. Analysis of branching ratios for these processes over a range of Mg atom densities shows that the ion beam is a mixture of two isomers in the ratio of about 7.3/1.0 for beams generated either by electron impact or chemical ionization methods. From neutral-precursor ion relationships we propose that the major and minor components of the ion beam are the bridged and classical C2H5+ structures, respectively. Analysis of neutral beam profiles in experiments with Na or K targets indicate the formation of a dissociative state of the classical radical lying about 4.2 eV above the ground state. An upper limit of 2.2 eV to the barrier to 1, 2 hydrogen migration in the classical radical is provided by the energy of the lowest state of the bridged radical observed

  5. Generation of structurally novel short carotenoids and study of their biological activity

    DEFF Research Database (Denmark)

    Kim, Se Hyeuk; Kim, Moon S.; Lee, Bun Y.;

    2016-01-01

    Recent research interest in phytochemicals has consistently driven the efforts in the metabolic engineering field toward microbial production of various carotenoids. In spite of systematic studies, the possibility of using C30 carotenoids as biologically functional compounds has not been explored...... thus far. Here, we generated 13 novel structures of C30 carotenoids and one C35 carotenoid, including acyclic, monocyclic, and bicyclic structures, through directed evolution and combinatorial biosynthesis, in Escherichia coli. Measurement of radical scavenging activity of various C30 carotenoid...... structures revealed that acyclic C30 carotenoids showed higher radical scavenging activity than did DL-atocopherol. We could assume high potential biological activity of the novel structures of C30 carotenoids as well, based on the neuronal differentiation activity observed for the monocyclic C30 carotenoid...

  6. Carotenoids in Marine Animals

    Directory of Open Access Journals (Sweden)

    Takashi Maoka

    2011-02-01

    Full Text Available Marine animals contain various carotenoids that show structural diversity. These marine animals accumulate carotenoids from foods such as algae and other animals and modify them through metabolic reactions. Many of the carotenoids present in marine animals are metabolites of β-carotene, fucoxanthin, peridinin, diatoxanthin, alloxanthin, and astaxanthin, etc. Carotenoids found in these animals provide the food chain as well as metabolic pathways. In the present review, I will describe marine animal carotenoids from natural product chemistry, metabolism, food chain, and chemosystematic viewpoints, and also describe new structural carotenoids isolated from marine animals over the last decade.

  7. Coherent spectroscopy and carotenoids

    Czech Academy of Sciences Publication Activity Database

    Niklas Christensson, N.; Chábera, P.; Pascher, T.; Dietzek, B.; Polívka, Tomáš; Yartsev, A.; Pullerits, T.

    Nové Hrady : Academic and University Center, 2008. s. 24. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Keywords : carotenoids * biophysics Subject RIV: BO - Biophysics

  8. Macular and serum carotenoid concentrations in patients with malabsorption syndromes.

    Science.gov (United States)

    Ward, Matthew S; Zhao, Da You; Bernstein, Paul S

    2008-03-01

    The carotenoids lutein and zeaxanthin are believed to protect the human macula by absorbing blue light and quenching free radicals. Intestinal malabsorption syndromes such as celiac and Crohn's disease are known to cause deficiencies of lipid-soluble nutrients. We hypothesized that subjects with nutrient malabsorption syndromes will demonstrate lower carotenoid levels in the macula and blood, and that these lower levels may correlate with early-onset maculopathy. Resonance Raman spectrographic (RRS) measurements of macular carotenoid levels were collected from subjects with and without a history of malabsorption syndromes. Carotenoids were extracted from serum and analyzed by high performance liquid chromatography (HPLC). Subjects with malabsorption (n = 22) had 37% lower levels of macular carotenoids on average versus controls (n = 25, P maculopathy were not observed. We conclude that intestinal malabsorption results in lower macular carotenoid levels. PMID:19081745

  9. Carotenoids in Marine Animals

    OpenAIRE

    Takashi Maoka

    2011-01-01

    Marine animals contain various carotenoids that show structural diversity. These marine animals accumulate carotenoids from foods such as algae and other animals and modify them through metabolic reactions. Many of the carotenoids present in marine animals are metabolites of β-carotene, fucoxanthin, peridinin, diatoxanthin, alloxanthin, and astaxanthin, etc. Carotenoids found in these animals provide the food chain as well as metabolic pathways. In the present review, I will describe marine a...

  10. Hydrophilic Carotenoids: Recent Progress

    OpenAIRE

    Attila Agócs; József Deli; Veronika Nagy; Magdolna Háda

    2012-01-01

    Carotenoids are substantially hydrophobic antioxidants. Hydrophobicity is this context is rather a disadvantage, because their utilization in medicine as antioxidants or in food chemistry as colorants would require some water dispersibility for their effective uptake or use in many other ways. In the past 15 years several attempts were made to synthetize partially hydrophilic carotenoids. This review compiles the recently synthetized hydrophilic carotenoid derivatives.

  11. Carotenoid Photoprotection in Artificial Photosynthetic Antennas

    Energy Technology Data Exchange (ETDEWEB)

    Kloz, Miroslav [VU Univ., Amsterdam (Netherlands); Pillai, Smitha [Arizona State Univ., Tempe, AZ (United States); Kodis, Gerdenis [Arizona State Univ., Tempe, AZ (United States); Gust, Devens [Arizona State Univ., Tempe, AZ (United States); Moore, Thomas A. [Arizona State Univ., Tempe, AZ (United States); Moore, Ana L. [Arizona State Univ., Tempe, AZ (United States); van Grondelle, Rienk [VU Univ., Amsterdam (Netherlands); Kennis, John T. M. [VU Univ., Amsterdam (Netherlands)

    2011-04-14

    A series of phthalocyanine-carotenoid dyads in which a phenylamino group links a phthalocyanine to carotenoids having 8-11 backbone double bonds were examined by visible and near-infrared femtosecond pump-probe spectroscopy combined with global fitting analysis. The series of molecules has permitted investigation of the role of carotenoids in the quenching of excited states of cyclic tetrapyrroles. The transient behavior varied dramatically with the length of the carotenoid and the solvent environment. Clear spectroscopic signatures of radical species revealed photoinduced electron transfer as the main quenching mechanism for all dyads dissolved in a polar solvent (THF), and the quenching rate was almost independent of carotenoid length. However, in a nonpolar solvent (toluene), quenching rates displayed a strong dependence on the conjugation length of the carotenoid and the mechanism did not include charge separation. The lack of any rise time components of a carotenoid S1 signature in all experiments in toluene suggests that an excitonic coupling between the carotenoid S1 state and phthalocyanine Q state, rather than a conventional energy transfer process, is the major mechanism of quenching. A pronounced inhomogeneity of the system was observed and attributed to the presence of a phenyl-amino linker between phthalocyanine and carotenoids. On the basis of accumulated work on various caroteno-phthalocyanine dyads and triads, we have now identified three mechanisms of tetrapyrrole singlet excited state quenching by carotenoids in artificial systems: (i) Car-Pc electron transfer and recombination; (ii)1Pc to Car S1 energy transfer and fast internal conversion to the Car ground state; (iii) excitonic coupling between 1Pc and Car S1 and ensuing internal conversion to the ground state of the carotenoid. The dominant mechanism depends upon the exact molecular architecture and solvent environment

  12. Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

    OpenAIRE

    Sidorenkova Cruz Gonzalez, Elena; Berclaz, Théo; Ndiaye, Bassirou; Jouaiti, Abdelaziz; Geoffroy, Michel

    2009-01-01

    A radical species characterized by a large g-anisotropy and a clearly resolved hyperfine structure with 95/97Mo and 31P nuclei is formed, at 77 K, by radiolysis of a single crystal of Mo(CO)5PPh3. The corresponding EPR signals disappear irreversibly with increasing temperature and the angular dependence of the various coupling constants imply a spin delocalization of not, vert, similar60% and not, vert, similar4% on the molybdenum and the phosphorus atoms, respectively and are, a priori, cons...

  13. Marine Carotenoids and Cardiovascular Risk Markers

    Directory of Open Access Journals (Sweden)

    Lorenza Speranza

    2011-06-01

    Full Text Available Marine carotenoids are important bioactive compounds with physiological activities related to prevention of degenerative diseases.found principally in plants, with potential antioxidant biological properties deriving from their chemical structure and interaction with biological membranes. They are substances with very special and remarkable properties that no other groups of substances possess and that form the basis of their many, varied functions and actions in all kinds of living organisms. The potential beneficial effects of marine carotenoids have been studied particularly in astaxanthin and fucoxanthin as they are the major marine carotenoids. Both these two carotenoids show strong antioxidant activity attributed to quenching singlet oxygen and scavenging free radicals. The potential role of these carotenoids as dietary anti-oxidants has been suggested to be one of the main mechanisms for their preventive effects against cancer and inflammatory diseases. The aim of this short review is to examine the published studies concerning the use of the two marine carotenoids, astaxanthin and fucoxanthin, in the prevention of cardiovascular diseases.

  14. Hydrophilic Carotenoids: Recent Progress

    Directory of Open Access Journals (Sweden)

    Attila Agócs

    2012-04-01

    Full Text Available Carotenoids are substantially hydrophobic antioxidants. Hydrophobicity is this context is rather a disadvantage, because their utilization in medicine as antioxidants or in food chemistry as colorants would require some water dispersibility for their effective uptake or use in many other ways. In the past 15 years several attempts were made to synthetize partially hydrophilic carotenoids. This review compiles the recently synthetized hydrophilic carotenoid derivatives.

  15. Macular and serum carotenoid concentrations in patients with malabsorption syndromes

    OpenAIRE

    Ward, Matthew S.; Zhao, Da You; Bernstein, Paul S

    2008-01-01

    The carotenoids lutein and zeaxanthin are believed to protect the human macula by absorbing blue light and quenching free radicals. Intestinal malabsorption syndromes such as celiac and Crohn’s disease are known to cause deficiencies of lipid-soluble nutrients. We hypothesized that subjects with nutrient malabsorption syndromes will demonstrate lower carotenoid levels in the macula and blood, and that these lower levels may correlate with early-onset maculopathy. Resonance Raman spectrographi...

  16. Marine Carotenoids against Oxidative Stress: Effects on Human Health

    OpenAIRE

    Maria Alessandra Gammone; Graziano Riccioni; Nicolantonio D'Orazio

    2015-01-01

    Carotenoids are lipid-soluble pigments that are produced in some plants, algae, fungi, and bacterial species, which accounts for their orange and yellow hues. Carotenoids are powerful antioxidants thanks to their ability to quench singlet oxygen, to be oxidized, to be isomerized, and to scavenge free radicals, which plays a crucial role in the etiology of several diseases. Unusual marine environments are associated with a great chemical diversity, resulting in novel bioactive molecules. Thus,...

  17. Encapsulation of Carotenoids

    Science.gov (United States)

    Ribeiro, Henelyta S.; Schuchmann, Heike P.; Engel, Robert; Walz, Elke; Briviba, Karlis

    Carotenoids are natural pigments, which are synthesized by microorganisms and plants. More than 600 naturally occurring carotenoids have been found in the nature. The main sources of carotenoids are fruits, vegetables, leaves, peppers, and certain types of fishes, sea foods, and birds. Carotenoids may protect cells against photosensitization and work as light-absorbing pigments during photosynthesis. Some carotenoids may inhibit the destructive effect of reactive oxygen species. Due to the antioxidative properties of carotenoids, many investigations regarding their protective effects against cardiovascular diseases and certain types of cancers, as well as other degenerative illnesses, have been carried out in the last years (Briviba et al. 2004; Krinsky et al. 2004; Kirsh et al. 2006). A diet rich in carotenoids may also contribute to photoprotection against UV radiation (Stahl et al. 2006). In vitro studies have shown that carotenoids such as β-cryptoxanthin and lycopene stimulate bone formation and mineralization. The results may be related to prevention of osteoporosis (Kim et al. 2003; Yamaguchi and Uchiyama 2003; 2004; Yamaguchi et al. 2005).

  18. Carotenoid metabolism in plants

    Science.gov (United States)

    Carotenoids are mostly C40 terpenoids, a class of hydrocarbons that participate in various biological processes in plants, such as photosynthesis, photomorphogenesis, photoprotection, and development. Carotenoids also serve as precursors for two plant hormones and a diverse set of apocarotenoids. Th...

  19. Antioxidant effects of carotenoids

    NARCIS (Netherlands)

    Bast, A.; Haenen, G.R.M.M.; Berg, R. van den; Berg, H. van den

    1998-01-01

    Surprisingly, neither the precise pharmacological effect nor the toxicological profile is usually established for food components. Carotenoids are no exception in this regard. Only limited insight into the pharmacology and toxicology of carotenoids exists. It is known that the antioxidant action of

  20. Carotenoids in Microalgae.

    Science.gov (United States)

    Henríquez, Vitalia; Escobar, Carolina; Galarza, Janeth; Gimpel, Javier

    2016-01-01

    Carotenoids are a class of isoprenoids synthesized by all photosynthetic organisms as well as by some non-photosynthetic bacteria and fungi with broad applications in food, feed and cosmetics, and also in the nutraceutical and pharmaceutical industries. Microalgae represent an important source of high-value products, which include carotenoids, among others. Carotenoids play key roles in light harvesting and energy transfer during photosynthesis and in the protection of the photosynthetic apparatus against photooxidative damage. Carotenoids are generally divided into carotenes and xanthophyls, but accumulation in microalgae can also be classified as primary (essential for survival) and secondary (by exposure to specific stimuli).In this chapter, we outline the high value carotenoids produced by commercially important microalgae, their production pathways, the improved production rates that can be achieved by genetic engineering as well as their biotechnological applications. PMID:27485224

  1. Carotenoids and Photosynthesis.

    Science.gov (United States)

    Hashimoto, Hideki; Uragami, Chiasa; Cogdell, Richard J

    2016-01-01

    Carotenoids are ubiquitous and essential pigments in photosynthesis. They absorb in the blue-green region of the solar spectrum and transfer the absorbed energy to (bacterio-)chlorophylls, and so expand the wavelength range of light that is able to drive photosynthesis. This is an example of singlet-singlet energy transfer, and so carotenoids serve to enhance the overall efficiency of photosynthetic light reactions. Carotenoids also act to protect photosynthetic organisms from the harmful effects of excess exposure to light. Triplet-triplet energy transfer from chlorophylls to carotenoids plays a key role in this photoprotective reaction. In the light-harvesting pigment-protein complexes from purple photosynthetic bacteria and chlorophytes, carotenoids have an additional role of structural stabilization of those complexes. In this article we review what is currently known about how carotenoids discharge these functions. The molecular architecture of photosynthetic systems will be outlined first to provide a basis from which to describe carotenoid photochemistry, which underlies most of their important functions in photosynthesis. PMID:27485220

  2. C---lH...O and O...H...O bonded intermediates in the dissociation of low energy methyl glycolate radical cations

    Science.gov (United States)

    Suh, Dennis; Kingsmill, Carol A.; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    1995-08-01

    Low energy methyl glycolate radical cations HOCH2C(=O)OCH3+, 1, abundantly lose HCO, yielding protonated methyl formate H---C(OH)OCH3+. Tandem mass spectrometry based experiments on 2H, 13C and 18O labelled isotopologues show that this loss is largely (about 75%) atom specific. Analysis of the atom connectivity in the product ions indicates that the reaction proceeds analogously to the loss of HCO and CH3CO from ionized acetol HOCH2C(=O)CH3+ and acetoin HOCH(CH3)C(=O)CH3+, respectively. The mechanism, it is proposed, involves isomerization of 1 to the key intermediate CH2=O... H---C(=O)OCH3+, an H-bridged ion-dipole complex of neutral formaldehyde and ionized methyl formate. Next, charge transfer takes place to produce CH3OC(H)=O...HC(H)=O+, an H-bridged ion-dipole complex of ionized formaldehyde and neutral methyl formate, followed by proton transfer to generate the products. Preliminary ab initio calculations executed at the UMP3/6-31G*//6-31G*+ZPVE level of theory are presented in support of this proposal. The non-specific loss of HCO from 1 (about 25%) is rationalized to occur via the same mechanism, but after communication with isomeric dimethyl carbonate ions CH3OC(=O)OCH3+, 2, via the O...H...O bonded intermediate [CH2=O...H...O=C---OCH3]+. The latter pathway is even more important in the formation of CH2OH+ ions from 1 which, it is shown, is not a simple bond cleavage reaction, but may involve consecutive or concerted losses of CH3 and CO2 from the above O...H...O bonded species. Ionized methyl lactate HOCH(CH3)C(=O)OCH3+, the higher homologue of 1, shows a unimolecular chemistry which is akin to that of 1.

  3. EPR Study on the Complex Formed by Charge-Transfer Processbetween Ground-state Acceptor 2,3-Dicyano-5, 6-dichloro-1,4-benzoquinone and Some Donors and on Cation Radical of Pery-lene (or Pyrene)

    Institute of Scientific and Technical Information of China (English)

    SHI Ji-Liang; ZHOU Cheng-Ming; ZHAO Xin; XU Jia-Yi; JIANG Xi-Kui

    2001-01-01

    EPR Study showed that semi-quinone radical anion of 2,3-dicyano-5,6-dichloro-1,4-benzoquinone (DDQ)was formed in a charge transfer process between groung-state DDQ as accep-tor and each one of following ground state donors,i.e.,4-methyl-4'-tridecyl-2,2'-bipyridyl;4-methyl-4'-nonyl-2,2'-bipyridyl)ruthenium(2+)perchlorate and perylene.EPRstdy also showed that there are perylene cation radical and pyrene catinon radical in thefollowing experimentaql conditions:(a)in98%sulfuric acid.(b)10-3mol/L perylene (orpyrene)was dissolved in trifluoroacetic acid-nitrlbenzene (1:1V/V).

  4. ASTAXANTHIN: A POTENTIAL CAROTENOID

    OpenAIRE

    Jyotika Dhankhar et al.

    2012-01-01

    Astaxanthin, a member of the carotenoid family, is a dark-red pigment which is the main carotenoid found in the marine world of algae and aquatic animals. Astaxanthin, is present in many types of seafood, including salmon, trout, red sea bream, shrimp and lobster, as well as in birds such as flamingo and quail. Synthetic Astaxanthin dominates the world market but recent interest in natural sources of the pigment has increased substantially. Common sources of natural Astaxanthin, are the gree...

  5. Raman measurement of carotenoid composition in human skin

    Science.gov (United States)

    Ermakov, Igor V.; Ermakova, Maia R.; Gellermann, Werner

    2004-07-01

    The carotenoids lycopene and beta-carotene are powerful antioxidants in skin and are thought to act as scavengers for free radicals and singlet oxygen. The role of carotenoid species in skin health is of strong current interest. We demonstrate the possibility to use Resonance Raman spectroscopy for fast, non-invasive, highly specific, and quantitative detection of beta-carotene and lycopene in human skin. Analyzing Raman signals originating from the carbon-carbon double bond stretch vibrations of the carotenoid molecules under blue and green laser excitation, we were able to characterize quantitatively the relative concentrations of each carotenoid species in-vivo. In the selective detection, we take advantage of different Raman cross-section spectral profiles for beta-carotene and lycopene molecules, and obtain a quantitative assessment of individual long-chain carotenoid species in the skin rather than their cumulative levels. Preliminary dual-wavelength Raman measurements reveal significant differences in the carotenoid composition of different subjects. The technique holds promise for rapid screening of carotenoid compositions in human skin in large populations and may be suitable in clinical studies for assessing the risk for cutaneous diseases.

  6. Crystalline bipyridinium radical complexes and uses thereof

    Energy Technology Data Exchange (ETDEWEB)

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  7. Crystalline bipyridinium radical complexes and uses thereof

    Science.gov (United States)

    Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

    2015-09-01

    Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

  8. Dietary factors that affect carotenoid bioavailability

    NARCIS (Netherlands)

    Hof, van het K.

    1999-01-01

    Carotenoids are thought to contribute to the beneficial effects of increased vegetable consumption. To better understand the potential benefits of carotenoids, we investigated the bioavailability of carotenoids from vegetables and dietary factors which might influence carotenoid bioavailability.In a

  9. Generation of structurally novel short carotenoids and study of their biological activity.

    Science.gov (United States)

    Kim, Se H; Kim, Moon S; Lee, Bun Y; Lee, Pyung C

    2016-01-01

    Recent research interest in phytochemicals has consistently driven the efforts in the metabolic engineering field toward microbial production of various carotenoids. In spite of systematic studies, the possibility of using C30 carotenoids as biologically functional compounds has not been explored thus far. Here, we generated 13 novel structures of C30 carotenoids and one C35 carotenoid, including acyclic, monocyclic, and bicyclic structures, through directed evolution and combinatorial biosynthesis, in Escherichia coli. Measurement of radical scavenging activity of various C30 carotenoid structures revealed that acyclic C30 carotenoids showed higher radical scavenging activity than did DL-α-tocopherol. We could assume high potential biological activity of the novel structures of C30 carotenoids as well, based on the neuronal differentiation activity observed for the monocyclic C30 carotenoid 4,4'-diapotorulene on rat bone marrow mesenchymal stem cells. Our results demonstrate that a series of structurally novel carotenoids possessing biologically beneficial properties can be synthesized in E. coli. PMID:26902326

  10. Mechanistic aspects of carotenoid biosynthesis

    KAUST Repository

    Moïse, Alexander R.

    2014-01-08

    Carotenoid synthesis is based on the analysis of the phenotype of several mutant strains of tomato lacking carotenoid synthetic genes. Carotenoids are tetraterpenes derived through the condensation of the five-carbon (C5) universal isoprenoid precursors isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP). A recently developed concept that could explain the role of the poly-cis pathway in carotenoid synthesis is that the intermediates of this pathway have additional physiological roles that extend beyond serving as precursors of lycopene. This concept is based on the analysis of the phenotype of several mutant strains of tomato lacking carotenoid synthetic genes. The feedback regulation of early carotenoid synthetic genes in response to a block in upstream metabolism represents a paradigm shift in our understanding of the mechanism and regulation of carotenoid synthesis and of metabolic regulation in general. The molecular details of a signaling pathway that regulates carotenogenesis in response to the levels of carotenoid precursors are still unclear.

  11. Dietary Carotenoids Regulate Astaxanthin Content of Copepods and Modulate Their Susceptibility to UV Light and Copper Toxicity

    OpenAIRE

    Carman, Kevin R.; Silva, Soraya J.; Maria-José Caramujo; Carla C. C. R. de Carvalho

    2012-01-01

    High irradiation and the presence of xenobiotics favor the formation of reactive oxygen species in marine environments. Organisms have developed antioxidant defenses, including the accumulation of carotenoids that must be obtained from the diet. Astaxanthin is the main carotenoid in marine crustaceans where, among other functions, it scavenges free radicals thus protecting cell compounds against oxidation. Four diets with different carotenoid composition were used to culture the meiobenthic c...

  12. Identification of carotenoids from the extremely halophilic archaeon Haloarcula japonica

    Directory of Open Access Journals (Sweden)

    Rie eYatsunami

    2014-03-01

    Full Text Available The carotenoids produced by extremely halophilic archaeon Haloarcula japonica were extracted and identified by their chemical, chromatographic, and spectroscopic characteristics (UV-Vis and mass spectrometry. The composition (mol% was 68.1% bacterioruberin, 22.5% monoanhydrobacterioruberin, 9.3% bisanhydrobacterioruberin, < 0.1% isopentenyldehydrorhodopin, and trace amounts of lycopene and phytoene. The in vitro scavenging capacity of a carotenoid, bacterioruberin, extracted from Ha. japonica cells against 1,1-diphenyl-2-picrylhydrazyl (DPPH radicals was evaluated. The antioxidant capacity of bacterioruberin was much higher than that of β-carotene.

  13. The antioxidant potential of carotenoid extract from Phaffia rhodozyma

    Directory of Open Access Journals (Sweden)

    Anna Gramza-Michałowska

    2010-06-01

    Full Text Available Background. Carotenoids are components playing an important role in biological systems, starting with light protection, immunoenhancement, protection against carcinogens and finishing with antioxidant activity. Food additives market is based mainly on synthetic additives; however, higher consumer awareness has resulted in an increased use of natural substances. One of the potentially antioxidant compounds could be a lipid soluble carotenoid – astaxanthin (xanthophyll, found in the microbial world. The aim of this study was to evaluate the antioxidant potential of carotenoid extract from Phaffia rhodozyma extract. Material and methods. Carotenoids extracted from Phaffia rhodozyma and the astaxanthin standard was selected for the investigations. Antioxidant potential was evaluated by radical scavenging activity (DPPH• and ABTS•+ radicals and in lipid oxidative stability measurements (Rancimat, Oxidograph and Schaal oven tests. Results. It was found that the examined extracts presented a significantly higher ability to scavenge the DPPH• radical in comparison to the ABTS•+ radical. Evaluations of linoleic acid emulsion oxidative stability showed a higher antioxidant effect of the Phaffia rhodozyma extract than that of astaxanthin during 19 h of incubation. That potential however, was not detected in linoleic acid emulsion incubated for 96 h, where both additives accelerated oxidation process. In bulk sunflower oil a protective effect of Phaffia rhodozyma extract was observed. In both Rancimat and Oxidograph tests antioxidant activity measured using the induction period was evaluated. However, results of the Schaal oven test indicated that a 144 h incubation of sunflower oil offered a significantly better protection of the lipid against oxidation when the Phaffia rhodozyma extract was added. Conclusions. On the basis of recorded results it was found that the Phaffia rhodozyma carotenoid extract showed moderate antioxidant properties

  14. Thermal Methane Activation by a Binary V-Nb Transition-Metal Oxide Cluster Cation: A Further Example for the Crucial Role of Oxygen-Centered Radicals

    Czech Academy of Sciences Publication Activity Database

    Wang, Z. C.; Liu, J. W.; Schlangen, M.; Weiske, T.; Schröder, Detlef; Sauer, J.; Schwarz, H.

    2013-01-01

    Roč. 19, č. 35 (2013), s. 11496-11501. ISSN 0947-6539 Institutional support: RVO:61388963 Keywords : binary oxide cluster * density functional calculations * mass spectrometry * methane activation * radical ions Subject RIV: CC - Organic Chemistry Impact factor: 5.696, year: 2013

  15. Carotenoid dynamics in Atlantic salmon

    OpenAIRE

    Omholt Stig W; Våge Dag; Øyehaug Leiv; Rajasingh Hannah

    2006-01-01

    Abstract Background Carotenoids are pigment molecules produced mainly in plants and heavily exploited by a wide range of organisms higher up in the food-chain. The fundamental processes regulating how carotenoids are absorbed and metabolized in vertebrates are still not fully understood. We try to further this understanding here by presenting a dynamic ODE (ordinary differential equation) model to describe and analyse the uptake, deposition, and utilization of a carotenoid at the whole-organi...

  16. Studies of radiation-produced radicals and radical ions

    International Nuclear Information System (INIS)

    The radiolytic oxidation of anti-5-methylbicyclo[2.1.0]pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10-8--10-9s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo[3.2.1]oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo[3.2.0]hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations

  17. Carotenoids, Phenolic Compounds and Tocopherols Contribute to the Antioxidative Properties of Some Microalgae Species Grown on Industrial Wastewater

    DEFF Research Database (Denmark)

    Safafar, Hamed; van Wagenen, Jonathan Myerson; Møller, Per;

    2015-01-01

    activity in all antioxidant tests while carotenoids were found to contribute to the 1,1-diphenyl-2-picryl-hydrazil (DPPH) radical scavenging activity, ferrous reduction power (FRAP), and ABTS-radical scavenging capacity activity. Desmodesmus sp. biomass represented a potentially rich source of natural...... antioxidants, such as carotenoids (lutein), tocopherols, and phenolic compounds when cultivated on industrial waste water as the main nutrient source....

  18. Marine Carotenoids against Oxidative Stress: Effects on Human Health.

    Science.gov (United States)

    Gammone, Maria Alessandra; Riccioni, Graziano; D'Orazio, Nicolantonio

    2015-10-01

    Carotenoids are lipid-soluble pigments that are produced in some plants, algae, fungi, and bacterial species, which accounts for their orange and yellow hues. Carotenoids are powerful antioxidants thanks to their ability to quench singlet oxygen, to be oxidized, to be isomerized, and to scavenge free radicals, which plays a crucial role in the etiology of several diseases. Unusual marine environments are associated with a great chemical diversity, resulting in novel bioactive molecules. Thus, marine organisms may represent an important source of novel biologically active substances for the development of therapeutics. In this respect, various novel marine carotenoids have recently been isolated from marine organisms and displayed several utilizations as nutraceuticals and pharmaceuticals. Marine carotenoids (astaxanthin, fucoxanthin, β-carotene, lutein but also the rare siphonaxanthin, sioxanthin, and myxol) have recently shown antioxidant properties in reducing oxidative stress markers. This review aims to describe the role of marine carotenoids against oxidative stress and their potential applications in preventing and treating inflammatory diseases. PMID:26437420

  19. Marine Carotenoids against Oxidative Stress: Effects on Human Health

    Directory of Open Access Journals (Sweden)

    Maria Alessandra Gammone

    2015-09-01

    Full Text Available Carotenoids are lipid-soluble pigments that are produced in some plants, algae, fungi, and bacterial species, which accounts for their orange and yellow hues. Carotenoids are powerful antioxidants thanks to their ability to quench singlet oxygen, to be oxidized, to be isomerized, and to scavenge free radicals, which plays a crucial role in the etiology of several diseases. Unusual marine environments are associated with a great chemical diversity, resulting in novel bioactive molecules. Thus, marine organisms may represent an important source of novel biologically active substances for the development of therapeutics. In this respect, various novel marine carotenoids have recently been isolated from marine organisms and displayed several utilizations as nutraceuticals and pharmaceuticals. Marine carotenoids (astaxanthin, fucoxanthin, β-carotene, lutein but also the rare siphonaxanthin, sioxanthin, and myxol have recently shown antioxidant properties in reducing oxidative stress markers. This review aims to describe the role of marine carotenoids against oxidative stress and their potential applications in preventing and treating inflammatory diseases.

  20. Carotenoids as a Source of Antioxidants in the Diet.

    Science.gov (United States)

    Xavier, Ana Augusta Odorissi; Pérez-Gálvez, Antonio

    2016-01-01

    Carotenoids, widely distributed fat-soluble pigments, are responsible for the attractive colorations of several fruits and vegetables commonly present in our daily diet. They are particularly abundant in yellow-orange fruits (carrots, tomatoes, pumpkins, peppers, among others) and, although masked by chlorophylls, in dark green leafy vegetables. Several health benefits have been attributed to carotenoids or to foods rich in these pigments, by means of different mechanisms-of-action, including the role as provitamin A of almost 50 different carotenoids and the antioxidant activity that protects cells and tissues from damage of free radicals and singlet oxygen, providing enhancement of the immune function, protection from sunburn reactions and delaying the onset of certain types of cancer. Common food sources and the efficiency of the absorption of carotenoids, analytical approaches used for measurement of their antioxidant effect and an overview of some epidemiological studies that have been performed to assess the beneficial impact of carotenoids in human health are outlined in this chapter. PMID:27485230

  1. How carotenoids protect bacterial photosynthesis.

    OpenAIRE

    Cogdell, R J; Howard, T. D.; Bittl, R.; Schlodder, E; Geisenheimer, I; Lubitz, W.

    2000-01-01

    The essential function of carotenoids in photosynthesis is to act as photoprotective agents, preventing chlorophylls and bacteriochlorophylls from sensitizing harmful photodestructive reactions in the presence of oxygen. Based upon recent structural studies on reaction centres and antenna complexes from purple photosynthetic bacteria, the detailed organization of the carotenoids is described. Then with specific reference to bacterial antenna complexes the details of the photoprotective role, ...

  2. Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH3 radical cations

    International Nuclear Information System (INIS)

    Coupled electron-nuclear dynamics has been studied, using the Ehrenfest method, for four conformations of the glycine molecule and a single conformation of Gly-Gly-NH-CH3. The initial electronic wavepacket was a superposition of eigenstates corresponding to ionization from the σ lone pairs associated with the carbonyl oxygens and the amine nitrogen. For glycine, oscillating charge migration (when the nuclei were frozen) was observed for the 4 conformers studied with periods ranging from 2 to 5 fs, depending on the energy gap between the lone pair cationic states. When coupled nuclear motion was allowed (which was mainly NH2 partial inversion), the oscillations hardly changed. For Gly-Gly-NH-CH3, charge migration between the carbonyl oxygens and the NH2 lone pair can be observed with a period similar to glycine itself, also without interaction with nuclear motion. These simulations suggest that charge migration between lone pairs can occur independently of the nuclear motion

  3. ASTAXANTHIN: A POTENTIAL CAROTENOID

    Directory of Open Access Journals (Sweden)

    Jyotika Dhankhar et al.

    2012-05-01

    Full Text Available Astaxanthin, a member of the carotenoid family, is a dark-red pigment which is the main carotenoid found in the marine world of algae and aquatic animals. Astaxanthin, is present in many types of seafood, including salmon, trout, red sea bream, shrimp and lobster, as well as in birds such as flamingo and quail. Synthetic Astaxanthin dominates the world market but recent interest in natural sources of the pigment has increased substantially. Common sources of natural Astaxanthin, are the green algae haematococcus pluvialis, the red yeast, Phaffia rhodozyma, as well as crustacean byproducts. Astaxanthin possesses unusual antioxidant property which has caused a surge in the nutraceutical market of the encapsulated products. Numerous studies have shown that astaxanthin has potential health-promoting effects in the prevention and treatment of various diseases, such as cancers, chronic inflammatory diseases, metabolic syndrome, diabetes, diabetic nephropathy, cardiovascular diseases, gastrointestinal diseases, liver diseases, neurodegenerative diseases, eye diseases, skin diseases, exercise-induced fatigue, male infertility, and renal failure. In this article, the currently available scientific literature regarding the most significant activities of astaxanthin is reviewed.

  4. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO2+) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO2+; therefore, cation-cation complexes indicate something unique about AnO2+ cations compared to actinide cations in general. The first cation-cation complex, NpO2+·UO22+, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO2+ species, the cation-cation complexes of NpO2+ have been studied most extensively while the other actinides have not. The only PuO2+ cation-cation complexes that have been studied are with Fe3+ and Cr3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO2+·UO22+, NpO2+·Th4+, PuO2+·UO22+, and PuO2+·Th4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M-1

  5. Energy-dependent reversal of secondary isotope effects on simple cleavage reactions: tertiary amine radical cations with deuterium at remote positions

    International Nuclear Information System (INIS)

    Deuterium substitution at remote sites gives rise to inverse secondary kinetic isotope effects on the α-cleavage of a number of tertiary amines in the ion source, but to normal isotope effects on reactions occurring in the field-free regions. The change from normal to inverse secondary isotope effects when the internal energy of the reacting ions increases is consistent with transition-state models that involve slight lowering of vibrational frequencies also for bonds well removed from the site of cleavage. The isotope effect on the reactions of ions of high internal energy is caused by the influence that even small changes of isotope-dependent frequencies have on the state sums (a statistical weight effect favouring loss of the labelled radical), whereas the behaviour of low-energy ions is determined by the zero-point energy changes which favour loss of the unlabelled fragment. (author)

  6. Carotenoid Biosynthesis in Daucus carota.

    Science.gov (United States)

    Simpson, Kevin; Cerda, Ariel; Stange, Claudia

    2016-01-01

    Carrot (Daucus carota) is one of the most important vegetable cultivated worldwide and the main source of dietary provitamin A. Contrary to other plants, almost all carrot varieties accumulate massive amounts of carotenoids in the root, resulting in a wide variety of colors, including those with purple, yellow, white, red and orange roots. During the first weeks of development the root, grown in darkness, is thin and pale and devoid of carotenoids. At the second month, the thickening of the root and the accumulation of carotenoids begins, and it reaches its highest level at 3 months of development. This normal root thickening and carotenoid accumulation can be completely altered when roots are grown in light, in which chromoplasts differentiation is redirected to chloroplasts development in accordance with an altered carotenoid profile. Here we discuss the current evidence on the biosynthesis of carotenoid in carrot roots in response to environmental cues that has contributed to our understanding of the mechanism that regulates the accumulation of carotenoids, as well as the carotenogenic gene expression and root development in D. carota. PMID:27485223

  7. Food Predictors of Plasma Carotenoids

    Directory of Open Access Journals (Sweden)

    Sara J. Hendrickson

    2013-10-01

    Full Text Available Empirical prediction models that weight food frequency questionnaire (FFQ food items by their relation to nutrient biomarker concentrations may estimate nutrient exposure better than nutrient intakes derived from food composition databases. Carotenoids may especially benefit because contributing foods vary in bioavailability and assessment validity. Our objective was to develop empirical prediction models for the major plasma carotenoids and total carotenoids and evaluate their validity compared with dietary intakes calculated from standard food composition tables. 4180 nonsmoking women in the Nurses’ Health Study (NHS blood subcohort with previously measured plasma carotenoids were randomly divided into training (n = 2787 and testing (n = 1393 subsets. Empirical prediction models were developed in the training subset by stepwise selection from foods contributing ≥0.5% to intake of the relevant carotenoid. Spearman correlations between predicted and measured plasma concentrations were compared to Spearman correlations between dietary intake and measured plasma concentrations for each carotenoid. Three to 12 foods were selected for the α-carotene, β-carotene, β-cryptoxanthin, lutein/zeaxanthin, lycopene, and total carotenoids prediction models. In the testing subset, Spearman correlations with measured plasma concentrations for the calculated dietary intakes and predicted plasma concentrations, respectively, were 0.31 and 0.37 for α-carotene, 0.29 and 0.31 for β-carotene, 0.36 and 0.41 for β-cryptoxanthin, 0.28 and 0.31 for lutein/zeaxanthin, 0.22 and 0.23 for lycopene, and 0.22 and 0.27 for total carotenoids. Empirical prediction models may modestly improve assessment of some carotenoids, particularly α-carotene and β-cryptoxanthin.

  8. Marine Carotenoids: Biological Functions and Commercial Applications

    OpenAIRE

    Vega, José M.; Inés Garbayo; Francisco Bédmar; María Cuaresma; Carlos Vílchez; Eduardo Forján

    2011-01-01

    Carotenoids are the most common pigments in nature and are synthesised by all photosynthetic organisms and fungi. Carotenoids are considered key molecules for life. Light capture, photosynthesis photoprotection, excess light dissipation and quenching of singlet oxygen are among key biological functions of carotenoids relevant for life on earth. Biological properties of carotenoids allow for wide range of commercial applications. Indeed, recent interest in the carotenoids has be...

  9. Fluphenazine hydrochloride radical cation assay: A new, rapid and precise method to determine in vitro total antioxidant capacity of fruit extracts

    Institute of Scientific and Technical Information of China (English)

    Muhammad Nadeem Asghar; Qadeer Alam; Sharoon Augusten

    2012-01-01

    A new procedure based on generation and subsequent reduction of orange-colored fluphenazine hydrochloride radical (FPH·+)is presented for the screening of total antioxidant capacity (TAC) of various fruit matrices.The FPH·+ was obtained by mixing fluphenazine hydrochloride with persulfate (final concentration 2 mmol/L and 0.05 mmmol/L,respectively) in 3 mol/L H2SO4 with constant shaking for 5 min.The solution formed showed maximum absorption as 0.8 ± 0.02 at 500 nm in first-order derivative spectrum.The percent inhibition of the solution increased linearly on addition of increasing mounts of standard antioxidants i.e.,ascorbic acid etc.The TACs of sample citrus juices were calculated in terms of ascorbic acid equivalents (AAEs) by comparing their inhibition curves with that of ascorbic acid.Comparison of AAE values of different commercial orange juices using the newly developed FPH·+ assay and the well-known ABTS/K2S2O8 and DMPD/FeCl3 assays indicated the precision and comparable sensitivity of the method.The proposed procedure is quick,economical,and more precise and gives results comparable to contemporary assays.

  10. Assembly of functional photosystem complexes in Rhodobacter sphaeroides incorporating carotenoids from the spirilloxanthin pathway.

    Science.gov (United States)

    Chi, Shuang C; Mothersole, David J; Dilbeck, Preston; Niedzwiedzki, Dariusz M; Zhang, Hao; Qian, Pu; Vasilev, Cvetelin; Grayson, Katie J; Jackson, Philip J; Martin, Elizabeth C; Li, Ying; Holten, Dewey; Neil Hunter, C

    2015-02-01

    Carotenoids protect the photosynthetic apparatus against harmful radicals arising from the presence of both light and oxygen. They also act as accessory pigments for harvesting solar energy, and are required for stable assembly of many light-harvesting complexes. In the phototrophic bacterium Rhodobacter (Rba.) sphaeroides phytoene desaturase (CrtI) catalyses three sequential desaturations of the colourless carotenoid phytoene, extending the number of conjugated carbon-carbon double bonds, N, from three to nine and producing the yellow carotenoid neurosporene; subsequent modifications produce the yellow/red carotenoids spheroidene/spheroidenone (N=10/11). Genomic crtI replacements were used to swap the native three-step Rba. sphaeroides CrtI for the four-step Pantoea agglomerans enzyme, which re-routed carotenoid biosynthesis and culminated in the production of 2,2'-diketo-spirilloxanthin under semi-aerobic conditions. The new carotenoid pathway was elucidated using a combination of HPLC and mass spectrometry. Premature termination of this new pathway by inactivating crtC or crtD produced strains with lycopene or rhodopin as major carotenoids. All of the spirilloxanthin series carotenoids are accepted by the assembly pathways for LH2 and RC-LH1-PufX complexes. The efficiency of carotenoid-to-bacteriochlorophyll energy transfer for 2,2'-diketo-spirilloxanthin (15 conjugated CC bonds; N=15) in LH2 complexes is low, at 35%. High energy transfer efficiencies were obtained for neurosporene (N=9; 94%), spheroidene (N=10; 96%) and spheroidenone (N=11; 95%), whereas intermediate values were measured for lycopene (N=11; 64%), rhodopin (N=11; 62%) and spirilloxanthin (N=13; 39%). The variety and stability of these novel Rba. sphaeroides antenna complexes make them useful experimental models for investigating the energy transfer dynamics of carotenoids in bacterial photosynthesis. PMID:25449968

  11. Carotenoid photoprotection in Diaptomus kenai

    Energy Technology Data Exchange (ETDEWEB)

    Hairston, N.G. Jr.

    1978-12-01

    Red copepods have been reported from a wide variety of aquatic environments. The red color is produced by a carotenoid pigment, in most cases astaxanthin and its esters, that the copepods cannot form de novo but derive from ingested pigments such as beta-carotene. In an earlier study, the adaptive advantage of carotenoid pigmentation was investigated. Copepods containing large amounts of astaxanthin had significantly better survival than copepods containing small amounts of the pigment when exposed to light of an intensity and color similar to that occurring in the lakes from which they were taken. This result suggested that the carotenoid pigment protected the copepods from photodamage by visible light. Here a second example of carotenoid photoprotection involving the copepod Diaptomus kenai found in fresh-water mountain lakes is described. Information on the vertical distributions of D. sicilis and D. nevadensis in relation to their pigmentation is summarized, as these data will be presented elsewhere.

  12. Free-radical chemistry of thiourea in aqueous solution, induced by OH radical, H atom, α-hydroxyalkyl radicals, photoexcited maleimide, and the solvated electron

    International Nuclear Information System (INIS)

    Hydroxyl radicals react with thiourea (and its tetramethyl derivative) yielding dimeric radical cations which are characterized by strong absorptions at 400 nm (450 nm). An analysis of the kinetics of the buildup of these absorptions gives evidence for the intermediacy of OH-adducts and the monomeric radical cations. The dimeric radical cations are also generated in the reactions of triplet-excited maleimide with those thioureas. Moreover, in acidic solutions even reducing radicals such as the H atom and α-hydroxy alkyl radicals give rise to these intermediates in full yields, albeit displaying different kinetics. Potential mechanistic implications are discussed. The dimeric thiourea radical cations are strong oxidants and readily oxidize the anions of phenol and 2'-deoxyguanosine. The solvated electron gives rise to an intermediate which is rapidly protonated by water (pKa > 11). Quantum mechanical calculations support the assignment of the 400 nm (450 nm) absorption to the respective dimeric thiourea radical cation. (author)

  13. Carotenoids from Marine Microalgae: A Valuable Natural Source for the Prevention of Chronic Diseases

    Directory of Open Access Journals (Sweden)

    Maria Filomena de Jesus Raposo

    2015-08-01

    Full Text Available Epidemiological studies have shown a relation between antioxidants and the prevention of several chronic diseases. Microalgae are a potential novel source of bioactive molecules, including a wide range of different carotenoids that can be used as nutraceuticals, food supplements and novel food products. The objective of this review is (i to update the research that has been carried out on the most known carotenoids produced by marine microalgae, including reporting on their high potentialities to produce other less known important compounds; (ii to compile the work that has been done in order to establish some relationship between carotenoids and oxidative protection and treatment; (iii to summarize the association of oxidative stress and the various reactive species including free radicals with several human diseases; and (iv to provide evidence of the potential of carotenoids from marine microalgae to be used as therapeutics to treat or prevent these oxidative stress-related diseases.

  14. Astaxanthin protecting membrane integrity against photosensitized oxidation through synergism with other carotenoids

    DEFF Research Database (Denmark)

    Du, Hui-Hui; Liang, Ran; Han, Rui-Min;

    2015-01-01

    using optical microscopy and digital image heterogeneity analysis. The lowest initial rate of GUV budding after the lag phase was seen for GUVs with astaxanthin as the least reducing carotenoid, while the lowest final level of entropy appeared for those with lycopene or β-carotene as a more reducing...... carotenoid. The combination of astaxanthin and lycopene gave optimal protection against budding with respect to both a longer lag phase and lower final level of entropy by combining good electron acceptance and good electron donation. Quenching of singlet oxygen by carotenoids close to chlorophyll...... a in the membrane interior in parallel with scavenging of superoxide radicals by astaxanthin anchored in the surface may explain the synergism between carotenoids involving both type I and type II photosensitization by chlorophyll a....

  15. Carotenoid dynamics in Atlantic salmon

    Directory of Open Access Journals (Sweden)

    Omholt Stig W

    2006-04-01

    Full Text Available Abstract Background Carotenoids are pigment molecules produced mainly in plants and heavily exploited by a wide range of organisms higher up in the food-chain. The fundamental processes regulating how carotenoids are absorbed and metabolized in vertebrates are still not fully understood. We try to further this understanding here by presenting a dynamic ODE (ordinary differential equation model to describe and analyse the uptake, deposition, and utilization of a carotenoid at the whole-organism level. The model focuses on the pigment astaxanthin in Atlantic salmon because of the commercial importance of understanding carotenoid dynamics in this species, and because deposition of carotenoids in the flesh is likely to play an important life history role in anadromous salmonids. Results The model is capable of mimicking feed experiments analyzing astaxanthin uptake and retention over short and long time periods (hours, days and years under various conditions. A sensitivity analysis of the model provides information on where to look for possible genetic determinants underlying the observed phenotypic variation in muscle carotenoid retention. Finally, the model framework is used to predict that a specific regulatory system controlling the release of astaxanthin from the muscle is not likely to exist, and that the release of the pigment into the blood is instead caused by the androgen-initiated autolytic degradation of the muscle in the sexually mature salmon. Conclusion The results show that a dynamic model describing a complex trait can be instrumental in the early stages of a project trying to uncover underlying determinants. The model provides a heuristic basis for an experimental research programme, as well as defining a scaffold for modelling carotenoid dynamics in mammalian systems.

  16. Calorimetric study of cationic photopolymerization

    International Nuclear Information System (INIS)

    The photopolymerization of penta-erythritol tetra-glycidyl ether (initiator Degacure KI-85) was studied by a du Pont 910 type DSC. From our experimental results the following conclusions can be drawn: (1) During the cationic polymerization reaction the lifetime of the initiating centers are long compared to the lifetime of free radicals in case of radical polymerization. (2) The rate of deactivation of the initiating centers increases with increasing temperature. (author)

  17. Potential production of carotenoids from Neurospora

    Directory of Open Access Journals (Sweden)

    SRI PRIATNI

    2014-05-01

    Full Text Available Priatni S. 2014. Review: Potential production of carotenoids from Neurospora. Nusantara Bioscience 6: 63-68. Carotenoids are abundant and widely distributed in plants, animals and microorganisms. Commercial use of carotenoids competes between microorganisms and synthetic manufacture. Carotenoids production can be increased by improving the efficiency of carotenoid synthesis in microbes. Some of the cultural and environmental stimulants are positively affecting the carotenoid content of carotenogenic strains such as Neurospora. Neurospora is a fungus that exhibits the formation of spores and conidia, the part of the cell for carotenoids biosynthesis. The Indonesian traditional fermented food, red peanut cake or oncom, especially in West Java, is produced from legume residues of Neurospora sp. This fungus has been isolated and identified as Neurospora intermedia. In order to apply this pigment for food and cosmetic colorants, encapsulation techniques of carotenoids have been developed to improve its solubility and stability.

  18. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  19. Detection of carotenoids present in blood of various animal species using Raman spectroscopy

    Science.gov (United States)

    Liaqat, Maryam; Younus, Ayesha; Saleem, Muhammad; Rashid, Imaad; Yaseen, Maria; Jabeen, Saher

    Raman spectroscopy is simple stable powerful diagnostic tool for body fluids, tissues and other biomolecules. Human blood possesses different kind of carotenoids that play a key role for protecting the cells from damaging by different viral and bacterial diseases. Carotenoids are antioxidative components which are capable to overcome the attack of different free radicals and reactive oxygen species. Carotenoids are not prepared by human body, therefore it is recommended to eat carotenoids enrich vegetable foods. No standard data is available on the concentration of useful carotenoids component in non-vegetable consumed items. In present research work, Raman spectroscopy is used to compare various blood components like plasma, serum, carotenoids present in blood of different animal species like goat, sheep, cow and buffalo consumed by human. Especially beta carotene is investigated. The Raman shift ranges from 600-1700 cm-1 for samples. Different characteristic peaks of the blood components are found which are not characterized before in animal samples. Doctrate Student in Photonics Deparatment of Electrical Engineering.

  20. Studies of radiation-produced radicals and radical ions. Progress report, September 1, 1982-August 31, 1983

    International Nuclear Information System (INIS)

    During the past year, radiation chemical and solid-state ESR techniques were combined to generate and characterize novel radical ions. Observations have been made on a variety of metastable organometallic radical cations derived from Group IV B metal alkyls. Matrix interactions have been discovered between radical cations and the Freon solvent. The radical cation formed from ethylene oxide is the ring-opened 2-oxa-trimethylene cation with a symmetrical C/sub 2v/ planar structure. The CF3CCl2 radical was formed after γ irradiation of the CF3CCl3 (Freon) matrix. Very large long-range proton hyperfine couplings were found in radical cations of carbonyl compounds. The C8F8- ion was studied in MTHF glass, using ESR. Two new inorganic radicals, SF4- and SF4O-, were discovered

  1. Tomato waste: Carotenoids content, antioxidant and cell growth activities.

    Science.gov (United States)

    Stajčić, Sladjana; Ćetković, Gordana; Čanadanović-Brunet, Jasna; Djilas, Sonja; Mandić, Anamarija; Četojević-Simin, Dragana

    2015-04-01

    The carotenoid content, antioxidant and cell growth activities of tomato waste extracts, obtained from five different tomato genotypes, was investigated. High performance liquid chromatography was used to identify and quantify the main carotenoids present in tomato waste extracts. The antioxidant activity of tomato waste extracts was tested using spectrophotometric methods, 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging activity and reducing power assay. The highest DPPH scavenging activity (IC50 = 0.057 mg/ml) was obtained for Bačka extract. The Knjaz extract showed the best reducing power (IC50 = 2.12 mg/ml). Cell growth effects were determined in HeLa, MCF7 and MRC-5 cell lines by sulforhodamine B test. Anti-proliferative effects were observed in all cell lines at higher concentrations (⩾ 0.125 mg/ml). The carotenoid contents exhibited a strong correlation with antioxidant and anti-proliferation activity. The results obtained indicated that tomato waste should be regarded as potential nutraceutic resource and may be used as a functional food ingredient. PMID:25442547

  2. Carotenoids in Adipose Tissue Biology and Obesity.

    Science.gov (United States)

    Bonet, M Luisa; Canas, Jose A; Ribot, Joan; Palou, Andreu

    2016-01-01

    Cell, animal and human studies dealing with carotenoids and carotenoid derivatives as nutritional regulators of adipose tissue biology with implications for the etiology and management of obesity and obesity-related metabolic diseases are reviewed. Most studied carotenoids in this context are β-carotene, cryptoxanthin, astaxanthin and fucoxanthin, together with β-carotene-derived retinoids and some other apocarotenoids. Studies indicate an impact of these compounds on essential aspects of adipose tissue biology including the control of adipocyte differentiation (adipogenesis), adipocyte metabolism, oxidative stress and the production of adipose tissue-derived regulatory signals and inflammatory mediators. Specific carotenoids and carotenoid derivatives restrain adipogenesis and adipocyte hypertrophy while enhancing fat oxidation and energy dissipation in brown and white adipocytes, and counteract obesity in animal models. Intake, blood levels and adipocyte content of carotenoids are reduced in human obesity. Specifically designed human intervention studies in the field, though still sparse, indicate a beneficial effect of carotenoid supplementation in the accrual of abdominal adiposity. In summary, studies support a role of specific carotenoids and carotenoid derivatives in the prevention of excess adiposity, and suggest that carotenoid requirements may be dependent on body composition. PMID:27485231

  3. Transient formation of the oxo-iron(IV) porphyrin radical cation during the reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin with hydrogen peroxide in aqueous solution.

    Science.gov (United States)

    Saha, Tapan Kumar; Karmaker, Subarna; Tamagake, Keietsu

    2003-01-01

    The reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) with hydrogen peroxide (H(2)O(2)) and the catalytic activity of the reaction intermediates on the luminescent peroxidation of luminol in aqueous solution were studied by using a double-mixing stopped-flow system. The observed luminescence intensities showed biphasic decay depending on the conditions. The initial flashlight decayed within flashlight appeared during the formation of the oxo-iron(IV) porphyrin, TMPyPFe(IV) = O, which is responsible for the sustained emission. The absorption spectra 0.0-0.5 s did not reproduce well by a simple combination of the two spectra of Fe(III)TMPyP and TMPyPFe(IV) = O, indicating that transient species was formed at the initial stage. Addition of uric acid (UA) caused a significant delay in the initiation of the luminol emission as well as in the formation of the TMPyPFe(IV) = O. Both of them were completely diminished in the presence of UA equimolar with H(2)O(2), while mannitol had no effect at all. The delay of the light emission as well as the appearance of TMPyPFe(IV) = O was directly proportional to the [UA](0) but other kinetic profiles were not changed significantly. Based on these observations and the kinetic analysis, we confirmed the involvement of the oxo-iron(IV) porphyrin radical cation, (TMPyP)(.+)Fe(IV) = O, as an obligatory intermediate in the rate-determining step of the overall reaction, Fe(III)TMPyP + H(2)O(2) --> TMPyPFe(IV) = O, with a rate constant of k = 4.3 x 10(4)/mol/L/s. The rate constants for the reaction between the (TMPyP)(.+)Fe(IV) = O and luminol, and between the TMPyPFe(IV) = O and luminol were estimated to be 3.6 x 10(6)/mol/L/s and 1.31 x 10(4)/mol/L/s, respectively. PMID:12701092

  4. Microalgae as Sources of Carotenoids

    Directory of Open Access Journals (Sweden)

    Francisco Xavier Malcata

    2011-04-01

    Full Text Available Marine microalgae constitute a natural source of a variety of drugs for pharmaceutical, food and cosmetic applications—which encompass carotenoids, among others. A growing body of experimental evidence has confirmed that these compounds can play important roles in prevention (and even treatment of human diseases and health conditions, e.g., cancer, cardiovascular problems, atherosclerosis, rheumatoid arthritis, muscular dystrophy, cataracts and some neurological disorders. The underlying features that may account for such favorable biological activities are their intrinsic antioxidant, anti-inflammatory and antitumoral features. In this invited review, the most important issues regarding synthesis of carotenoids by microalgae are described and discussed—from both physiological and processing points of view. Current gaps of knowledge, as well as technological opportunities in the near future relating to this growing field of interest, are also put forward in a critical manner.

  5. Carotenoid changes of intact watermelons after storage.

    Science.gov (United States)

    Perkins-Veazie, Penelope; Collins, Julie K

    2006-08-01

    Watermelon contains lycopene, a red carotenoid pigment that has strong antioxidant properties. The lycopene content of watermelon is substantial, contributing 8-20 mg per 180 g serving. There are no reports on carotenoid changes in whole watermelon during storage. Three types of watermelon, open-pollinated seeded, hybrid seeded, and seedless types, were stored at 5, 13, and 21 degrees C for 14 days and flesh color, composition, and carotenoid content were compared to those of fruit not stored. Watermelons stored at 21 degrees C had increased pH, chroma, and carotenoid content compared to fresh fruit. Compared to fresh fruit, watermelons stored at 21 degrees C gained 11-40% in lycopene and 50-139% in beta-carotene, whereas fruit held at 13 degrees C changed little in carotenoid content. These results indicate that carotenoid biosynthesis in watermelons can be affected by temperature and storage. PMID:16881688

  6. Carotenoids content and sunlight susceptibility

    International Nuclear Information System (INIS)

    Full text: An environmental pink pigmented bacterium was isolated and identified as Rhodococcus sp. Pigmentation mutants were obtained by chemical mutagenesis. Pigments present in the wild type strain (RMB90), in a pale yellow mutant (RMB91) and in two mutants exhibiting increased pigmentation (RMB92 and RMB93), were extracted with chloroform-methanol and analyzed by reverse phase HPLC. Survival of these strains after exposure to sunlight and ultraviolet radiation from artificial sources was studied under different physiological and irradiation conditions. The ability of RMB91 to survive sunlight exposure was reduced with respect to that of RMB90. Resistance was similar in both strains when bacteria grew in the presence of a carotenoid synthesis inhibitor, which had no effect on survival of RMB91. Reduced sunlight resistance in RMB91 was also observed during irradiations under N2. Using artificial radiation sources, non pigmented bacteria were less resistant to UVA, but not to UVB or UVC. Lethal effects of sunlight and UVA on RMB92 and RMB93 were increased with respect to the wild type strain. Carotenoids protect Rhodococcus sp against deleterious effects of sunlight. In non-photosynthetic bacteria studied to date, photo protection by carotenoids was dependent on [O2]. This is not the case with Rhodococcus sp RMB90, suggesting the occurrence of a different mechanism for protection. UVA radiation seems to playa key role in photo-damage. (author)

  7. Allometric deviations of plasma carotenoids in raptors

    OpenAIRE

    Blanco, Guillermo; Bautista, Luis M.; Hornero-Méndez, Dámaso; Lambertucci, Guillermo W.; Sánchez-Zapata, José A.; Hiraldo, Fernando; Donázar, José A.

    2014-01-01

    Because large species ingest proportionally less food than small ones, it may be predicted that they should incorporate relatively fewer carotenoids to a proportionally equal volume of blood. However, some species may increase their levels of circulating carotenoids by ingesting unusual food. We tested whether the plasma concentration of carotenoids scales to the three-quarter power of mass in nine predatory and scavenger raptor species. No significant allometric relationships were found due ...

  8. Carotenoids in Aquaculture: Fish and Crustaceans

    Science.gov (United States)

    Bjerkeng, Bjorn

    This Chapter deals with selected topics on the use of carotenoids for colouration in aquaculture and incudes examples from ecological studies which support our understanding of functions and actions of carotenoids and colouration in fishes and crustaceans. Animal colours may be physical or structural in origin [1], e.g. Tyndall blues and iridescent diffraction colours, or they may be due to pigments, including carotenoids (Chapter 10).

  9. Carotenoids in Algae: Distributions, Biosyntheses and Functions

    OpenAIRE

    Shinichi Takaichi

    2011-01-01

    For photosynthesis, phototrophic organisms necessarily synthesize not only chlorophylls but also carotenoids. Many kinds of carotenoids are found in algae and, recently, taxonomic studies of algae have been developed. In this review, the relationship between the distribution of carotenoids and the phylogeny of oxygenic phototrophs in sea and fresh water, including cyanobacteria, red algae, brown algae and green algae, is summarized. These phototrophs contain division- or class-specific carote...

  10. Fermentative production of carotenoids from marine actinomycetes

    Directory of Open Access Journals (Sweden)

    B Ashokkumar

    2009-12-01

    Full Text Available Background and Objectives: In marine actinomycetes, carotenoid production occurs in constitutive, light-dependent or cryptic manner. The present work deals with the fermentative production of carotenoids from marine actinomycetes."nMaterials and Methods: Marine actinomycetes namely Streptomyces strain AQBMM35 was isolated from the marine sponge Mycale mytilorum collected from South West coast of India using ISP media. The Streptomyces isolates were characterized for their colony characteristics, morphological properties, physiological and biochemical properties and were tentatively identified. Fermentation of the strain under fluorescent white light was carried out for the production of carotenoids. UV spectrum, TLC and HPLC analysis were done for the confirmation of carotenoids."nResults: The characteristics studied strongly suggest that the strain AQBMM35 belongs to the genus Streptomyces sp. It has been found that Streptomyces strain (AQBMM35 fermenting under fluorescent white light produced carotenoids. Spectrophotometric analysis of the carotenoid fraction revealed a peak at 280 nm. TLC analysis of the carotenoid extract showed the presence of phytoene (Rf of 0.81. HPLC confirmed the production of phytoene when compared with standards."nConclusion: The fermenting sponge-associated Streptomyces isolate (AQBMM35 produced carotenoids namely phytoene. If this symbiotic Streptomyces strain, from which secondary metabolite like carotenoids are derived, can be cultured under light, then it can be used for mass production of precursor pigment and it can be used as an antioxidant and also as a food additive.

  11. Regulation of Carotenoid Biosynthesis During Fruit Development.

    Science.gov (United States)

    Lado, Joanna; Zacarías, Lorenzo; Rodrigo, María Jesús

    2016-01-01

    Carotenoids are recognized as the main pigments in most fruit crops, providing colours that range from yellow and pink to deep orange and red. Moreover, the edible portion of widely consumed fruits or their derived products represent a major dietary source of carotenoids for animals and humans. Therefore, these pigments are crucial compounds contributing to fruit aesthetic and nutritional quality but may also have protecting and ecophysiological functions in coloured fruits. Among plant organs, fruits display one of the most heterogeneous carotenoids patterns in terms of diversity and abundance. In this chapter a comprehensive list of the carotenoid content and profile in the most commonly cultivated fleshy fruits is reported. The proposed fruit classification systems attending to carotenoid composition are revised and discussed. The regulation of carotenoids in fruits can be rather complex due to the dramatic changes in content and composition during ripening, which are also dependent on the fruit tissue and the developmental stage. In addition, carotenoid accumulation is a dynamic process, associated with the development of chromoplasts during ripening. As a general rule, carotenoid accumulation is highly controlled at the transcriptional level of the structural and accessory proteins of the biosynthetic and degradation pathways, but other mechanisms such as post-transcriptional modifications or the development of sink structures have been recently revealed as crucial factors in determining the levels and stability of these pigments. In this chapter common key metabolic reactions regulating carotenoid composition in fruit tissues are described in addition to others that are restricted to certain species and generate unique carotenoids patterns. The existence of fruit-specific isoforms for key steps such as the phytoene synthase, lycopene β-cyclases or catabolic carotenoid cleavage dioxygenases has allowed an independent regulation of the pathway in fruit tissues

  12. Triplet excitation dynamics of two keto-carotenoids in n-hexane and in methanol as studied by ns flash photolysis spectroscopy

    Science.gov (United States)

    Li, Li; Hu, Feng; Chang, Yu-Qiang; Zhou, Yan; Wang, Peng; Zhang, Jian-Ping

    2015-07-01

    Siphonaxanthin and siphonein are two keto-carotenoids. Upon anthracene-sensitizing, triplet excitation dynamics of these two carotenoids were studied in n-hexane and in methanol, respectively, by ns flash photolysis spectroscopy. In n-hexane, bleaching of the ground state absorption (GSB) and the excitation triplet (3Car*) absorption were observed. In methanol, upon the decay of the 3Car*, the cation dehydrodimer of carotenoid, #[Car]2+, generated by the same rate, while an additional GSB generated synchronously, a polar solvent assisted and anthracene-sensitized mechanism was addressed based on the discussion. The environment-sensitive triplet excitation dynamics imply their potential role in photo-protection in vivo.

  13. Metabolomic engineering for the microbial production of cartenoids and related products with a focus on the rare C50 carotenoids

    NARCIS (Netherlands)

    Heider, S.A.E.; Peters-Wendisch, P.; Wendisch, V.F.; Beekwilder, M.J.

    2014-01-01

    Carotenoids, a subfamily of terpenoids, are yellowtored-colored pigments synthesized by plants, fungi, algae, and bacteria. They are ubiquitous in nature and take over crucial roles in many biological processes as for example photosynthesis, vision, and the quenching of free radicals and singlet oxy

  14. Excited-state properties of hydrophilic carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Naqvi, K.R.; Melo, T.B.; Sliwka, H.R.; Partali, V.; Lockwood, S.; Nodolski, G.; Polívka, Tomáš

    Nové Hrady : Academic and University Center, 2008. s. 40. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * biophysics Subject RIV: BO - Biophysics

  15. Apocarotenoids: A New Carotenoid-Derived Pathway.

    Science.gov (United States)

    Beltran, Juan Camilo Moreno; Stange, Claudia

    2016-01-01

    Carotenoids are precursors of carotenoid derived molecules termed apocarotenoids, which include isoprenoids with important functions in plant-environment interactions such as the attraction of pollinators and the defense against pathogens and herbivores. Apocarotenoids also include volatile aromatic compounds that act as repellents, chemoattractants, growth simulators and inhibitors, as well as the phytohormones abscisic acid and strigolactones. In plants, apocarotenoids can be found in several types of plastids (etioplast, leucoplast and chromoplast) and among different plant tissues such as flowers and roots. The structural similarity of some flower and spice isoprenoid volatile organic compounds (β-ionone and safranal) to carotenoids has led to the recent discovery of carotenoid-specific cleavage oxygenases, including carotenoid cleavage dioxygenases and 9-cis-epoxydioxygenases, which tailor and transform carotenoids into apocarotenoids. The great diversity of apocarotenoids is a consequence of the huge amount of carotenoid precursors, the variations in specific cleavage sites and the modifications after cleavage. Lycopene, β-carotene and zeaxanthin are the precursors of the main apocarotenoids described to date, which include bixin, crocin, picrocrocin, abscisic acid, strigolactone and mycorradicin.The current chapter will give rise to an overview of the biosynthesis and function of the most important apocarotenoids in plants, as well as the current knowledge about the carotenoid cleavage oxygenase enzymes involved in these biosynthetic pathways. PMID:27485225

  16. Method of producing purified carotenoid compounds

    Science.gov (United States)

    Eggink, Laura (Inventor)

    2007-01-01

    A method of producing a carotenoid in solid form includes culturing a strain of Chlorophyta algae cells in a minimal inorganic medium and separating the algae comprising a solid form of carotenoid. In one embodiment f the invention, the strain of Chlorophyta algae cells includes a strain f Chlamydomonas algae cells.

  17. Carotenoid metabolism and regulation in horticultural crops

    Science.gov (United States)

    Carotenoids are a diverse group of pigments widely distributed in nature. The vivid yellow, orange, and red colors in many horticultural crops attribute to overaccumulation of carotenoids, which contribute to a critical agronomic trait for flowers and an important quality trait for fruits and vegeta...

  18. Marine Carotenoids: Biological Functions and Commercial Applications

    NARCIS (Netherlands)

    Vilchez, C.; Forján, E.; Cuaresma, M.; Bédmar, F.; Garbayo, I.; Vega, J.M.

    2011-01-01

    Carotenoids are the most common pigments in nature and are synthesized by all photosynthetic organisms and fungi. Carotenoids are considered key molecules for life. Light capture, photosynthesis photoprotection, excess light dissipation and quenching of singlet oxygen are among key biological functi

  19. Carotenoid Metabolism: Biosynthesis, Regulation,and Beyond

    Institute of Scientific and Technical Information of China (English)

    Shan Lu; Li Li

    2008-01-01

    Carotenoids are Indispensable to plants and play a critical role in human nutrition and health. Significant progress has been made in our understanding of carotenoid metabolism in plants. The biosynthetic pathway has been extensively studied.Nearly all the genes encoding the biosynthetic enzymes have been isolated and characterized from various organisms. In recent years, there is an increasing body of work on the signaling pathways and plastid development, which might provide global control of carotenoid biosynthesis and accumulation. Herein, we will highlight recent progress on the biosynthesis,regulation, and metabolic engineering of carotenoids in plants, as well as the future research towards elucidating the regulatory mechanisms and metabolic network that control carotenoid metabolism.

  20. The intake of carotenoids in Denmark

    DEFF Research Database (Denmark)

    Leth, Torben; Jakobsen, Jette; Andersen, N. L.

    2000-01-01

    To estimate the intake of carotenoids in the Danish population Danish fruits and vegetables were screened with an HPLC method consisting of extraction with ethanol:tetrahydrofuran, separation by reversed phase HPLC with the mobile phase acetonitril:methanol:dichlormethan, triethylamin, BHT...... in the foods the mean intake and intake distribution of the carotenoids were calculated. Carrots and tomatoes have both high contents of carotenoids (8,450 mu g/100 g alpha- + beta-carotene and 4,790 mu g/100 g lycopene, respectively) and high intakes (19 and 15 g/day, respectively) and were responsible for 47......% and 32%, respectively, of the mean intake of carotenoids of 4.8 mg/day A median value of 4.1 mg/day was found indicating skewed intake distributions. The difference between men and women was 0.4 mg/day (p carotenoids, alpha-carotene, beta-carotene, lutein and lycopene, contributed...

  1. Scavenging Capacity of Marine Carotenoids against Reactive Oxygen and Nitrogen Species in a Membrane-Mimicking System

    Directory of Open Access Journals (Sweden)

    Lilian R. B. Mariutti

    2012-08-01

    Full Text Available Carotenoid intake has been associated with the decrease of the incidence of some chronic diseases by minimizing the in vivo oxidative damages induced by reactive oxygen (ROS and nitrogen species (RNS. The carotenoids are well-known singlet oxygen quenchers; however, their capacity to scavenge other reactive species, such as peroxyl radical (ROO, hydroxyl radical (HO, hypochlorous acid (HOCl and anion peroxynitrite (ONOO, still needs to be more extensively studied, especially using membrane-mimicking systems, such as liposomes. Moreover, the identification of carotenoids possessing high antioxidant capacity can lead to new alternatives of drugs or nutritional supplements for prophylaxis or therapy of pathological conditions related to oxidative damages, such as cardiovascular diseases. The capacity to scavenge ROO, HO, HOCl and ONOO of seven carotenoids found in marine organisms was determined in liposomes based on the fluorescence loss of a fluorescent lipid (C11-BODIPY581/591 due to its oxidation by these reactive species. The carotenoid-bearing hydroxyl groups were generally more potent ROS scavengers than the carotenes, whilst β-carotene was the most efficient ONOO scavenger. The role of astaxanthin as an antioxidant should be highlighted, since it was a more potent scavenger of ROO, HOCl and ONOO than α-tocopherol.

  2. Dietary Carotenoids Regulate Astaxanthin Content of Copepods and Modulate Their Susceptibility to UV Light and Copper Toxicity

    Directory of Open Access Journals (Sweden)

    Kevin R. Carman

    2012-04-01

    Full Text Available High irradiation and the presence of xenobiotics favor the formation of reactive oxygen species in marine environments. Organisms have developed antioxidant defenses, including the accumulation of carotenoids that must be obtained from the diet. Astaxanthin is the main carotenoid in marine crustaceans where, among other functions, it scavenges free radicals thus protecting cell compounds against oxidation. Four diets with different carotenoid composition were used to culture the meiobenthic copepod Amphiascoides atopus to assess how its astaxanthin content modulates the response to prooxidant stressors. A. atopus had the highest astaxanthin content when the carotenoid was supplied as astaxanthin esters (i.e., Haematococcus meal. Exposure to short wavelength UV light elicited a 77% to 92% decrease of the astaxanthin content of the copepod depending on the culture diet. The LC50 values of A. atopus exposed to copper were directly related to the initial astaxanthin content. The accumulation of carotenoids may ascribe competitive advantages to certain species in areas subjected to pollution events by attenuating the detrimental effects of metals on survival, and possibly development and fecundity. Conversely, the loss of certain dietary items rich in carotenoids may be responsible for the amplification of the effects of metal exposure in consumers.

  3. Free radical scavenging activity of papaya juice

    International Nuclear Information System (INIS)

    Papaya juice is an efficient scavenger of highly reactive hydroxyl radicals (OH radical) formed during 60Co irradiation of water. The OH anion radicals were detected by the electron spin resonance (ESR) technique of spin trapping using DMPO (5,5-dimethyl-1-pyrroline-N-oxide) or by a colorimetric assay in which salicylate is converted into polyhydroxybenzoic acids. Papaya juice is also able to quench the ESR signal of a stable free radical (TEMPOL) and the ESR signal of the DMPO-OH adduct. The active substance(s) in papaya juice are heat-stable, dialyzable, and soluble in water but not in lipid solvents. The active agents do not appear to be ascorbate, tocopherol, or carotenoids. (author)

  4. Structures and Analysis of Carotenoid Molecules.

    Science.gov (United States)

    Rodriguez-Amaya, Delia B

    2016-01-01

    Modifications of the usual C40 linear and symmetrical carotenoid skeleton give rise to a wide array of structures of carotenes and xanthophylls in plant tissues. These include acyclic, monocyclic and dicyclic carotenoids, along with hydroxy and epoxy xanthophylls and apocarotenoids. Carotenols can be unesterified or esterified (monoester) in one or two (diester) hydroxyl groups with fatty acids. E-Z isomerization increases the array of possible plant carotenoids even further. Screening and especially quantitative analysis are being carried out worldwide. Visible absorption spectrometry and near infrared reflectance spectroscopy have been used for the initial estimation of the total carotenoid content or the principal carotenoid content when large numbers of samples needed to be analyzed within a short time, as would be the case in breeding programs. Although inherently difficult, quantitative analysis of the individual carotenoids is essential. Knowledge of the sources of errors and means to avoid them has led to a large body of reliable quantitative compositional data on carotenoids. Reverse-phase HPLC with a photodiode array detector has been the preferred analytical technique, but UHPLC is increasingly employed. HPLC-MS has been used mainly for identification and NMR has been useful in unequivocally identifying geometric isomers. PMID:27485219

  5. Carotenoids quench evolution of excited species in epidermis exposed to UV-B (290-320 nm) light

    International Nuclear Information System (INIS)

    Reactions involving singlet oxygen and other free radicals have been identified in epidermis containing either exogenous or endogenous photosensitizers, soaked in a singlet oxygen/free radical trap, and then exposed to visible or UV-A (320-400 nm) light. Such reactions can be quenched by the presence of the carotenoid pigments β-carotene and canthaxanthin which accumulate in epidermis after oral administration. It is reported that the carotenoid pigments β-carotene, canthaxanthin and phytoene accumulating in epidermis can also quench to some degree those photochemical reactions involving singlet oxygen and free radicals that occur when epidermis is exposed to the sunburn spectrum of light (UV-B, 290-320 nm). (author)

  6. Holographic films from carotenoid pigments

    Science.gov (United States)

    Toxqui-López, S.; Lecona-Sánchez, J. F.; Santacruz-Vázquez, C.; Olivares-Pérez, A.; Fuentes-Tapia, I.

    2014-02-01

    Carotenoids pigments presents in pineapple can be more than just natural dyes, which is one of the applications that now at day gives the chemical industry. In this research shown that can be used in implementing of holographic recording Films. Therefore we describe the technique how to obtain this kind of pigments trough spay drying of natural pineapple juice, which are then dissolved with water in a proportion of 0.1g to 1mL. The obtained sample is poured into glass substrates using the gravity method, after a drying of 24 hours in laboratory normal conditions the films are ready. The films are characterized by recording transmission holographic gratings (LSR 445 NL 445 nm) and measuring the diffraction efficiency holographic parameter. This recording material has good diffraction efficiency and environmental stability.

  7. Carotenoid maintenance handicap and the physiology of carotenoid-based signalisation of health

    Science.gov (United States)

    Vinkler, Michal; Albrecht, Tomáš

    2010-01-01

    Despite a reasonable scientific interest in sexual selection, the general principles of health signalisation via ornamental traits remain still unresolved in many aspects. This is also true for the mechanism preserving honesty of carotenoid-based signals. Although it is widely accepted that this type of ornamentation reflects an allocation trade-off between the physiological utilisation of carotenoids (mainly in antioxidative processes) and their deposition in ornaments, some recent evidence suggests more complex interactions. Here, we further develop the models currently proposed to explain the honesty of carotenoid-based signalisation of heath status by adding the handicap principle concept regulated by testosterone. We propose that under certain circumstances carotenoids may be dangerous for the organism because they easily transform into toxic cleavage products. When reserves of other protective antioxidants are insufficient, physiological trade-offs may exist between maintenance of carotenoids for ornament expression and their removal from the body. Furthermore, we suggest that testosterone which enhances ornamentation by increasing carotenoid bioavailability may also promote oxidative stress and hence lower antioxidant reserves. The presence of high levels of carotenoids required for high-quality ornament expression may therefore represent a handicap and only individuals in prime health could afford to produce elaborate colourful ornaments. Although further testing is needed, this ‘carotenoid maintenance handicap’ hypothesis may offer a new insight into the physiological aspects of the relationship between carotenoid function, immunity and ornamentation.

  8. Availability of non-carotenoid antioxidants affects the expression of a carotenoid-based sexual ornament.

    Science.gov (United States)

    Pike, Thomas W; Blount, Jonathan D; Lindström, Jan; Metcalfe, Neil B

    2007-08-22

    Carotenoids are responsible for much of the yellow, orange and red pigmentation in the animal kingdom, and the importance of such coloration as an honest signal of individual quality has received widespread attention. In particular, owing to the multiple roles of carotenoids as pigments, antioxidants and immunostimulants, carotenoid-based coloration has been suggested to advertise an individual's antioxidant or immune defence capacity. However, it has recently been argued that carotenoid-based signals may in fact be advertising the availability of different antioxidants, many of which (including various vitamins, antioxidant enzymes and minerals) are colourless and so would be uninformative as components of a visual signal, yet often have greater biological activity than carotenoids. We tested this hypothesis by feeding male sticklebacks (Gasterosteus aculeatus) a diet containing a fixed level of carotenoids and either low or high, but biologically realistic levels of the colourless antioxidant vitamins C and E. High-antioxidant diet males produced significantly more intensely coloured (but not larger) carotenoid-based regions of nuptial coloration and were preferred over size-matched males of the opposite diet treatment in mate-choice trials. Furthermore, there were positive correlations between an individual's somatic antioxidant activity and signal intensity. Our data suggest that carotenoid-based ornaments may honestly signal an individual's availability of non-carotenoid antioxidants, allowing females to make adaptive mate-choice decisions. PMID:17472903

  9. Diversity in the carotenoid profiles and the expression of genes related to carotenoid accumulation among citrus genotypes

    OpenAIRE

    Ikoma, Yoshinori; Matsumoto, Hikaru; Kato, Masaya

    2016-01-01

    Carotenoids are not only important to the plants themselves but also are beneficial to human health. Since citrus fruit is a good source of carotenoids for the human diet, it is important to study carotenoid profiles and the accumulation mechanism in citrus fruit. Thus, in the present paper, we describe the diversity in the carotenoid profiles of fruit among citrus genotypes. In regard to carotenoids, such as β-cryptoxanthin, violaxanthin, lycopene, and β-citraurin, the relationship between t...

  10. Excited-state properties of hydrophilic carotenoids

    Czech Academy of Sciences Publication Activity Database

    Fuciman, M.; Chábera, P.; Naqvi, K.R.; Melo, T.B.; Sliwka, H.R.; Partali, V.; Lockwood, S.; Jackson, H.L.; Polívka, Tomáš

    - : -, 2009. s. 408. ISBN N. [International Conference on Photochemistry /24./. 19.07.2009-24.07.2009, Toledo] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited-state dynamics * femtosecond spectroscopy Subject RIV: BO - Biophysics

  11. Regulation of Carotenoid Biosynthesis in Photosynthetic Organs.

    Science.gov (United States)

    Llorente, Briardo

    2016-01-01

    A substantial proportion of the dazzling diversity of colors displayed by living organisms throughout the tree of life is determined by the presence of carotenoids, which most often provide distinctive yellow, orange and red hues. These metabolites play fundamental roles in nature that extend far beyond their importance as pigments. In photosynthetic lineages, carotenoids are essential to sustain life, since they have been exploited to maximize light harvesting and protect the photosynthetic machinery from photooxidative stress. Consequently, photosynthetic organisms have evolved several mechanisms that adjust the carotenoid metabolism to efficiently cope with constantly fluctuating light environments. This chapter will focus on the current knowledge concerning the regulation of the carotenoid biosynthetic pathway in leaves, which are the primary photosynthetic organs of most land plants. PMID:27485221

  12. Latin American food sources of carotenoids.

    Science.gov (United States)

    Rodriguez-Amaya, D B

    1999-09-01

    Latin America has a wide variety of carotenogenic foods, notable for the diversity and high levels of carotenoids. A part of this natural wealth has been analyzed. Carrot, red palm oil and some cultivars of squash and pumpkin are sources of both beta-carotene and alpha-carotene. beta-carotene is the principal carotenoid of the palm fruits burití, tucumã and bocaiuva, other fruits such as loquat, marolo and West Indian cherry, and sweet potato. Buriti also has high amounts of alpha-carotene and gamma-carotene. beta-Cryptoxanthin is the major carotenoid in caja, nectarine, orange-fleshed papaya, orange, peach, tangerine and the tree tomato. Lycopene predominates in tomato, red-fleshed papaya, guava, pitanga and watermelon. Pitanga also has substantial amounts of beta-cryptoxanthin, gamma-carotene and rubixanthin. Zeaxanthin, principal carotenoid of corn, is also predominant only in piquí. delta-Carotene is the main carotenoid of the peach palm and zeta-carotene of passion fruit. Lutein and beta-carotene, in high concentrations, are encountered in the numerous leafy vegetables of the region, as well as in other green vegetables and in some varieties of squash and pumpkin. Violaxanthin is the principal carotenoid of mango and mamey and is also found in appreciable amounts in green vegetables. Quantitative, in some cases also qualitative, differences exist among cultivars of the same food. Generally, carotenoids are in greater concentrations in the peel than in the pulp, increase considerably during ripening and are in higher levels in foods produced in hot places. Other Latin America indigenous carotenogenic foods must be investigated before they are supplanted by introduced crops, which are often poorer sources of carotenoids. PMID:10971848

  13. Astaxanthin Protecting Membrane Integrity against Photosensitized Oxidation through Synergism with Other Carotenoids.

    Science.gov (United States)

    Du, Hui-Hui; Liang, Ran; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2015-10-21

    Incorporation of astaxanthin or zeaxanthin in giant unilamellar vesicles (GUVs) of phosphatidylcholine resulted in a longer lag phase than incorporation of β-carotene or lycopene for the onset of budding induced by chlorophyll a photosensitization and quantified by a dimensionless entropy parameter using optical microscopy and digital image heterogeneity analysis. The lowest initial rate of GUV budding after the lag phase was seen for GUVs with astaxanthin as the least reducing carotenoid, while the lowest final level of entropy appeared for those with lycopene or β-carotene as a more reducing carotenoid. The combination of astaxanthin and lycopene gave optimal protection against budding with respect to both a longer lag phase and lower final level of entropy by combining good electron acceptance and good electron donation. Quenching of singlet oxygen by carotenoids close to chlorophyll a in the membrane interior in parallel with scavenging of superoxide radicals by astaxanthin anchored in the surface may explain the synergism between carotenoids involving both type I and type II photosensitization by chlorophyll a. PMID:26429551

  14. Effect of carotenoid structure on excited state dynamics of carbonyl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    Messina : Universitá di Messina, 2008. s. 53. [ESF Workshop on Ultrafast Excited-State Processes in Condensed Phases. 18.06.2008-21.06.2008, Santa Tecla] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * carotenoid structure Subject RIV: BO - Biophysics

  15. Heterologous Carotenoid-Biosynthetic Enzymes: Functional Complementation and Effects on Carotenoid Profiles in Escherichia coli

    OpenAIRE

    Song, Gyu Hyeon; Kim, Se Hyeuk; Choi, Bo Hyun; Han, Se Jong; Lee, Pyung Cheon

    2013-01-01

    A limited number of carotenoid pathway genes from microbial sources have been studied for analyzing the pathway complementation in the heterologous host Escherichia coli. In order to systematically investigate the functionality of carotenoid pathway enzymes in E. coli, the pathway genes of carotenogenic microorganisms (Brevibacterium linens, Corynebacterium glutamicum, Rhodobacter sphaeroides, Rhodobacter capsulatus, Rhodopirellula baltica, and Pantoea ananatis) were modified to form syntheti...

  16. Diversity in the carotenoid profiles and the expression of genes related to carotenoid accumulation among citrus genotypes.

    Science.gov (United States)

    Ikoma, Yoshinori; Matsumoto, Hikaru; Kato, Masaya

    2016-01-01

    Carotenoids are not only important to the plants themselves but also are beneficial to human health. Since citrus fruit is a good source of carotenoids for the human diet, it is important to study carotenoid profiles and the accumulation mechanism in citrus fruit. Thus, in the present paper, we describe the diversity in the carotenoid profiles of fruit among citrus genotypes. In regard to carotenoids, such as β-cryptoxanthin, violaxanthin, lycopene, and β-citraurin, the relationship between the carotenoid profile and the expression of carotenoid-biosynthetic genes is discussed. Finally, recent results of quantitative trait locus (QTL) analyses of carotenoid contents and expression levels of carotenoid-biosynthetic genes in citrus fruit are shown. PMID:27069398

  17. Carotenoid-enriched transgenic corn delivers bioavailable carotenoids to poultry and protects them against coccidiosis.

    Science.gov (United States)

    Nogareda, Carmina; Moreno, Jose A; Angulo, Eduardo; Sandmann, Gerhard; Portero, Manuel; Capell, Teresa; Zhu, Changfu; Christou, Paul

    2016-01-01

    Carotenoids are health-promoting organic molecules that act as antioxidants and essential nutrients. We show that chickens raised on a diet enriched with an engineered corn variety containing very high levels of four key carotenoids (β-carotene, lycopene, zeaxanthin and lutein) are healthy and accumulate more bioavailable carotenoids in peripheral tissues, muscle, skin and fat, and more retinol in the liver, than birds fed on standard corn diets (including commercial corn supplemented with colour additives). Birds were challenged with the protozoan parasite Eimeria tenella and those on the high-carotenoid diet grew normally, suffered only mild disease symptoms (diarrhoea, footpad dermatitis and digital ulcers) and had lower faecal oocyst counts than birds on the control diet. Our results demonstrate that carotenoid-rich corn maintains poultry health and increases the nutritional value of poultry products without the use of feed additives. PMID:25846059

  18. Carotenóides: propriedades, aplicações e biotransformação para formação de compostos de aroma Carotenoids: properties, applications and biotransformation in flavor compounds

    Directory of Open Access Journals (Sweden)

    Mariana Uenojo

    2007-06-01

    Full Text Available Carotenoids are widely distributed in nature, providing yellow, orange or red color in a great number of vegetables, microorganisms and in some animals. Carotenoids act as biological antioxidants and seem to play an important role in human health by protecting cells and tissues from the damaging effects of free radicals and singlet oxygen. Several authors describe the oxidative cleavage of carotenoids in flavor compounds as occuring through chemical or photochemical degradations or through biotechnological processes. Biotransformation of carotenoids seems to be a reasonable alternative to produce flavor compounds since these compounds are considered 'natural' ingredients. In this work we describe the properties of some carotenoids, as well as biotechnological approaches to obtain its oxyfunctionalized derivatives.

  19. Photochemical generation of a primary vinyl cation from (E)-bromostyrene: Mechanisms of formation and reaction

    NARCIS (Netherlands)

    Gronheid, R.; Zuilhof, H.; Hellings, M.G.

    2003-01-01

    The photochemistry of (E)-bromostyrene was investigated to determine the nature of the product-forming intermediates and to clarify the mechanism of formation of vinylic cations and vinylic radicals. Both a cation- and a radical-derived product are formed, and the ionic origin of the former product

  20. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  1. Carotenoids: potential allies of cardiovascular health?

    Directory of Open Access Journals (Sweden)

    Maria Alessandra Gammone

    2015-02-01

    Full Text Available Carotenoids are a class of natural, fat-soluble pigments found principally in plants. They have potential antioxidant biological properties because of their chemical structure and interaction with biological membranes. Epidemiologic studies supported the hypothesis that antioxidants could be used as an inexpensive means of both primary and secondary cardiovascular disease (CVD prevention. In fact, the oxidation of low-density lipoproteins (LDL in the vessels plays a key role in the development of atherosclerotic lesions. The resistance of LDL to oxidation is increased by high dietary antioxidant intake, so that carotenoids, as part of food patterns such as the Mediterranean diet, may have beneficial effects on cardiovascular health too. Further properties of carotenoids leading to a potential reduction of cardiovascular risk are represented by lowering of blood pressure, reduction of pro-inflammatory cytokines and markers of inflammation (such as C-reactive protein, and improvement of insulin sensitivity in muscle, liver, and adipose tissues. In addition, recent nutrigenomics studies have focused on the exceptional ability of carotenoids in modulating the expression of specific genes involved in cell metabolism. The aim of this review is to focus attention to this effect of some carotenoids to prevent CVD.

  2. Supercritical Fluid Extraction of Palm Carotenoids

    Directory of Open Access Journals (Sweden)

    Puah C. Wei

    2005-01-01

    Full Text Available The extraction of carotenoids from crude palm oil was carried out in a dynamic (flow- through supercritical fluid extraction system. The carotenoids obtained were quantified using off-line UV-visible spectrophotometry. The effects of operating pressure and temperature, flow rate of the supercritical carbon dioxide (SC-CO2, sample size of feed used on the solubility of palm carotenoids were investigated. The results showed that the extraction of carotenoids was governed by its solubility in the SC-CO2 and can be enhanced by increasing pressure at a constant temperature or decreasing temperature at a constant pressure. Increasing the flow rate and decreasing the sample size can reduce the extraction time but do not enhance the solubility. Palm carotenoids have very low solubility in SC-CO2 in the range of 1.31 x 10-4 g kg-1 to 1.58 x 10-3 g kg-1 for the conditions investigated in this study. The experimental data obtained were compared with those published by other workers and correlated by a density-based equation as proposed by Chrastil.

  3. Radiochemical study of gas-phase reactions of free methyl cations with tetraalkylsilanes

    International Nuclear Information System (INIS)

    Interaction of free methyl-cations with tetraalkylsilanes was studied. Free methyl-cations were prepared by the nuclear-chemical method, based on processes of tritium β-decomposition in the content of many times tritiated methane. Reactions of methyl-cations with tetraalkylsilanes (C1-C4) are accompanied by formation of saturated hydrocarbons. This testifies to elimination of alkyl anions on Si-C and C-C bonds. Intensity of carbamin elimination on Si-C bonds decreases with increase of radical chain length. Processes of methyl-cation substitution for alkyl radical in tetraalkylsilanes with charge transfer to this radical take place along with processes of carbanion elimination

  4. Role of B800 in carotenoid-bacteriochlorophyll energy and electron transfer in LH2 complexes from the purple bacterium Rhodobacter sphaeroides

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Niedzwiedzki, D.; Fuciman, M.; Sundström, V.; Frank, H.A.

    2007-01-01

    Roč. 111, č. 25 (2007), s. 7422-7431. ISSN 1520-6106 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoid radicals * energy transfer Subject RIV: BO - Biophysics Impact factor: 4.086, year: 2007

  5. Fotofísica de carotenóides e o papel antioxidante de b-caroteno Photophysics of carotenoids and the antioxidant role of b-carotene

    OpenAIRE

    Sergio Luis Cardoso

    1997-01-01

    Carotenoid polyenes play a wide role in nature and their photophysical properties make of these pigments a focus of research in photochemistry, photobiology and photomedicine. Some aspects of the singlet and triplet states and, their interaction with molecular and singlet oxygen and free radicals are briefly reviewed in this article.

  6. Fotofísica de carotenóides e o papel antioxidante de b-caroteno Photophysics of carotenoids and the antioxidant role of b-carotene

    Directory of Open Access Journals (Sweden)

    Sergio Luis Cardoso

    1997-10-01

    Full Text Available Carotenoid polyenes play a wide role in nature and their photophysical properties make of these pigments a focus of research in photochemistry, photobiology and photomedicine. Some aspects of the singlet and triplet states and, their interaction with molecular and singlet oxygen and free radicals are briefly reviewed in this article.

  7. Dietary carotenoids predict plumage coloration in wild house finches.

    OpenAIRE

    Hill, Geoffrey E.; Inouye, Caron Y; Montgomerie, Robert

    2002-01-01

    Carotenoid pigments are a widespread source of ornamental coloration in vertebrates and expression of carotenoid-based colour displays has been shown to serve as an important criterion in female mate choice in birds and fishes. Unlike other integumentary pigments, carotenoids cannot be synthesized; they must be ingested. Carotenoid-based coloration is condition-dependent and has been shown to be affected by both parasites and nutritional condition. A controversial hypothesis is that the expre...

  8. Molecular Characterization of Carotenoid Biosynthetic Genes and Carotenoid Accumulation in Lycium chinense

    Directory of Open Access Journals (Sweden)

    Shicheng Zhao

    2014-07-01

    Full Text Available Lycium chinense is a shrub that has health benefits and is used as a source of medicines in Asia. In this study, a full-length cDNA clone encoding β-ring carotene hydroxylase (LcCHXB and partial-length cDNA clones encoding phytoene synthase (LcPSY, phytoene desaturase (LcPDS, ξ-carotene desaturase (LcZDS, lycopene β-cyclase (LcLCYB, lycopene ε-cyclase (LcLCYE, ε-ring carotene hydroxylase (LcCHXE, zeaxanthin epoxidase (LcZEP, carotenoid cleavage dioxygenase (LcCCD1, and 9-cis epoxycarotenoid dioxygenase (LcNCED were identified in L. chinense. The transcripts were constitutively expressed at high levels in leaves, flowers and red fruits, where the carotenoids are mostly distributed. In contrast, most of the carotenoid biosynthetic genes were weakly expressed in the roots and stems, which contained only small amounts of carotenoids. The level of LcLCYE transcripts was very high in leaves and correlated with the abundance of lutein in this plant tissue. During maturation, the levels of lutein and zeaxanthin in L. chinense fruits dramatically increased, concomitant with a rise in the level of β-cryptoxanthin. LcPSY, LcPDS, LcZDS, LcLCYB, and LcCHXE were highly expressed in red fruits, leading to their substantially higher total carotenoid content compared to that in green fruits. Total carotenoid content was high in both the leaves and red fruits of L. chinense. Our findings on the biosynthesis of carotenoids in L. chinense provide insights into the molecular mechanisms involved in carotenoid biosynthesis and may facilitate the optimization of carotenoid production in L. chinense.

  9. Carotenoid content of 50 watermelon cultivars.

    Science.gov (United States)

    Perkins-Veazie, Penelope; Collins, Julie K; Davis, Angela R; Roberts, Warren

    2006-04-01

    The lycopene content of 50 commercial cultivars of seeded and seedless red-fleshed watermelons was determined. Scanning colorimetric and spectrophotometric assays of total lycopene were used to separate watermelon cultivars into low (90 mg/kg fw). Cultivars varied greatly in lycopene content, ranging from 33 to 100 mg/kg. Most of the seeded hybrid cultivars had average lycopene contents. Sixteen of the 33 seedless types had lycopene contents in the high and very high ranges. All-trans-lycopene was the predominant carotenoid (84-97%) in all watermelon cultivars measured by high-performance liquid chromatography, but the germplasm differed in the relative amounts of cis-lycopene, beta-carotene, and phytofluene. Red-fleshed watermelon genotypes vary extensively in carotenoid content and offer opportunities for developing watermelons with specifically enhanced carotenoids. PMID:16569049

  10. Photodegradation of carotenoids in human subjects

    International Nuclear Information System (INIS)

    Photodegradation of vitamins in vitro is responsible for large losses of these nutrients in foods, beverages, and semisynthetic liquid formula diets. In vivo photodegradation of vitamins has been reported for riboflavin in jaundiced infants exposed to blue light and for folate in patients with chronic psoriasis given photochemotherapy. Two recent studies of normal subjects have also shown that photodegradation of carotenoids in plasma occurs with cumulative exposure of the skin to an artificial light source having maximal spectral emission in the UVA range. Females showed a larger effect of the UV light on their plasma carotenoid levels than males. These observations have identified a need for further investigation of the role of sunlight exposure as a determinant of plasma carotenoid levels and vitamin A status in human subjects

  11. Dietary intake of carotenoids and risk of type 2 diabetes

    NARCIS (Netherlands)

    Sluijs, I.; Cadier, E.; Beulens, J. W J; van der A, D. L.; Spijkerman, A. M W; van der Schouw, Y. T.

    2015-01-01

    Background and aims: Carotenoids may reduce diabetes risk, due to their antioxidant properties. However, the association between dietary carotenoids intake and type 2 diabetes risk is still unclear. Therefore, the objective of this study was to examine whether higher dietary carotenoid intakes assoc

  12. The fate of carotenoids in sediments: An overview

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Koopmans, M.P.

    1997-01-01

    Despite carotenoids being abundant natural products, there are only scattered literature reports of carotenoid derivatives (mainly in the form of their 'perhydro' derivatives) in ancient sediments and petroleum. This was thought to be due to the sensitivity of carotenoids toward oxygen and their pre

  13. Dehydrolutein: a metabolically derived carotenoid never observed in raptors

    Institute of Scientific and Technical Information of China (English)

    David COSTANTINI; Vittorio BERTACCHE; Barbara PASTURA; Anthony TURK

    2009-01-01

    @@ Carotenoids are fat-soluble pigments synthesised by photosynthetic organisms (Brush, 1990). Conversely, animals are incapable of synthesizing carotenoids de novo, and they must obtain them through their diet. However, some animal species are able to make some alterations to the basic chemical structure, converting ingested carotenoids into more oxidized and differently coloured forms (Schiedt, 1998).

  14. Dietary factors that affect the bioavailability of carotenoids

    NARCIS (Netherlands)

    Hof, van het K.H.; West, C.E.; Weststrate, J.A.; Hautvast, J.G.A.J.

    2000-01-01

    Carotenoids are thought to contribute to the beneficial effects of increased vegetable consumption. Various dietary factors have an effect on the bioavailability of carotenoids. The type of food matrix in which carotenoids are located is a major factor. The bioavailability of ß-carotene from vegetab

  15. Reactions of alkoxy radicals in aqueous solutions

    International Nuclear Information System (INIS)

    The kinetic and mechanistic properties of alkoxy radicals in organic solvents are briefly reviewed. Owing to the scarcity of such data in aqueous solutions and since reactions at the membrane/water interface may be also biologically important, we have studied the reactivity of these radicals in water and the results of our investigations are reported. Alkoxy radicals were generated by photolytic or radiolytic cleavage of peroxide precursors (tert-butyl hydroperoxide and di-tert-butyl peroxide as well as hydroperoxides of polyunsaturated fatty acids). A quantitative correlation between the structure of various substances, in particular, phenolic antioxidants, and their activity in inhibiting the alkoxy radical-induced bleaching of the water-soluble carotenoid crocin will be discussed. Rate constants for intermolecular reactions of t-BuO. radicals were determined by pulse radiolysis. The diffusion-controlled reaction with the catechol antioxidant nordihydroguaiaretic acid demonstrates an effective competition with the very rapid intra molecular β-fragmentation in water. The results aupport the view that a considerable amount of alkoxy radicals interact with substrates before they can rearrange intramolecularly

  16. Reactions of alkoxy radicals in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Bors, W.; Tait, D.; Michel, C.; Saran, M.; Erben-Russ, M. (Gesellschaft fuer Strahlen- und Umweltforschung m.b.H. Muenchen, Neuherberg (Germany, F.R.). Abt. fuer Strahlenbiologie)

    1984-01-01

    The kinetic and mechanistic properties of alkoxy radicals in organic solvents are briefly reviewed. Owing to the scarcity of such data in aqueous solutions and since reactions at the membrane/water interface may be also biologically important, we have studied the reactivity of these radicals in water and the results of our investigations are reported. Alkoxy radicals were generated by photolytic or radiolytic cleavage of peroxide precursors (tert-butyl hydroperoxide and di-tert-butyl peroxide as well as hydroperoxides of polyunsaturated fatty acids). A quantitative correlation between the structure of various substances, in particular, phenolic antioxidants, and their activity in inhibiting the alkoxy radical-induced bleaching of the water-soluble carotenoid crocin will be discussed. Rate constants for intermolecular reactions of t-BuO. radicals were determined by pulse radiolysis. The diffusion-controlled reaction with the catechol antioxidant nordihydroguaiaretic acid demonstrates an effective competition with the very rapid intra molecular ..beta..-fragmentation in water. The results aupport the view that a considerable amount of alkoxy radicals interact with substrates before they can rearrange intramolecularly.

  17. Regulation of carotenoid accumulation and the expression of carotenoid metabolic genes in citrus juice sacs in vitro

    OpenAIRE

    Zhang, Lancui; Ma, Gang; Kato, Masaya; Yamawaki, Kazuki; Takagi, Toshihiko; Kiriiwa, Yoshikazu; Ikoma, Yoshinori; Matsumoto, Hikaru; Yoshioka, Terutaka; Nesumi, Hirohisa

    2011-01-01

    In the present study, to investigate the mechanisms regulating carotenoid accumulation in citrus, a culture system was set up in vitro with juice sacs of three citrus varieties, Satsuma mandarin (Citrus unshiu Marc.), Valencia orange (Citrus sinensis Osbeck), and Lisbon lemon (Citrus limon Burm.f.). The juice sacs of all the three varieties enlarged gradually with carotenoid accumulation. The changing patterns of carotenoid content and the expression of carotenoid metabolic genes in juice sac...

  18. ZEAXANTHIN EPOXIDASE Activity Potentiates Carotenoid Degradation in Maturing Seed.

    Science.gov (United States)

    Gonzalez-Jorge, Sabrina; Mehrshahi, Payam; Magallanes-Lundback, Maria; Lipka, Alexander E; Angelovici, Ruthie; Gore, Michael A; DellaPenna, Dean

    2016-07-01

    Elucidation of the carotenoid biosynthetic pathway has enabled altering the composition and content of carotenoids in various plants, but to achieve desired nutritional impacts, the genetic components regulating carotenoid homeostasis in seed, the plant organ consumed in greatest abundance, must be elucidated. We used a combination of linkage mapping, genome-wide association studies (GWAS), and pathway-level analysis to identify nine loci that impact the natural variation of seed carotenoids in Arabidopsis (Arabidopsis thaliana). ZEAXANTHIN EPOXIDASE (ZEP) was the major contributor to carotenoid composition, with mutants lacking ZEP activity showing a remarkable 6-fold increase in total seed carotenoids relative to the wild type. Natural variation in ZEP gene expression during seed development was identified as the underlying mechanism for fine-tuning carotenoid composition, stability, and ultimately content in Arabidopsis seed. We previously showed that two CAROTENOID CLEAVAGE DIOXYGENASE enzymes, CCD1 and CCD4, are the primary mediators of seed carotenoid degradation, and here we demonstrate that ZEP acts as an upstream control point of carotenoid homeostasis, with ZEP-mediated epoxidation targeting carotenoids for degradation by CCD enzymes. Finally, four of the nine loci/enzymatic activities identified as underlying natural variation in Arabidopsis seed carotenoids also were identified in a recent GWAS of maize (Zea mays) kernel carotenoid variation. This first comparison of the natural variation in seed carotenoids in monocots and dicots suggests a surprising overlap in the genetic architecture of these traits between the two lineages and provides a list of likely candidates to target for selecting seed carotenoid variation in other species. PMID:27208224

  19. Carotenoid-protein interaction alters the S1 energy of hydroxyechinenone in the Orange Carotenoid Protein

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Chábera, P.; Kerfeld, C.A.

    2013-01-01

    Roč. 1827, č. 3 (2013), s. 248-254. ISSN 0005-2728 Institutional support: RVO:60077344 Keywords : orange-carotenoid protein * excited states * photoprotection Subject RIV: BO - Biophysics Impact factor: 4.829, year: 2013

  20. Radical Geography

    Directory of Open Access Journals (Sweden)

    H. Hataminezhad

    2012-07-01

    Full Text Available Interdisciplinary sciences emerging and specialization were result of historical conditions. Lack of common and grand theories have caused social sciences such as Geography disintegrated to many courses. The Geography science has been divided two main courses, Physical and Human through the time. Every one used another similar science in theoretical principles and methodologies for their domain development and strengthening of their bases. The Human Geography was influenced by Anthropology during nineteenth century and was affected by nineteenth century and dawn twentieth century by Sociology and from mid twentieth century until present time by Biological sciences, Psychology, Political economics and social theories. Radical Geography was one of the Human Geography branches that was influenced by Political economics and left ideology. Radical Geography emphasizes on investigation about quality of life in different spaces and attempts to change socio-economic and spatial relationships, therefore critical Geography is one of its similar approaches.

  1. The carotenoid-continuum: carotenoid-based plumage ranges from conspicuous to cryptic and back again

    Directory of Open Access Journals (Sweden)

    Roberts Mark L

    2010-05-01

    Full Text Available Abstract Background Carotenoids are frequently used by birds to colour their plumage with green, yellow, orange or red hues, and carotenoid-based colours are considered honest signals of quality, although they may have other functions, such as crypsis. It is usually assumed that red through yellow colours have a signalling function while green is cryptic. Here we challenge this notion using the yellow and green colouration of blue tits (Cyanistes caeruleus, great tits (Parus major and greenfinches (Carduelis chloris as a model. Results The relationship between colouration (chroma, computed using visual sensitivities of conspecifics and detectability (contrast against natural backgrounds as perceived by conspecifics and avian predators followed a similar curvilinear pattern for yellow and green plumage with minimum detectability at intermediate levels of carotenoid deposition. Thus, for yellow and green plumage, colours at or close to the point of minimum detectability may aid in crypsis. This may be the case for blue and great tit green and yellow plumage, and greenfinch green plumage, all of which had comparably low levels of detectability, while greenfinch yellow plumage was more chromatic and detectable. As yellow and green blue tit colouration are strongly affected by carotenoid availability during moult, variation in pigment availability between habitats may affect the degree of background-matching or the costliness of producing cryptic plumage. Conclusions Increasing carotenoid-deposition in the integument does not always lead to more conspicuous colours. In some cases, such as in blue or great tits, carotenoid deposition may be selected through enhanced background-matching, which in turn suggests that producing cryptic plumage may entail costs. We stress however, that our data do not rule out a signalling function of carotenoid-based plumage in tits. Rather, it shows that alternative functions are plausible and that assuming a signalling

  2. Carotenoids from Haloarchaea and Their Potential in Biotechnology

    Science.gov (United States)

    Rodrigo-Baños, Montserrat; Garbayo, Inés; Vílchez, Carlos; Bonete, María José; Martínez-Espinosa, Rosa María

    2015-01-01

    The production of pigments by halophilic archaea has been analysed during the last half a century. The main reasons that sustains this research are: (i) many haloarchaeal species possess high carotenoids production availability; (ii) downstream processes related to carotenoid isolation from haloarchaea is relatively quick, easy and cheap; (iii) carotenoids production by haloarchaea can be improved by genetic modification or even by modifying several cultivation aspects such as nutrition, growth pH, temperature, etc.; (iv) carotenoids are needed to support plant and animal life and human well-being; and (v) carotenoids are compounds highly demanded by pharmaceutical, cosmetic and food markets. Several studies about carotenoid production by haloarchaea have been reported so far, most of them focused on pigments isolation or carotenoids production under different culture conditions. However, the understanding of carotenoid metabolism, regulation, and roles of carotenoid derivatives in this group of extreme microorganisms remains mostly unrevealed. The uses of those haloarchaeal pigments have also been poorly explored. This work summarises what has been described so far about carotenoids production by haloarchaea and their potential uses in biotechnology and biomedicine. In particular, new scientific evidence of improved carotenoid production by one of the better known haloarchaeon (Haloferax mediterranei) is also discussed. PMID:26308012

  3. Biologically active polymers from spontaneous carotenoid oxidation: a new frontier in carotenoid activity.

    Directory of Open Access Journals (Sweden)

    James B Johnston

    Full Text Available In animals carotenoids show biological activity unrelated to vitamin A that has been considered to arise directly from the behavior of the parent compound, particularly as an antioxidant. However, the very property that confers antioxidant activity on some carotenoids in plants also confers susceptibility to oxidative transformation. As an alternative, it has been suggested that carotenoid oxidative breakdown or metabolic products could be the actual agents of activity in animals. However, an important and neglected aspect of the behavior of the highly unsaturated carotenoids is their potential to undergo addition of oxygen to form copolymers. Recently we reported that spontaneous oxidation of ß-carotene transforms it into a product dominated by ß-carotene-oxygen copolymers. We now report that the polymeric product is biologically active. Results suggest an overall ability to prime innate immune function to more rapidly respond to subsequent microbial challenges. An underlying structural resemblance to sporopollenin, found in the outer shell of spores and pollen, may allow the polymer to modulate innate immune responses through interactions with the pattern recognition receptor system. Oxygen copolymer formation appears common to all carotenoids, is anticipated to be widespread, and the products may contribute to the health benefits of carotenoid-rich fruits and vegetables.

  4. Energy transfer from carotenoids to bacteriochlorophylls

    Czech Academy of Sciences Publication Activity Database

    Frank, H.A.; Polívka, Tomáš

    Dordrecht : Springer, 2008 - (Hunter, C.; Daldal, F.; Thurnauer, M.; Beatty, J.), s. 218-230 ISBN 978-1-4020-8814-8. - (Advances in Photosynthesis and Respiration. 28) Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * Energy transfer Subject RIV: BO - Biophysics

  5. Excited state properties of aryl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Fuciman, M.; Chábera, P.; Župčanová, Anita; Hříbek, P.; Arellano, J.B.; Vácha, František; Pšenčík, J.; Polívka, Tomáš

    2010-01-01

    Roč. 12, č. 13 (2010), s. 3112-3120. ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited-states * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 3.454, year: 2010

  6. Carotenoid excited states - beyond the standard model

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš

    Göttingen : University of Göttingen, 2007. s. 25. [CERC3 Young Chemists Workshop "Time-resolved methods for studies of chemical reactions". 25.04.2007-27.04.2007, Göttingen] Keywords : Carotenoids Subject RIV: BO - Biophysics

  7. Long-lived coherence in carotenoids

    International Nuclear Information System (INIS)

    We use two-colour vibronic coherence spectroscopy to observe long-lived vibrational coherences in the ground electronic state of carotenoid molecules, with decoherence times in excess of 1 ps. Lycopene and spheroidene were studied isolated in solution, and within the LH2 light-harvesting complex extracted from purple bacteria. The vibrational coherence time is shown to increase significantly for the carotenoid in the complex, providing further support to previous assertions that long-lived electronic coherences in light-harvesting complexes are facilitated by in-phase motion of the chromophores and surrounding proteins. Using this technique, we are also able to follow the evolution of excited state coherences and find that for carotenoids in the light-harvesting complex the (S2|S0) superposition remains coherent for more than 70 fs. In addition to the implications of this long electronic decoherence time, the extended coherence allows us to observe the evolution of the excited state wavepacket. These experiments reveal an enhancement of the vibronic coupling to the first vibrational level of the C-C stretching mode and/or methyl-rocking mode in the ground electronic state 70 fs after the initial excitation. These observations open the door to future experiments and modelling that may be able to resolve the relaxation dynamics of carotenoids in solution and in natural light-harvesting systems.

  8. Continuous production of carotenoids from Dunaliella salina

    NARCIS (Netherlands)

    Kleinegris, D.M.M.; Janssen, M.G.J.; Brandenburg, W.A.; Wijffels, R.H.

    2011-01-01

    During the in situ extraction of ß-carotene from Dunaliella salina, the causal relationship between carotenoid extraction and cell death indicated that cell growth and cell death should be at equilibrium for a continuous in situ extraction process. In a flat-panel photobioreactor that was operated a

  9. Ion-radical intermediates of the radiation-chemical transformations of organic carbonates

    Science.gov (United States)

    Shiryaeva, Ekaterina S.; Sosulin, Ilya S.; Saenko, Elizaveta V.; Feldman, Vladimir I.

    2016-07-01

    The spectral features and reactions of ion-radical intermediates produced from organic carbonates in low-temperature matrices were investigated by EPR spectroscopy and quantum-chemical calculations. It was shown that radical cations of diethyl carbonate and dimethyl carbonate underwent intramolecular hydrogen transfer to yield alkyl-type species, as was suggested previously. Meanwhile, radical cation of EC demonstrates a ring cleavage even at 77 K, while radical cation of PC is probably intrinsically stable and undergo an ion-molecule reaction with a neighboring neutral molecule in dimers or associates. Radical anions were obtained in glassy matrices of diethyl ether or perdeuteroethanol. The radical anions of linear carbonates show photoinduced fragmentation to yield the corresponding alkyl radicals; such process may also occur directly under radiolysis. Radical anions of cyclic carbonates are relatively stable and yield only trace amounts of fragmentation products under similar conditions.

  10. Oligorotaxane Radicals under Orders.

    Science.gov (United States)

    Wang, Yuping; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S; Botros, Youssry Y; Goddard, William A; Wasielewski, Michael R; Stoddart, J Fraser

    2016-02-24

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components-namely oligoviologens-in which different numbers of 4,4'-bipyridinium (BIPY(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations suggest that the reduced oligopseudorotaxanes fold into highly ordered secondary structures as a result of the formation of BIPY(•+) radical cation pairs. Furthermore, by installing bulky stoppers at each end of the oligopseudorotaxanes by means of Cu-free alkyne-azide cycloadditions, their analogous oligorotaxanes, which retain the same stoichiometries as their progenitors, can be prepared. Solution-state studies of the oligorotaxanes indicate that their mechanically interlocked structures lead to the enforced interactions between the dumbbell and ring components, allowing them to fold (contract) in their reduced states and unfold (expand) in their fully oxidized states as a result of Coulombic repulsions. This electrochemically controlled reversible folding and unfolding process, during which the oligorotaxanes experience length contractions and expansions, is reminiscent of the mechanisms of actuation associated with muscle fibers. PMID:27163033

  11. What are carotenoids signaling? Immunostimulatory effects of dietary vitamin E, but not of carotenoids, in Iberian green lizards

    Science.gov (United States)

    Kopena, Renata; López, Pilar; Martín, José

    2014-12-01

    In spite that carotenoid-based sexual ornaments are one of the most popular research topics in sexual selection of animals, the antioxidant and immunostimulatory role of carotenoids, presumably signaled by these colorful ornaments, is still controversial. It has been suggested that the function of carotenoids might not be as an antioxidant per se, but that colorful carotenoids may indirectly reflect the levels of nonpigmentary antioxidants, such as melatonin or vitamin E. We experimentally fed male Iberian green lizards ( Lacerta schreiberi) additional carotenoids or vitamin E alone, or a combination of carotenoids and vitamin E dissolved in soybean oil, whereas a control group only received soybean oil. We examined the effects of the dietary supplementations on phytohaemagglutinin (PHA)-induced skin-swelling immune response and body condition. Lizards that were supplemented with vitamin E alone or a combination of vitamin E and carotenoids had greater immune responses than control lizards, but animals supplemented with carotenoids alone had lower immune responses than lizards supplemented with vitamin E and did not differ from control lizards. These results support the hypothesis that carotenoids in green lizards are not effective as immunostimulants, but that they may be visually signaling the immunostimulatory effects of non-pigmentary vitamin E. In contrast, lizards supplemented with carotenoids alone have higher body condition gains than lizards in the other experimental groups, suggesting that carotenoids may be still important to improve condition.

  12. Stability of polyphenols and carotenoids in strawberry and peach yoghurt throughout in vitro gastrointestinal digestion.

    Science.gov (United States)

    Oliveira, Ana; Pintado, Manuela

    2015-05-01

    The aim of this research was to evaluate the influence of in vitro gastrointestinal digestion on the stability and bio-accessibility of phenolic compounds and carotenoids, as well as on the antioxidant activity in strawberry and peach enriched yoghurt. The radical scavenging capacity of strawberry and peach yoghurt was 480 and 550% higher, respectively, at the level of the intestine than in fruit yoghurt not subjected to digestion. In strawberry the amount of bio-accessible anthocyanins increased during gastric digestion and the transition to the intestinal compartment produced a decrease in all the analyzed classes of polyphenols, being more pronounced in pelargonidin-3-glucoside (65%) and pelargonidin-3-rutinoside (58%). In peach the (+)-catechin content strongly decreased (80%), and neochlorogenic, chlorogenic acid, rutin and the carotenoid zeaxanthin decreased at lower levels, between 32-45%, while β-carotene was rather stable under gastric conditions (increased by 12%) during intestinal digestion. Despite the decrease in the concentration of these bioactive compounds after being subjected to in vitro gastrointestinal digestion, results suggest that fruit yoghurt is an important source of bio-accessible polyphenols and carotenoids and that despite some losses induced by digestion conditions, it still releases relevant amounts at the level of the intestine to be absorbed and to promote health benefits. PMID:25882006

  13. Roaming Radicals

    Science.gov (United States)

    Bowman, Joel M.; Shepler, Benjamin C.

    2011-05-01

    Roaming is a recently verified unusual pathway to molecular products from unimolecular dissociation of an energized molecule. Here we present the evidence for this pathway for H2CO and CH3CHO. Theoretical analysis shows that this path visits the plateau region of the potential energy surface near dissociation to radical products. It is not clear whether roaming is a distinct isolated pathway, in addition to the conventional one via the well-known molecular saddle-point transition state. Evidence is presented to suggest that the two pathways may originate from a single, but highly complicated, dividing surface. Other examples of unusual reaction dynamics are also reviewed.

  14. Mate choice for a male carotenoid-based ornament is linked to female dietary carotenoid intake and accumulation

    Directory of Open Access Journals (Sweden)

    Toomey Matthew B

    2012-01-01

    Full Text Available Abstract Background The coevolution of male traits and female mate preferences has led to the elaboration and diversification of sexually selected traits; however the mechanisms that mediate trait-preference coevolution are largely unknown. Carotenoid acquisition and accumulation are key determinants of the expression of male sexually selected carotenoid-based coloration and a primary mechanism maintaining the honest information content of these signals. Carotenoids also influence female health and reproduction in ways that may alter the costs and benefits of mate choice behaviours and thus provide a potential biochemical link between the expression of male traits and female preferences. To test this hypothesis, we manipulated the dietary carotenoid levels of captive female house finches (Carpodacus mexicanus and assessed their mate choice behavior in response to color-manipulated male finches. Results Females preferred to associate with red males, but carotenoid supplementation did not influence the direction or strength of this preference. Females receiving a low-carotenoid diet were less responsive to males in general, and discrimination among the colorful males was positively linked to female plasma carotenoid levels at the beginning of the study when the diet of all birds was carotenoid-limited. Conclusions Although female preference for red males was not influenced by carotenoid intake, changes in mating responsiveness and discrimination linked to female carotenoid status may alter how this preference is translated into choice. The reddest males, with the most carotenoid rich plumage, tend to pair early in the breeding season. If carotenoid-related variations in female choice behaviour shift the timing of pairing, then they have the potential to promote assortative mating by carotenoid status and drive the evolution of carotenoid-based male plumage coloration.

  15. The effects of ionizing radiations on the main beneficial free radical in Spirulina platensis

    International Nuclear Information System (INIS)

    The methods of mass spectrometry, gas chromatography - mass spectrometry and high performance liquid chromatography were used in the analytical studies performed in order to establish the effects of ionizing radiation on the main beneficial free radical (C Phycocyanin, a-chlorophylls, b-chlorophylls, carotenoids and unsaturated fatty acids) in Spirulina platensis biomass. (author)

  16. Carotenoid Production by Halophilic Archaea Under Different Culture Conditions.

    Science.gov (United States)

    Calegari-Santos, Rossana; Diogo, Ricardo Alexandre; Fontana, José Domingos; Bonfim, Tania Maria Bordin

    2016-05-01

    Carotenoids are pigments that may be used as colorants and antioxidants in food, pharmaceutical, and cosmetic industries. Since they also benefit human health, great efforts have been undertaken to search for natural sources of carotenoids, including microbial ones. The optimization of culture conditions to increase carotenoid yield is one of the strategies used to minimize the high cost of carotenoid production by microorganisms. Halophilic archaea are capable of producing carotenoids according to culture conditions. Their main carotenoid is bacterioruberin with 50 carbon atoms. In fact, the carotenoid has important biological functions since it acts as cell membrane reinforcement and it protects the microorganism against DNA damaging agents. Moreover, carotenoid extracts from halophilic archaea have shown high antioxidant capacity. Therefore, current review summarizes the effect of different culture conditions such as salt and carbon source concentrations in the medium, light incidence, and oxygen tension on carotenoid production by halophilic archaea and the strategies such as optimization methodology and two-stage cultivation already used to increase the carotenoid yield of these microorganisms. PMID:26750123

  17. Carotenoids intake and asthma prevalence in Thai children

    Directory of Open Access Journals (Sweden)

    Sanguansak Rerksuppaphol

    2012-02-01

    Full Text Available Several antioxidant nutrients have been described to inversely correlate with asthma. In order to quantify the intake of these substances, it is possible to measure skin levels by Raman spectroscopy, a novel non-invasive technique that can also be used in children. This cross-sectional school-based study involved 423 children from a rural area of Thailand. Asthmatic children were diagnosed according to a Health Interview for Asthma Control questionnaire. Skin carotenoid levels were measured with Raman spectroscopy. Demographic data were obtained by directly interviewing children and their parents, whereas anthropometric parameters were measured by trained staff. Intake of carotenoids, vitamin A and C were evaluated by a food frequency questionnaire. Overall incidence of asthma in Thai schoolchildren (aged 3.5-17.8 years was 17.3%. There was no significant difference in dietary intake of carotenoids and vitamin A and C, and skin carotenoid level between asthmatic and nonasthmatic children. Skin carotenoid level significantly correlated with all carotenoids and vitamin A intake (P<0.05. Carotenoids and vitamin A and C intakes, and skin carotenoid levels were not associated with the risk of asthma in Thai children. Skin carotenoids correlated with all carotenoids and vitamin A intake in mild to moderate degrees. Raman spectroscopy was confirmed to be a useful tool to determine antioxidant skin levels.

  18. Carotenoids exclusively synthesized in red pepper (capsanthin and capsorubin) protect human dermal fibroblasts against UVB induced DNA damage.

    Science.gov (United States)

    Fernández-García, Elisabet; Carvajal-Lérida, Irene; Pérez-Gálvez, Antonio

    Photoprotection by dietary carotenoids has been linked to their antioxidant properties, in particular quenching of singlet molecular oxygen and scavenging of peroxyl radicals. Here, we compared the DNA-protection and antioxidant effects of selected carotenoids exclusively synthesized in red pepper (capsanthin and capsorubin) to the xanthophyll lutein. Preincubation of human dermal fibroblasts (hdf) with capsanthin and capsorubin significantly counteracted UVB induced cytotoxicity at doses between 0 and 300 mJ cm(-2). Pretreatment of hdf with capsanthin, capsorubin or lutein (1 μM) significantly decreased the formation of DNA strand breaks following irradiation with UVB light. All carotenoids studied decreased caspase-3 cleavage (a marker for UVB-induced apoptosis), however, caspase dependent PARP-1 cleavage was not affected suggesting that the remaining caspase activity is sufficient to promote UVB-induced apoptosis. It is conceivable that carotenoids selectively interfere with cellular responses activated by UVB-mediated damage. Our findings indicate that capsanthin and capsorubin exhibit similar properties to lutein and could be used as a dietary supplement to improve natural photoprotection. PMID:27537377

  19. Evidence of Epigenetic Mechanisms Affecting Carotenoids.

    Science.gov (United States)

    Arango, Jacobo; Beltrán, Jesús; Nuñez, Jonathan; Chavarriaga, Paul

    2016-01-01

    Epigenetic mechanisms are able to regulate plant development by generating non-Mendelian allelic interactions. An example of these are the responses to environmenal stimuli that result in phenotypic variability and transgression amongst important crop traits. The need to predict phenotypes from genotypes to understand the molecular basis of the genotype-by-environment interaction is a research priority. Today, with the recent discoveries in the field of epigenetics, this challenge goes beyond analyzing how DNA sequences change. Here we review examples of epigenetic regulation of genes involved in carotenoid synthesis and degradation, cases in which histone- and/or DNA-methylation, and RNA silencing at the posttranscriptional level affect carotenoids in plants. PMID:27485227

  20. Raman spectra of carotenoids in natural products

    Science.gov (United States)

    Withnall, Robert; Chowdhry, Babur Z.; Silver, Jack; Edwards, Howell G. M.; de Oliveira, Luiz F. C.

    2003-08-01

    Resonance Raman spectra of naturally occurring carotenoids have been obtained from nautilus, periwinkle ( Littorina littorea) and clam shells under 514.5 nm excitation and these spectra are compared with the resonance Raman spectra obtained in situ from tomatoes, carrots, red peppers and saffron. The tomatoes, carrots and red peppers gave rise to resonance Raman spectra exhibiting a ν1 band at ca. 1520 cm -1, in keeping with its assignment to carotenoids with ca. nine conjugated carboncarbon double bonds in their main chains, whereas the resonance Raman spectrum of saffron showed a ν1 band at 1537 cm -1 which can be assigned to crocetin, having seven conjugated carboncarbon double bonds. A correlation between ν1 wavenumber location and effective conjugated chain length has been used to interpret the data obtained from the shells, and the wavenumber position (1522 cm -1) of the ν1 band of the carotenoid in the orange clam shell suggests that it contains nine conjugated double bonds in the main chain. However, the black periwinkle and nautilus shells exhibit ν1 bands at 1504 and 1496 cm -1, respectively. On the basis of the correlation between ν1 wavenumber location and effective conjugated chain length, this indicates that they contain carotenoids with longer conjugated chains, the former having ca. 11 double bonds and the latter ca. 13 or even more. Raman spectra of the nautilus, periwinkle and clam shells also exhibited a strong band at 1085 cm -1 and a doublet with components at 701 and 705 cm -1, which can be assigned to biogenic calcium carbonate in the aragonite crystallographic form.

  1. A Unified Picture of S* in Carotenoids.

    Science.gov (United States)

    Balevičius, Vytautas; Abramavicius, Darius; Polívka, Tomáš; Galestian Pour, Arpa; Hauer, Jürgen

    2016-09-01

    In π-conjugated chain molecules such as carotenoids, coupling between electronic and vibrational degrees of freedom is of central importance. It governs both dynamic and static properties, such as the time scales of excited state relaxation as well as absorption spectra. In this work, we treat vibronic dynamics in carotenoids on four electronic states (|S0⟩, |S1⟩, |S2⟩, and |Sn⟩) in a physically rigorous framework. This model explains all features previously associated with the intensely debated S* state. Besides successfully fitting transient absorption data of a zeaxanthin homologue, this model also accounts for previous results from global target analysis and chain length-dependent studies. Additionally, we are able to incorporate findings from pump-deplete-probe experiments, which were incompatible to any pre-existing model. Thus, we present the first comprehensive and unified interpretation of S*-related features, explaining them by vibronic transitions on either S1, S0, or both, depending on the chain length of the investigated carotenoid. PMID:27509302

  2. Study on cationic photopolymerization reaction of epoxy polysiloxane

    Science.gov (United States)

    Sun, F.; Jiang, S. L.; Liu, J.

    2007-11-01

    The effects of epoxy monomers, concentration of photoinitiator and radical photoinitiators on the photosensitive properties of cationic phopolymerization system with a novel epoxy polysiloxane oligomer (CEPS) were investigated via a gel yield method. The results showed that among the tested epoxy monomers, the reactivity of ERL-4221 with cycloaliphatic epoxy groups was the highest. The optimum concentration of diaryldiodonium salt (SR-1012) was determined as 4-5 wt.%. Increasing the amounts of ERL-4221 in the CEPS cationic photopolymerization system, UV-curing rate increased. Radical photoinitiators with ArC dbnd O structure possessed sensitization capacity to the cationic photoinitiator SR-1012. The photosensitivity of the CEPS system could be up to 165 mJ/cm 2. Adding a small amount of IPA and BP could greatly improve the photosensitivity of CEPS cationic photosensitive system. The optimal quantity of isopropanol added to the system was not more than 2 wt.%.

  3. Study on cationic photopolymerization reaction of epoxy polysiloxane

    International Nuclear Information System (INIS)

    The effects of epoxy monomers, concentration of photoinitiator and radical photoinitiators on the photosensitive properties of cationic phopolymerization system with a novel epoxy polysiloxane oligomer (CEPS) were investigated via a gel yield method. The results showed that among the tested epoxy monomers, the reactivity of ERL-4221 with cycloaliphatic epoxy groups was the highest. The optimum concentration of diaryldiodonium salt (SR-1012) was determined as 4-5 wt.%. Increasing the amounts of ERL-4221 in the CEPS cationic photopolymerization system, UV-curing rate increased. Radical photoinitiators with ArC=O structure possessed sensitization capacity to the cationic photoinitiator SR-1012. The photosensitivity of the CEPS system could be up to 165 mJ/cm2. Adding a small amount of IPA and BP could greatly improve the photosensitivity of CEPS cationic photosensitive system. The optimal quantity of isopropanol added to the system was not more than 2 wt.%

  4. Optimization of carotenoids extraction from Penaeus semisulcatus shrimp wastes

    OpenAIRE

    Gholamreza jahed Khaniki; Parisa Sadighara; Ramin Nabizadeh Nodehi; Mahmood Alimohammadi; Naiema Vakili Saatloo

    2013-01-01

    Objective: To find effective method for carotenoids extraction from shrimp waste which is one of the important sources of natural carotenoids and produced in large quantities in Iran. Methods: Two methods of carotenoids extraction, enzymatic and alkaline (NaOH 1 normal) treatment, were assayed. About 5 g of gritted shrimp wastes were used at each stage. For alkaline treatment, sodium hydroxide were added to shrimp waste. After 48 h, the mixture was filtered and centrifuged. ...

  5. Structure of the principal carotenoid pigment of Cellulomonas biazotea.

    OpenAIRE

    Weeks, O B; Montes, A R; Andrewes, A G

    1980-01-01

    The yellow-pigmented Cellulomonas biazotea, ATCC 486, contains a mixture of carotenoids. The principal compound is a decapreno carotenoid (C50H72O2) tentatively characterized as 2,2'-bis(4-hydroxy-3-methyl-2-butenyl)-gamma,gamma-carotene on the basis of electronic absorption, infrared, proton magnetic resonance, and mass spectrometries. The carotenoid is presumed to be identical to sarcinaxanthin from Sarcina lutea pro-synon. Micrococcus luteus and, therefore, is isomeric with decaprenoxanthi...

  6. Dietary carotenoids in normal and pathological tissues of corpus uteri.

    Directory of Open Access Journals (Sweden)

    Sławomir Wołczyński

    2008-12-01

    Full Text Available Carotenoids and retinyl esters are the source of vitamin A in the human body and its natural derivatives takes part in the regulation of cell replication and differentiation in the human endometrium, may induce the leiomyoma growth and has a role in differentiation of endometrial adenocarcinoma. The aim of the study was to demonstrate the presence of carotenoids in tissues from the normal uterus and from various tumors of the uterine corpus, as well as to compare the total content, major carotenoids and % of carotenoids belonging to the provitamin A group between the tissues examined. Using three independent methods of chromatography (CC, TLC, HPLC we analysed 140 human samples. We identified 13 carotenoids belonging to the eg. provitamin A group and epoxy carotenoids. In all the samples beta-carotene, beta-cryptoxanthin, lutein, neoxanthin, violaxanthin and mutatoxanthin were isolated. In normal tissues, the mean carotenoid content was the highest in the follicular phase endometrium (9.9 microg/g, while the highest percentage of carotenoids belonging to provitamin A group was found in the luteal phase (18.2%. In the pathological group, the highest mean values were demonstrated for epithelial lesions (8.0 microg/g, and within this group - in endometrioid adenocarcinoma (10.8 microg/g. In both groups, violaxanthin, beta-cryptoxanthin, lutein epoxide and mutatoxanthin were the predominant carotenoids. We have demonstrated that all uterine tissues show a concentration of beta-carotene and beta-cryptoxanthin, being the source of vitamin A. The highest total values of carotenoids obtained in the group of endometrioid adenocarcinoma seem to confirm certain enzymatic defects in carotenoid metabolism in the course of the neoplastic process or some metabolic modifications. The finding of astaxanthin - the major antioxidant among carotenoids - in 63% of tissues examined is also significant.

  7. Specific appetite for carotenoids in a colorful bird.

    Directory of Open Access Journals (Sweden)

    Juan Carlos Senar

    Full Text Available BACKGROUND: Since carotenoids have physiological functions necessary for maintaining health, individuals should be selected to actively seek and develop a specific appetite for these compounds. METHODOLOGY/PRINCIPAL FINDINGS: Great tits Parus major in a diet choice experiment, both in captivity and the field, preferred carotenoid-enriched diets to control diets. The food items did not differ in any other aspects measured besides carotenoid content. CONCLUSIONS/SIGNIFICANCE: Specific appetite for carotenoids is here demonstrated for the first time, placing these compounds on a par with essential nutrients as sodium or calcium.

  8. Carboidratos e carotenoides totais em duas variedades de mangarito

    Directory of Open Access Journals (Sweden)

    Ana Paula Sato Ferreira

    2014-05-01

    Full Text Available O objetivo deste trabalho foi avaliar a composição de carboidratos e carotenoides em rizomas mãe e filhos das variedades de mangarito (Xanthosoma riedelianum pequeno e gigante. Amostras dos rizomas coletadas ao longo do ciclo cultural e após 90 dias de armazenamento foram avaliadas quanto aos teores de carboidratos e carotenoides totais. Os rizomas apresentaram aumento no teor de carboidratos, e o rizoma-mãe da variedade pequeno apresentou acréscimos lineares no teor de carotenoides, ao longo do cultivo. O armazenamento reduz os teores de carboidratos e de carotenoides totais em todos os rizomas.

  9. Cyclisation and aromatisation of carotenoids during sediment diagenesis

    OpenAIRE

    Sinninghe Damsté, J. S.; Koster, J; Baas, M.; Koopmans, M.; Kaam-Peters, H.M.E. van; Geenevasen, J.A.J.; Kruk, C.

    1995-01-01

    A novel diaryl isoprenoid with an additional aromatic ring, formed from the diaromatic carotenoid isorenieratene by cyclisation and aromatisation during sediment diagenesis, is identified in carbonaceous sedimentary rocks.

  10. Carotenoid biosynthetic genes in Brassica rapa: comparative genomic analysis, phylogenetic analysis, and expression profiling

    OpenAIRE

    Li, Peirong; Zhang, Shujiang; Zhang, Shifan; Li, Fei; Zhang, Hui; Cheng, Feng; Wu, Jian; Wang, Xiaowu; Sun, Rifei

    2015-01-01

    Background Carotenoids are isoprenoid compounds synthesized by all photosynthetic organisms. Despite much research on carotenoid biosynthesis in the model plant Arabidopsis thaliana, there is a lack of information on the carotenoid pathway in Brassica rapa. To better understand its carotenoid biosynthetic pathway, we performed a systematic analysis of carotenoid biosynthetic genes at the genome level in B. rapa. Results We identified 67 carotenoid biosynthetic genes in B. rapa, which were ort...

  11. Carotenoids in Staple Cereals: Metabolism, Regulation, and Genetic Manipulation.

    Science.gov (United States)

    Zhai, Shengnan; Xia, Xianchun; He, Zhonghu

    2016-01-01

    Carotenoids play a critical role in animal and human health. Animals and humans are unable to synthesize carotenoids de novo, and therefore rely upon diet as sources of these compounds. However, major staple cereals often contain only small amounts of carotenoids in their grains. Consequently, there is considerable interest in genetic manipulation of carotenoid content in cereal grain. In this review, we focus on carotenoid metabolism and regulation in non-green plant tissues, as well as genetic manipulation in staple cereals such as rice, maize, and wheat. Significant progress has been made in three aspects: (1) seven carotenogenes play vital roles in carotenoid regulation in non-green plant tissues, including 1-deoxyxylulose-5-phosphate synthase influencing isoprenoid precursor supply, phytoene synthase, β-cyclase, and ε-cyclase controlling biosynthesis, 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate reductase and carotenoid cleavage dioxygenases responsible for degradation, and orange gene conditioning sequestration sink; (2) provitamin A-biofortified crops, such as rice and maize, were developed by either metabolic engineering or marker-assisted breeding; (3) quantitative trait loci for carotenoid content on chromosomes 3B, 7A, and 7B were consistently identified, eight carotenogenes including 23 loci were detected, and 10 gene-specific markers for carotenoid accumulation were developed and applied in wheat improvement. A comprehensive and deeper understanding of the regulatory mechanisms of carotenoid metabolism in crops will be beneficial in improving our precision in improving carotenoid contents. Genomic selection and gene editing are emerging as transformative technologies for provitamin A biofortification. PMID:27559339

  12. Carotenoids in Staple Cereals: Metabolism, Regulation, and Genetic Manipulation

    Science.gov (United States)

    Zhai, Shengnan; Xia, Xianchun; He, Zhonghu

    2016-01-01

    Carotenoids play a critical role in animal and human health. Animals and humans are unable to synthesize carotenoids de novo, and therefore rely upon diet as sources of these compounds. However, major staple cereals often contain only small amounts of carotenoids in their grains. Consequently, there is considerable interest in genetic manipulation of carotenoid content in cereal grain. In this review, we focus on carotenoid metabolism and regulation in non-green plant tissues, as well as genetic manipulation in staple cereals such as rice, maize, and wheat. Significant progress has been made in three aspects: (1) seven carotenogenes play vital roles in carotenoid regulation in non-green plant tissues, including 1-deoxyxylulose-5-phosphate synthase influencing isoprenoid precursor supply, phytoene synthase, β-cyclase, and ε-cyclase controlling biosynthesis, 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate reductase and carotenoid cleavage dioxygenases responsible for degradation, and orange gene conditioning sequestration sink; (2) provitamin A-biofortified crops, such as rice and maize, were developed by either metabolic engineering or marker-assisted breeding; (3) quantitative trait loci for carotenoid content on chromosomes 3B, 7A, and 7B were consistently identified, eight carotenogenes including 23 loci were detected, and 10 gene-specific markers for carotenoid accumulation were developed and applied in wheat improvement. A comprehensive and deeper understanding of the regulatory mechanisms of carotenoid metabolism in crops will be beneficial in improving our precision in improving carotenoid contents. Genomic selection and gene editing are emerging as transformative technologies for provitamin A biofortification. PMID:27559339

  13. Effect of carotenoid structure on excited-state dynamics of carbonyl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    2009-01-01

    Roč. 11, - (2009), s. 8795-8703. ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : excited-state dynamics * carbonyl carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.116, year: 2009

  14. A molecular genetic analysis of carotenoid biosynthesis and the effects of carotenoid mutations on other photosynthetic genes in Rhodobacter capsulatus

    International Nuclear Information System (INIS)

    The nine known R. capsulatus carotenoid genes are contained within the 46 kilobase (kb) photosynthesis gene cluster. An 11 kb subcluster containing eight of these genes has been cloned and its nucleotide sequence determined. A new gene, crtK, has been located in the middle of the subcluster. The carotenoid gene cluster contains sequences homologous to Escherichia coli ω70 promoters, rho-independent transcription terminators, and prokaryotic transcriptional factor binding sites. The phenotypes and genotypes of ten transposon Tn5.7 insertion mutations within the carotenoid gene cluster have been analyzed, by characterization of the carotenoids accumulated and high resolution mapping of the Tn5.7 insertions. The enzymatic blockages in previously uncharacterized early carotenoid mutants have been determined using a new in vitro synthesis system, suggesting specific roles for the CrtB and CrtE gene products. The expression of six of the eight carotenoid genes in the cluster is induced upon the shift from dark chemoheterotrophic to anaerobic photosynthetic growth. The magnitude of the induction is equivalent to that of genes encoding structural photosynthesis polypeptides, although the carotenoid genes are induced earlier after the growth shift. Different means of regulating photosynthesis genes in R. capsulatus are discussed, and a rationale for the temporal pattern of expression of the carotenoid genes during photosynthetic adaptation is presented. Comparison of the deduced amino acid sequences of the two dehydrogenases of the R. capsulatus carotenoid biosynthesis pathway reveals two regions of strong similarity. The effect of carotenoid mutations on the photosynthetic phenotype has been studied by examining growth rates, pigments, pigment-protein complexes and gene expression for a complete set of carotenoid mutants. 161 refs

  15. The effects of dietary carotenoid supplementation and retinal carotenoid accumulation on vision-mediated foraging in the house finch.

    Directory of Open Access Journals (Sweden)

    Matthew B Toomey

    Full Text Available BACKGROUND: For many bird species, vision is the primary sensory modality used to locate and assess food items. The health and spectral sensitivities of the avian visual system are influenced by diet-derived carotenoid pigments that accumulate in the retina. Among wild House Finches (Carpodacus mexicanus, we have found that retinal carotenoid accumulation varies significantly among individuals and is related to dietary carotenoid intake. If diet-induced changes in retinal carotenoid accumulation alter spectral sensitivity, then they have the potential to affect visually mediated foraging performance. METHODOLOGY/PRINCIPAL FINDINGS: In two experiments, we measured foraging performance of house finches with dietarily manipulated retinal carotenoid levels. We tested each bird's ability to extract visually contrasting food items from a matrix of inedible distracters under high-contrast (full and dimmer low-contrast (red-filtered lighting conditions. In experiment one, zeaxanthin-supplemented birds had significantly increased retinal carotenoid levels, but declined in foraging performance in the high-contrast condition relative to astaxanthin-supplemented birds that showed no change in retinal carotenoid accumulation. In experiments one and two combined, we found that retinal carotenoid concentrations predicted relative foraging performance in the low- vs. high-contrast light conditions in a curvilinear pattern. Performance was positively correlated with retinal carotenoid accumulation among birds with low to medium levels of accumulation (∼0.5-1.5 µg/retina, but declined among birds with very high levels (>2.0 µg/retina. CONCLUSION/SIGNIFICANCE: Our results suggest that carotenoid-mediated spectral filtering enhances color discrimination, but that this improvement is traded off against a reduction in sensitivity that can compromise visual discrimination. Thus, retinal carotenoid levels may be optimized to meet the visual demands of specific

  16. A molecular genetic analysis of carotenoid biosynthesis and the effects of carotenoid mutations on other photosynthetic genes in Rhodobacter capsulatus

    Energy Technology Data Exchange (ETDEWEB)

    Armstrong, G.A.

    1989-04-01

    The nine known R. capsulatus carotenoid genes are contained within the 46 kilobase (kb) photosynthesis gene cluster. An 11 kb subcluster containing eight of these genes has been cloned and its nucleotide sequence determined. A new gene, crtK, has been located in the middle of the subcluster. The carotenoid gene cluster contains sequences homologous to Escherichia coli ..omega../sup 70/ promoters, rho-independent transcription terminators, and prokaryotic transcriptional factor binding sites. The phenotypes and genotypes of ten transposon Tn5.7 insertion mutations within the carotenoid gene cluster have been analyzed, by characterization of the carotenoids accumulated and high resolution mapping of the Tn5.7 insertions. The enzymatic blockages in previously uncharacterized early carotenoid mutants have been determined using a new in vitro synthesis system, suggesting specific roles for the CrtB and CrtE gene products. The expression of six of the eight carotenoid genes in the cluster is induced upon the shift from dark chemoheterotrophic to anaerobic photosynthetic growth. The magnitude of the induction is equivalent to that of genes encoding structural photosynthesis polypeptides, although the carotenoid genes are induced earlier after the growth shift. Different means of regulating photosynthesis genes in R. capsulatus are discussed, and a rationale for the temporal pattern of expression of the carotenoid genes during photosynthetic adaptation is presented. Comparison of the deduced amino acid sequences of the two dehydrogenases of the R. capsulatus carotenoid biosynthesis pathway reveals two regions of strong similarity. The effect of carotenoid mutations on the photosynthetic phenotype has been studied by examining growth rates, pigments, pigment-protein complexes and gene expression for a complete set of carotenoid mutants. 161 refs.

  17. Genotype and Environment Effects on Carotenoid Content of Broccoli

    Science.gov (United States)

    Carotenoids are secondary plant metabolites in vegetables reported to confer various positive health-promoting effects when consumed. Brassica oleracea L. vegetables are recognized as excellent sources of dietary carotenoids. Broccoli has emerged as the most important B. oleracea crop in the US an...

  18. Regulatory control of carotenoid accumulation in winter squash during storage

    Science.gov (United States)

    Postharvest storage of fruits and vegetables is often required and frequently results in nutritional quality change. In this study, we investigated carotenoid storage plastids, carotenoid content, and its regulation during 3-month storage of winter squash butternut fruits. We showed that storage imp...

  19. Optimization of carotenoids extraction from Penaeus semisulcatus shrimp wastes

    Directory of Open Access Journals (Sweden)

    Gholamreza jahed Khaniki

    2013-09-01

    Full Text Available Objective: To find effective method for carotenoids extraction from shrimp waste which is one of the important sources of natural carotenoids and produced in large quantities in Iran. Methods: Two methods of carotenoids extraction, enzymatic and alkaline (NaOH 1 normal treatment, were assayed. About 5 g of gritted shrimp wastes were used at each stage. For alkaline treatment, sodium hydroxide were added to shrimp waste. After 48 h, the mixture was filtered and centrifuged. Results: Alcalase extraction produced (234.00±2.00 mg/L carotenoid and NaOH extraction produced (170.00±1.53 mg/L carotenoid. Based on the samples analyzed, alcalase enzyme showed more efficiency than NaOH extraction to achieve carotenoids from shrimp waste. Conclusions: It can be concluded that using alcalase enzyme for carotenoids extraction can produce higher carotenoids concentration than NaOH extraction method. So alcalase enzyme method can be used for achieving this kind of antioxidant.

  20. Non-invasive in vivo measurement of macular carotenoids

    Science.gov (United States)

    Lambert, James L. (Inventor); Borchert, Mark S. (Inventor)

    2009-01-01

    A non-invasive in vivo method for assessing macular carotenoids includes performing Optical Coherence Tomography (OCT) on a retina of a subject. A spatial representation of carotenoid levels in the macula based on data from the OCT of the retina can be generated.

  1. Manipulation of Carotenoid Content in Plants to Improve Human Health.

    Science.gov (United States)

    Alós, Enriqueta; Rodrigo, Maria Jesús; Zacarias, Lorenzo

    2016-01-01

    Carotenoids are essential components for human nutrition and health, mainly due to their antioxidant and pro-vitamin A activity. Foods with enhanced carotenoid content and composition are essential to ensure carotenoid feasibility in malnourished population of many countries around the world, which is critical to alleviate vitamin A deficiency and other health-related disorders. The pathway of carotenoid biosynthesis is currently well understood, key steps of the pathways in different plant species have been characterized and the corresponding genes identified, as well as other regulatory elements. This enables the manipulation and improvement of carotenoid content and composition in order to control the nutritional value of a number of agronomical important staple crops. Biotechnological and genetic engineering-based strategies to manipulate carotenoid metabolism have been successfully implemented in many crops, with Golden rice as the most relevant example of β-carotene improvement in one of the more widely consumed foods. Conventional breeding strategies have been also adopted in the bio-fortification of carotenoid in staple foods that are highly consumed in developing countries, including maize, cassava and sweet potatoes, to alleviate nutrition-related problems. The objective of the chapter is to summarize major breakthroughs and advances in the enhancement of carotenoid content and composition in agronomical and nutritional important crops, with special emphasis to their potential impact and benefits in human nutrition and health. PMID:27485228

  2. Optimization of carotenoids extraction from Penaeus semisulcatus shrimp wastes

    Institute of Scientific and Technical Information of China (English)

    Gholamreza jahed Khaniki; Parisa Sadighara; Ramin Nabizadeh Nodehi; Mahmood Alimohammadi; Naiema Vakili Saatloo

    2013-01-01

    Objective: To find effective method for carotenoids extraction from shrimp waste which is one of the important sources of natural carotenoids and produced in large quantities in Iran. Methods: Two methods of carotenoids extraction, enzymatic and alkaline (NaOH 1 normal) treatment, were assayed. About 5 g of gritted shrimp wastes were used at each stage. For alkaline treatment, sodium hydroxide were added to shrimp waste. After 48 h, the mixture was filtered and centrifuged.Results:Alcalase extraction produced (234.00±2.00) mg/L carotenoid and NaOH extraction produced (170.00±1.53) mg/L carotenoid. Based on the samples analyzed, alcalase enzyme showed more efficiency than NaOH extraction to achieve carotenoids from shrimp waste.Conclusions:It can be concluded that using alcalase enzyme for carotenoids extraction can produce higher carotenoids concentration than NaOH extraction method. So alcalase enzyme method can be used for achieving this kind of antioxidant.

  3. Promotion of radiation-induced cationic polymerization by onium salts

    International Nuclear Information System (INIS)

    The radiation-induced cationic polymerization of styrene derivatives was studied in the presence of diphenyliodonium and triphenylsulfonium hexafluorophosphates in dichloromethane. A remarkable promotion of the polymerization was observed in the presence of the salts. The pulse radiolysis study revealed that the promotion of the polymerization is due to the ion-pair formation between the initiating cations and the nonnucleophilic complex metal halide anions of the salts resulting in the stabilization of the cations toward neutralization. An additional effect observed in the case of diphenyliodonium salt is the oxidation of free radical species to the cations responsible for the polymerization. An increase in molecular weight at low temperature suggested that the propagating cations are also paired with the counterions derived from the salts. (author)

  4. Importancia nutricional de los pigmentos carotenoides

    OpenAIRE

    Meléndez Martínez, Antonio Jesús; Vicario Romero, Isabel; Heredia Mira, Francisco José

    2004-01-01

    Los pigmentos carotenoides son compuestos responsables de la coloración de gran número de alimentos vegetales y animales, como zanahorias, zumo de naranja, tomates, salmón y yema del huevo. Desde hace muchos años, se sabe que algunos de estos compuestos, como a y b-caroteno, así como la b-criptoxantina, son provitaminas A. No obstante, estudios recientes han puesto de manifiesto las propiedades antioxidantes de estos pigmentos, así como su eficacia en la prevención de ciertas enfermedades del...

  5. Carotenoids and health signalling in animals

    Czech Academy of Sciences Publication Activity Database

    Vinkler, Michal; Svobodová, J.; Maršík, Petr; Albrecht, Tomáš

    Hauppauge : Nova Science Publishers, 2011 - (Yamaguchi, M.), s. 189-234 ISBN 978-1-61209-713-8 R&D Projects: GA ČR GA206/08/1281; GA ČR GA206/08/0640; GA ČR GAP505/10/1871; GA MŠk LC06073 Institutional research plan: CEZ:AV0Z60930519; CEZ:AV0Z50380511 Keywords : carotenoids * condition * diseases * health * ornamentation * oxidative stress * parasites * sexual signalling Subject RIV: EG - Zoology https://www.novapublishers.com/catalog/product_info.php?products_id=22091

  6. The intake of carotenoids in Denmark

    DEFF Research Database (Denmark)

    Leth, Torben; Jakobsen, Jette; Andersen, N. L.

    2000-01-01

    To estimate the intake of carotenoids in the Danish population Danish fruits and vegetables were screened with an HPLC method consisting of extraction with ethanol:tetrahydrofuran, separation by reversed phase HPLC with the mobile phase acetonitril:methanol:dichlormethan, triethylamin, BHT and...... detection at 450 nm. Food intakes were estimated by the national dietary surveys (1995) from 7 days' food registration (n = 1837 adults), which allows the whole diet to be described by the mean intake and intake distribution of 207 raw or semiprepared foods. By multiplication with the mean content in the...

  7. Carotenoids and Their Isomers: Color Pigments in Fruits and Vegetables

    Directory of Open Access Journals (Sweden)

    Yueming Jiang

    2011-02-01

    Full Text Available Fruits and vegetables are colorful pigment-containing food sources. Owing to their nutritional benefits and phytochemicals, they are considered as ‘functional food ingredients’. Carotenoids are some of the most vital colored phytochemicals, occurring as all-trans and cis-isomers, and accounting for the brilliant colors of a variety of fruits and vegetables. Carotenoids extensively studied in this regard include β-carotene, lycopene, lutein and zeaxanthin. Coloration of fruits and vegetables depends on their growth maturity, concentration of carotenoid isomers, and food processing methods. This article focuses more on several carotenoids and their isomers present in different fruits and vegetables along with their concentrations. Carotenoids and their geometric isomers also play an important role in protecting cells from oxidation and cellular damages.

  8. Carotenoids in Marine Invertebrates Living along the Kuroshio Current Coast

    Directory of Open Access Journals (Sweden)

    Yoshikazu Sakagami

    2011-08-01

    Full Text Available Carotenoids of the corals Acropora japonica, A. secale, and A. hyacinthus, the tridacnid clam Tridacna squamosa, the crown-of-thorns starfish Acanthaster planci, and the small sea snail Drupella fragum were investigated. The corals and the tridacnid clam are filter feeders and are associated with symbiotic zooxanthellae. Peridinin and pyrrhoxanthin, which originated from symbiotic zooxanthellae, were found to be major carotenoids in corals and the tridacnid clam. The crown-of-thorns starfish and the sea snail D. fragum are carnivorous and mainly feed on corals. Peridinin-3-acyl esters were major carotenoids in the sea snail D. fragum. On the other hand, ketocarotenoids such as 7,8-didehydroastaxanthin and astaxanthin were major carotenoids in the crown-of-thorns starfish. Carotenoids found in these marine animals closely reflected not only their metabolism but also their food chains.

  9. Biosynthesis of Carotenoids in Plants: Enzymes and Color.

    Science.gov (United States)

    Rosas-Saavedra, Carolina; Stange, Claudia

    2016-01-01

    Carotenoids are the most important biocolor isoprenoids responsible for yellow, orange and red colors found in nature. In plants, they are synthesized in plastids of photosynthetic and sink organs and are essential molecules for photosynthesis, photo-oxidative damage protection and phytohormone synthesis. Carotenoids also play important roles in human health and nutrition acting as vitamin A precursors and antioxidants. Biochemical and biophysical approaches in different plants models have provided significant advances in understanding the structural and functional roles of carotenoids in plants as well as the key points of regulation in their biosynthesis. To date, different plant models have been used to characterize the key genes and their regulation, which has increased the knowledge of the carotenoid metabolic pathway in plants. In this chapter a description of each step in the carotenoid synthesis pathway is presented and discussed. PMID:27485218

  10. Metabolism of carotenoids and apocarotenoids during ripening of raspberry fruit

    DEFF Research Database (Denmark)

    Beekwilder, J; van der Meer, IM; Simicb, A;

    2008-01-01

    Carotenoids are important lipophilic antioxidants in fruits. Apocarotenoids such as α-ionone and β-ionone, which are breakdown products of carotenoids, are important for the flavor characteristics of raspberry fruit, and have also been suggested to have beneficial effects on human health. Raspberry...... is one of the few fruits where fruit ripening is accompanied by the massive production of apocarotenoids. In this paper, changes in levels of carotenoids and apocarotenoids during raspberry fruit ripening are described. In addition, the isolation and characterization of a gene encoding a carotenoid...... cleavage dioxygenase (CCD), which putatively mediates the degradation of carotenoids to apocarotenoids during raspberry fruit ripening, is reported. Such information helps us to better understand how these compounds are produced in plants and may also enable us to develop novel strategies for improved...

  11. On the role of labile oxocomplexes in carotenoids antioxidant activity

    International Nuclear Information System (INIS)

    Early stages of the interaction of carotenoids and molecular oxygen are studied and role of its interaction in the processes responsible for radiation resistance of carotenoids, superoxide dismutase activity to the singlet oxygen quenching. Ethanol and aqueous solutions of the carotenoids (phosphate buffer with pH 7.5) were exposed to accelerated electron flux at pulse regime and dose rate (0.7-2.0)x1017 eV/ml imp in the dark and in case of combined effect of radiation and light. It is concluded that at the early stages of processes with the participation of carotenoids the formation of reversible complexes with charge transfer plays the important role. Properties and reaction capability of these complexes are determined by the peculiarities in chemical structure of carotenoid molecules

  12. Variation in Content of Carotenoids and Vitamin C in Carrots

    Directory of Open Access Journals (Sweden)

    Jana MATĚJKOVÁ

    2010-12-01

    Full Text Available Carrots are the most popular and wide-spread of all root vegetables, and are the principal source of carotenoids in human diet. The purpose of this study was to examine differences between cultivars and the effect of storage regarding the carotenoid and vitamin C content in carrots. Six carrot cultivars were used in this study, ranging from early to late ones. Observed carotenoid content ranged from 60 mg kg-1 to 134 mg kg-1. Significantly higher levels of carotenoids were found in late and moderately late cultivars in comparison to early ones. Vitamin C content in these cultivars ranged from 54 mg kg-1 to 132 mg kg-1. Significantly higher contents of vitamin C were also found in the late cultivars. 30-day storage resulted in a significant reduction in vitamin C content, on average of 47%. There was also a reduction in the carotenoids content, but to a lesser extent, on average of 11%.

  13. Isomerization of metastable amine radical cations by dissociation-recombination

    DEFF Research Database (Denmark)

    Pedersen, Anders Holmen; Nielsen, Christian Benedikt; Bojesen, Gustav;

    2015-01-01

    The metastable molecular ions of primary aliphatic amines branched at C2 can isomerize by cleavage-recombination, thereby facilitating fragmentation reactions that require less energy than simple cleavage of the initial molecular ion. This process complements the reactions described by Audier to...

  14. Oxidative stress and astaxanthin: The novel supernutrient carotenoid

    Directory of Open Access Journals (Sweden)

    Sasmita Biswal

    2014-01-01

    Full Text Available Background: Oxidative stress and inflammation leads to, generation and overproduction of the reactive oxygen species and reactive nitrogen species and hence are responsible for many diseases such as Alzheimer′s disease, Parkinson′s disease, diabetes mellitus, rheumatoid arthritis, and neurodegenerative motor neuron diseases. Antioxidants are found in varying amounts in vegetables, fruits, grain cereals, eggs, meat, legumes and nuts. However, there is always a search for antioxidants that can quench and breakup the chain of generation of free-radicals. Aims: Astaxanthin, a ketocarotenoid, has exceptional antioxidant activity and hence can be used for prevention of cardiovascular diseases, inflammatory and neurodegenerative diseases, boosting of the immune system, anti-Helicobacter pylori activity, and cataract prevention. Hence, an attempt has performed in this review to compile data on astaxanthin and its several diverse applications over the last decade with an aim to escalate the intense interest in undertaking new research on this natural fascinating molecule. Materials and Methods: A literature search using astaxanthin and antioxidants as keywords using Google as the search engine was done and the data obtained were compiled and presented. Results and Conclusions: Astaxanthin can be a great supplement for everyone in enhancing immunity, preventing a myriad of diseases in our hectic lifestyle by providing more energy, reducing oxidative damage, producing clarity of vision as well as protection from the harmful ultraviolet rays of the sun! Further the immunomodulatory, antioxidative, and antiinflammatory activity of astaxanthin a bioactive natural supernutrient carotenoid may be very important to human health in treating many such untreatable diseases.

  15. Intraspecific Variation in Carotenoids of Brassica oleracea var. sabellica.

    Science.gov (United States)

    Mageney, Vera; Baldermann, Susanne; Albach, Dirk C

    2016-04-27

    Carotenoids are best known as a source of natural antioxidants. Physiologically, carotenoids are part of the photoprotection in plants as they act as scavengers of reactive oxygen species (ROS). An important source of carotenoids in European food is Brassica oleracea. Focusing on the most abundant carotenoids, we estimated the contents of ß-carotene, (9Z)-neoxanthin, zeaxanthin, and lutein as well as those of chlorophylls a and b to assess their variability in Brassica oleracea var. sabellica. Our analyses included more than 30 cultivars categorized in five distinct sets grouped according to morphological characteristics or geographical origin. Our results demonstrated specific carotenoid patterns characteristic for American, Italian, and red-colored kale cultivars. Moreover, we demonstrated a tendency of high zeaxanthin proportions under traditional harvest conditions, which accord to low-temperature regimes. We also compared the carotenoid patterns of self-generated hybrid lines. Corresponding findings indicated that crossbreeding has a high potential for carotenoid content optimization in kale. PMID:27045759

  16. A complex carotenoid palette tunes avian colour vision.

    Science.gov (United States)

    Toomey, Matthew B; Collins, Aaron M; Frederiksen, Rikard; Cornwall, M Carter; Timlin, Jerilyn A; Corbo, Joseph C

    2015-10-01

    The brilliantly coloured cone oil droplets of the avian retina function as long-pass cut-off filters that tune the spectral sensitivity of the photoreceptors and are hypothesized to enhance colour discrimination and improve colour constancy. Although it has long been known that these droplets are pigmented with carotenoids, their precise composition has remained uncertain owing to the technical challenges of measuring these very small, dense and highly refractile optical organelles. In this study, we integrated results from high-performance liquid chromatography, hyperspectral microscopy and microspectrophotometry to obtain a comprehensive understanding of oil droplet carotenoid pigmentation in the chicken (Gallus gallus). We find that each of the four carotenoid-containing droplet types consists of a complex mixture of carotenoids, with a single predominant carotenoid determining the wavelength of the spectral filtering cut-off. Consistent with previous reports, we find that the predominant carotenoid type in the oil droplets of long-wavelength-sensitive, medium-wavelength-sensitive and short-wavelength-sensitive type 2 cones are astaxanthin, zeaxanthin and galloxanthin, respectively. In addition, the oil droplet of the principal member of the double cone contains a mixture of galloxanthin and two hydroxycarotenoids (lutein and zeaxanthin). Short-wavelength-absorbing apocarotenoids are present in all of the droplet types, providing filtering of light in a region of the spectrum where filtering by hydroxy- and ketocarotenoids may be incomplete. Thus, birds rely on a complex palette of carotenoid pigments within their cone oil droplets to achieve finely tuned spectral filtering. PMID:26446559

  17. The carotenoid biosynthetic pathway: thinking in all dimensions.

    Science.gov (United States)

    Shumskaya, Maria; Wurtzel, Eleanore T

    2013-07-01

    The carotenoid biosynthetic pathway serves manifold roles in plants related to photosynthesis, photoprotection, development, stress hormones, and various volatiles and signaling apocarotenoids. The pathway also produces compounds that impact human nutrition and metabolic products that contribute to fragrance and flavor of food and non-food crops. It is no surprise that the pathway has been a target of metabolic engineering, most prominently in the case of Golden Rice. The future success and predictability of metabolic engineering of carotenoids rests in the ability to target carotenoids for specific physiological purposes as well as to simultaneously modify carotenoids along with other desired traits. Here, we ask whether predictive metabolic engineering of the carotenoid pathway is indeed possible. Despite a long history of research on the pathway, at this point in time we can only describe the pathway as a parts list and have almost no knowledge of the location of the complete pathway, how it is assembled, and whether there exists any trafficking of the enzymes or the carotenoids themselves. We discuss the current state of knowledge regarding the "complete" pathway and make the argument that predictive metabolic engineering of the carotenoid pathway (and other pathways) will require investigation of the three dimensional state of the pathway as it may exist in plastids of different ultrastructures. Along with this message we point out the need to develop new types of visualization tools and resources that better reflect the dynamic nature of biosynthetic pathways. PMID:23683930

  18. Radicals of DNA and DNA nucleotides generated by ionising radiation

    International Nuclear Information System (INIS)

    A first stage of cell processes leading to DNA damage of initiated by radical reactions. In a model system such transformations were generated by ionising radiation which involves production of electron loss and electron gain centers of the substrate and radical formation. Using cryogenic ESR spectroscopy it was found that the DNA nucleotides, which convert to radical anions upon electron capture undergo the separation of unpaired spin and charge due to protonation. Circular and linear dichroism studies enabled to conclude that iron ions(III) induce strong changes in the DNA helical structure indicating their coordination with nitrogen bases. The repair of DNA radicals produced via radiolytic oxidation, i.e. the guanine radical cation and the allyl type radical of thymine, is possible at elevated temperatures due to the involvement of sulphydryl groups. The influence of the thiol charge is then limited

  19. The Capability of Rhodotorula slooffiae to Produce Carotenoid

    Directory of Open Access Journals (Sweden)

    Farzaneh Sadat Naghavi

    2015-02-01

    Full Text Available Background: Rhodotorula is characterized by the absence of ballistoconidia, fermentation ability, and starch-like compounds. Biology of the species is not well-identified; therefore molecular identification is required. Sequence analysis of the D1/D2 region can be used for the identification of the majority of Basidiomycetous species. Carotenoids which are natural pigments can be synthesized by some genera of yeasts such as Rhodotorula. The increase of demand for carotenoids obtained from natural sources has promoted major efforts to recognize potential microbial sources. The aims of this study were to identify a strain isolated from leather wastewater and to investigate its carotenoid production ability. The effect of 2 different medium (Semi-synthetic medium (MMS and yeast malt extract medium (YM on biomass and carotenoid production was studied. Materials and Methods: In this experimental study, sequence analysis of the D1/D2 region in addition to morphological and biochemical characterization to identify the strain was carried out. To isolate the carotenoid pigment, cells were suspended in acetone and broken using a homogenizer, followed by centrifugation and supernatant was separated; thus pigments were measured spectrophotometrically at 450 nM using the extinction coefficient E1%450=2500. Results: Identification processes represented strain SG006 as a Rhodotorula slooffiae. The sequence was deposited in the Gene Bank database with accession number JX997835. The results showed that SG006 are able to produce carotenoid and MMS medium promoted carotenoid production. Conclusion: We found that Rhodotorula slooffiae showed the ability to produce carotenoid. However, further work is needed to optimize of the amount of product and to characterize the carotenoids.

  20. Carotenoid maintenance handicap and the physiology of carotenoid-based signalisation of health

    Czech Academy of Sciences Publication Activity Database

    Vinkler, Michal; Albrecht, Tomáš

    2010-01-01

    Roč. 97, č. 1 (2010), s. 19-28. ISSN 0028-1042 R&D Projects: GA ČR GA206/06/0851; GA MŠk LC06073; GA ČR GA206/08/1281 Institutional research plan: CEZ:AV0Z60930519 Keywords : Carotenoids * Ornamentation * Oxidative stress * Testosterone * Trade-off Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.250, year: 2010

  1. Synthetic Biology and Metabolic Engineering for Marine Carotenoids: New Opportunities and Future Prospects

    OpenAIRE

    Chonglong Wang; Jung-Hun Kim; Seon-Won Kim

    2014-01-01

    Carotenoids are a class of diverse pigments with important biological roles such as light capture and antioxidative activities. Many novel carotenoids have been isolated from marine organisms to date and have shown various utilizations as nutraceuticals and pharmaceuticals. In this review, we summarize the pathways and enzymes of carotenoid synthesis and discuss various modifications of marine carotenoids. The advances in metabolic engineering and synthetic biology for carotenoid production ...

  2. Potential implications for epigenetic regulation of carotenoid biosynthesis during root and shoot development

    OpenAIRE

    Cazzonelli, Christopher Ian; Yin, Kuide; Pogson, Barry J.

    2009-01-01

    Major regulators of carotenoid biosynthesis have remained rather elusive even though the flux through the branch in the carotenoid pathway can affect plant development in response to environmental stimuli, such as light. Our recent investigations demonstrated that the production of the most abundant carotenoid in plants, lutein, is regulated by carotenoid isomerase (CRTISO) activity at a rate-limiting step of this branch point in carotenoid biosynthesis. CRTISO is required to isomerase cis-ca...

  3. Carboidratos e carotenoides totais em duas variedades de mangarito

    OpenAIRE

    Ana Paula Sato Ferreira; Mário Puiatti; Ariana Mota Pereira; Paulo Roberto Cecon; Aline da Silva Bhering; Teresa Drummond Correia Mendes

    2014-01-01

    O objetivo deste trabalho foi avaliar a composição de carboidratos e carotenoides em rizomas mãe e filhos das variedades de mangarito (Xanthosoma riedelianum) pequeno e gigante. Amostras dos rizomas coletadas ao longo do ciclo cultural e após 90 dias de armazenamento foram avaliadas quanto aos teores de carboidratos e carotenoides totais. Os rizomas apresentaram aumento no teor de carboidratos, e o rizoma-mãe da variedade pequeno apresentou acréscimos lineares no teor de carotenoides, ao long...

  4. Cloning and Characterization of a Lycium chinense Carotenoid Isomerase Gene Enhancing Carotenoid Accumulation in Transgenic Tobacco

    Institute of Scientific and Technical Information of China (English)

    李招娣; 季静; 王罡

    2015-01-01

    Carotenoid isomerase(CRTISO)is a key enzyme that catalyzes the conversion of cis-lycopene to all-trans lycopene. In this study, we isolated and characterized the CRTISO gene from Lycium chinense (LcCRTISO) for the first time. The open reading frame of LcCRTISO was 1 815 bp encoding a protein of 604 amino acids with a molecular mass of 66.24 kDa. Amino acid sequence analysis revealed that the LcCRTISO had a high level of simi-larity to other CRTISO. Phylogenetic analysis displayed that LcCRTISO kept a closer relationship with the CRTISO of plants than with those of other species. Semi-quantitative PCR analysis indicated that LcCRTISO gene was expressed in all tissues tested with the highest expression in maturing fruits. The overexpression of LcCRTISO gene in transgenic tobacco resulted in an increase of total carotenoids in the leaves withβ-carotene and lutein being the predominants. The results obtained here clearly suggested that the LcCRTISO gene was a promising candidate for carotenoid production.

  5. Photo- and radio-induced radical oxidation of the purine and pyrimidine bases of nucleic acids

    International Nuclear Information System (INIS)

    Our current knowledge of the hydroxyl radical-mediated oxidations of the base moiety of the four main DNA 2'-deoxyribonucleosides, in aerated aqueous solutions, is reviewed. Included are kinetic and mechanistic aspects of transient radicals and structural features of the diamagnetic decomposition products. Another major topic addressed in this survey involves the chemical reactions of the purine and pyrimidine radical cations of the above DNA model compounds. These radicals are the main reactive intermediates of the direct effect of ionizing radiation and photosensitized reactions involving type I processes. Emphasis is placed on the similarities between the formation of oxidizing radicals via hydroxyl radical addition to the base moieties and chemical reactions of the radical cations (hydration and/or deprotonation). A survey of the main base lesions which have been characterized within isolated and cellular DNAs under conditions of oxidative stress, including exposure to ionizing radiation and various radiomimetic agents, is also presented. 97 refs

  6. Individual carotenoid content of SRM 1548 total diet and influence of storage temperature, lyophilization, and irradiation on dietary carotenoids

    International Nuclear Information System (INIS)

    A modified version of the AOAC procedure for the extraction of carotenoids from mixed feeds was coupled with an isocratic reversed-phase liquid chromatography (LC) method to measure individual carotenoids in SRM 1548 total diet and in a high-carotenoid mixed diet (HCMD). The major carotenoids identified in SRM 1548 were lycopene, beta-carotene, lutein, alpha-carotene, and zeaxanthin in descending order of concentration. The concentration of all carotenoids in SRM 1548 decreased as storage temperature increased. Significant differences in carotenoid concentrations occurred between -80 and 4 degrees C storage temperatures. Lyophilization of the HCMD significantly decreased beta-carotene and lycopene concentrations and produced an apparent increase in xanthophyll concentrations. Exposure to gamma-irradiation significantly decreased alpha-carotene and beta-carotene concentrations and led to an apparent increase in P-cryptoxanthin. SRM 1548 was found to be unsuitable for use as a reference material for carotenoid measurements, while HCMD has greater potential as a reference material

  7. Comparative Evaluation of the Radical-Scavenging Activities of Fucoxanthin and Its Stereoisomers

    Directory of Open Access Journals (Sweden)

    Yiping Zhang

    2014-02-01

    Full Text Available Fucoxanthin (Fuco is a characteristic carotenoid of brown seaweeds. In the present study, Fuco and its stereoisomers 9'Z-Fuco, 13Z- and 13'Z-Fuco were extracted from Laminaria japonica Aresch. They were isolated and purified by silica gel column chromatography, Sephadex LH-20, and reversed-phase HPLC. The radical-scavenging activities of the three stereoisomers were evaluated toward 1,1-diphenyl-2-picrylhydrazyl (DPPH radical, 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS radical, hydroxyl radical, and superoxide radical. The order of 1,1-diphenyl-2-picrylhydrazyl (DPPH radical-scavenging activity was 13Z- and 13'Z-Fuco > (all-E-Fuco > 9'Z-Fuco. The order of 2-2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS and hydroxyl radical-scavenging activities were 9'Z-Fuco > (all-E-Fuco > 13Z-and 13'Z-Fuco. The order of superoxide radical-scavenging activity was 13Z- and 13'Z-Fuco > (all-E-Fuco > 9'Z-Fuco. The scavenging activities of Fuco and its stereoisomers toward the four radical types were all dose-dependent. The ABTS, DPPH, and superoxide radical-scavenging activities were all weaker than that of tocopherol (VE, while their hydroxyl radical-scavenging activities were stronger than that of VE. The results confirmed that Fuco and its stereoisomers have potent antioxidant activities.

  8. The azide radical and its reaction with tryptophan and tyrosine

    International Nuclear Information System (INIS)

    Azide radicals react with azide ions according to N3 + N3- N6-, K = 0.33 dm3 mol-1. The species N6- has an absorption maximum at 645 nm epsilon = 6600 dm3 mol-1 cm-1. The reaction between the azide radical and ferrocyanide at an azide concentration of 0.05 mol dm-3 is independent of ionic strength, showing that N3 is the reacting form of the radical. From the reduction potentials of the azide radical and tryptophan, azide radicals can react with tryptophan by electron transfer. Reaction of azide radicals with tyrosine can also proceed by electron transfer. Whereas the formation of the tryptophan radical cation can be demonstrated in the reaction of Br2- with tryptophan, its formation could not be observed directly in the reaction of N3 with tryptophan because the azide ion deprotonates the tryptophan radical cation at high concentrations of azide. Reactions are proposed to account for observations made in previous pulse radiolysis studies of solutions containing azide and tryptophan or tyrosine. (author)

  9. Macular carotenoids and age-related maculopathy.

    Science.gov (United States)

    O'Connell, Eamonn; Neelam, Kumari; Nolan, John; Au Eong, Kah-Guan; Beatty, Stephan

    2006-11-01

    Lutein (L) and zeaxanthin (Z) are concentrated at the macula, where they are collectively known as macular pigment (MP), and where they are believed to play a major role in protecting retinal tissues against oxidative stress. Whilst the exact pathogenesis of age-related maculopathy (ARM) remains unknown, the disruption of cellular processes by oxidative stress may play an important role. Manipulation of dietary intake of L and Z has been shown to augment MP, thereby raising hopes that dietary supplementation with these carotenoids might prevent, delay, or modify the course of ARM. This article discusses the scientific rationale supporting the hypothesis that L and Z are protective against ARM, and presents the recent evidence germane to this theory. PMID:17160199

  10. Free-radical polymerization of some dental and medical materials by pulse radiolysis

    International Nuclear Information System (INIS)

    Complete text of publication follows. The extensive use of N-P-tolylglycine (NPG) analogues in adhesive bonding technologies calls for a better understanding of their role in initiating free-radical polymerization. The fast oxidation and reductions of NTG proceed via the formation of various types of free radicals and radical cation and anion intermediates. These intermediates were identified and their reactivity with oxygen, to produce the corresponding peroxyl radicals, has been measured. Hydroxyl radicals (OH) were used to initiate oxidation reactions of NTG, while the reduction reactions were initiated with hydrated electrons (eaq-). In the presence and absence of oxygen, the oxidation reaction mechanism of NTG by OH proceeded predominately by addition to the aromatic ring followed by OH- elimination reactions to produce NTG+ radical cations. In the presence of oxygen, OH-NTG also reacted with oxygen to produce peroxyl radicals. The reduction reaction of NTG with eaq- proceed via addition to the aromatic ring and amine-elimination, to produce various radicals: addition to the aromatic ring was followed by a fast protonation reaction to produce cyclohexadienyl radicals, and the amine-elimination reaction produced acetic acid free radicals and 4-methylaniline. In addition, it was found that the H-atom reaction with NTG also produced radical cations

  11. Cation-cation interaction in neptunyl(V) compounds

    International Nuclear Information System (INIS)

    The original manuscript was prepared by Professor N.N. Krot of Institute of Physical Chemistry, Russian Academy of Sciences, in 1997. Saeki tried to translate that into Japanese and to add some new data since 1997. The contents include the whole picture of cation-cation interactions mainly in 5-valence neptunium compounds. Firstly, characteristic structures of neptunium are summarized of the cation-cation bonding in compounds. Secondly, it is mentioned how the cation-cation bonding affects physical and chemical properties of the compounds. Then, characterization-methods for the cation-cation bonding in the compounds are discussed. Finally, the cation-cation interactions in compounds of other actinide-ions are shortly reviewed. (author)

  12. Introduction of new carotenoids into the bacterial photosynthetic apparatus by combining the carotenoid biosynthetic pathways of Erwinia herbicola and Rhodobacter sphaeroides.

    OpenAIRE

    Hunter, C N; Hundle, B S; Hearst, J E; Lang, H.P.; Gardiner, A.T.; Takaichi, S; Cogdell, R. J.

    1994-01-01

    Carotenoids have two major functions in bacterial photosynthesis, photoprotection and accessory light harvesting. The genes encoding many carotenoid biosynthetic pathways have now been mapped and cloned in several different species, and the availability of cloned genes which encode the biosynthesis of carotenoids not found in the photosynthetic genus Rhodobacter opens up the possibility of introducing a wider range of foreign carotenoids into the bacterial photosynthetic apparatus than would ...

  13. Regulation of orange carotenoid protein activity in cyanobacterial photoprotection

    NARCIS (Netherlands)

    Thurotte, A.; Lopez Igual, R.; Wilson, A.; Comolet, L.; Bourcier de Carbon, C.; Xiao, F.; Kirilovsky, D.

    2015-01-01

    Plants, algae, and cyanobacteria have developed mechanisms to decrease the energy arriving at reaction centers to protect themselves from high irradiance. In cyanobacteria, the photoactive Orange Carotenoid Protein (OCP) and the Fluorescence Recovery Protein are essential elements in this mechanism.

  14. Radical prostatectomy - discharge

    Science.gov (United States)

    ... prostatectomy - discharge; Laparoscopic radical prostatectomy - discharge; LRP - discharge; Robotic-assisted laparoscopic prostatectomy - discharge ; RALP - discharge; Pelvic lymphadenectomy - ...

  15. Carotenoids and Their Isomers: Color Pigments in Fruits and Vegetables

    OpenAIRE

    Yueming Jiang; Amin Ismail; Kin-Weng Kong; Hock-Eng Khoo; K. Nagendra Prasad

    2011-01-01

    Fruits and vegetables are colorful pigment-containing food sources. Owing to their nutritional benefits and phytochemicals, they are considered as ‘functional food ingredients’. Carotenoids are some of the most vital colored phytochemicals, occurring as all-trans and cis-isomers, and accounting for the brilliant colors of a variety of fruits and vegetables. Carotenoids extensively studied in this regard include β-carotene, lycopene, lutein and zeaxanthin. Coloration of fruits and vegetables d...

  16. Biochemical Study on the Carotenoids in the Anemonefish, Amphiprion spp.

    OpenAIRE

    Tanaka, Yoshito; Yamamoto, Atsushi; KAMATA, Tadashi; Simpson, Kenneth L.; タナカ, ヨシト; ヤマモト, アツシ; カマタ, タダシ; 田中, 淑人; 山本, 任; 釜田, 忠; シンプソン, ケネス L.

    1992-01-01

    The carotenoid compositions of four species of wild anemonefish, Amphiprion ocellaris, A. biacleatus, A. frenatus and A. clarkii, were analyzed. Alltrans-zeaxanthin was found to be a dominant pigment followed by cis-isomers of zeaxanthin in all four species of anemonefish. Astaxanthin was also isolated as a major carotenoid in these species except A. clarkii, in which no astaxanthin was detected. Astaxanthin, however, was isolated from the eggs of A. clarkii. A feeding experiment was co...

  17. Free radical inactivation of trypsin

    International Nuclear Information System (INIS)

    Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl3COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 200C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl3COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl3COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

  18. Carotenoids are essential for the assembly of cyanobacterial photosynthetic complexes.

    Science.gov (United States)

    Tóth, Tünde N; Chukhutsina, Volha; Domonkos, Ildikó; Knoppová, Jana; Komenda, Josef; Kis, Mihály; Lénárt, Zsófia; Garab, Győző; Kovács, László; Gombos, Zoltán; van Amerongen, Herbert

    2015-10-01

    In photosynthetic organisms, carotenoids (carotenes and xanthophylls) are important for light harvesting, photoprotection and structural stability of a variety of pigment-protein complexes. Here, we investigated the consequences of altered carotenoid composition for the functional organization of photosynthetic complexes in wild-type and various mutant strains of the cyanobacterium Synechocystis sp. PCC 6803. Although it is generally accepted that xanthophylls do not play a role in cyanobacterial photosynthesis in low-light conditions, we have found that the absence of xanthophylls leads to reduced oligomerization of photosystems I and II. This is remarkable because these complexes do not bind xanthophylls. Oligomerization is even more disturbed in crtH mutant cells, which show limited carotenoid synthesis; in these cells also the phycobilisomes are distorted despite the fact that these extramembranous light-harvesting complexes do not contain carotenoids. The number of phycocyanin rods connected to the phycobilisome core is strongly reduced leading to high amounts of unattached phycocyanin units. In the absence of carotenoids the overall organization of the thylakoid membranes is disturbed: Photosystem II is not formed, photosystem I hardly oligomerizes and the assembly of phycobilisomes remains incomplete. These data underline the importance of carotenoids in the structural and functional organization of the cyanobacterial photosynthetic machinery. PMID:26045333

  19. Seeking carotenoid pigments in amber-preserved fossil feathers

    Science.gov (United States)

    Thomas, Daniel B.; Nascimbene, Paul C.; Dove, Carla J.; Grimaldi, David A.; James, Helen F.

    2014-06-01

    Plumage colours bestowed by carotenoid pigments can be important for visual communication and likely have a long evolutionary history within Aves. Discovering plumage carotenoids in fossil feathers could provide insight into the ecology of ancient birds and non-avian dinosaurs. With reference to a modern feather, we sought chemical evidence of carotenoids in six feathers preserved in amber (Miocene to mid-Cretaceous) and in a feather preserved as a compression fossil (Eocene). Evidence of melanin pigmentation and microstructure preservation was evaluated with scanning electron and light microscopies. We observed fine microstructural details including evidence for melanin pigmentation in the amber and compression fossils, but Raman spectral bands did not confirm the presence of carotenoids in them. Carotenoids may have been originally absent from these feathers or the pigments may have degraded during burial; the preservation of microstructure may suggest the former. Significantly, we show that carotenoid plumage pigments can be detected without sample destruction through an amber matrix using confocal Raman spectroscopy.

  20. Raman spectroscopic analysis of the increase of the carotenoid antioxidant concentration in human skin after a 1-week diet with ecological eggs

    Science.gov (United States)

    Hesterberg, Karoline; Lademann, Jürgen; Patzelt, Alexa; Sterry, Wolfram; Darvin, Maxim E.

    2009-03-01

    Skin aging is mainly caused by the destructive action of free radicals, produced by the UV light of the sun. The human skin has developed a protection system against these highly reactive molecules in the form of the antioxidative potential. Carotenoids are one of the main components of the antioxidants of the human skin. From former studies, it is known that skin aging is reduced in individuals with high levels of carotenoids. Because most of the antioxidants cannot be produced by the human organism, they must be up taken by nutrition. Using noninvasive Raman spectroscopic measurements it is demonstrated that not only fruits and vegetables but also eggs contain high concentrations of antioxidants including carotenoids, which are even doubled in the case of ecological eggs. After a 1-week diet with ecological eggs performed by six volunteers, it is found that the concentration of the carotenoids in the skin of the volunteers increased by approx. 20%. Our study does not intend to recommend exorbitant egg consumption, as eggs also contain harmful cholesterol. But in the case of egg consumption, ecological eggs from hens kept on pasture should be preferred to also receive a benefit for the skin.

  1. Triplet excited state spectra and dynamics of carotenoids from the thermophilic purple photosynthetic bacterium Thermochromatium tepidum

    Energy Technology Data Exchange (ETDEWEB)

    Niedzwiedzki, Dariusz; Kobayashi, Masayuki; Blankenship, R. E.

    2011-01-13

    Light-harvesting complex 2 from the anoxygenic phototrophic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption, fluorescence and flash photolysis spectroscopy. Steady-state absorption and fluorescence measurements show that carotenoids play a negligible role as supportive energy donors and transfer excitation to bacteriochlorophyll-a with low energy transfer efficiency of ~30%. HPLC analysis determined that the dominant carotenoids in the complex are rhodopin and spirilloxanthin. Carotenoid excited triplet state formation upon direct (carotenoid) or indirect (bacteriochlorophyll-a Q{sub x} band) excitation shows that carotenoid triplets are mostly localized on spirilloxanthin. In addition, no triplet excitation transfer between carotenoids was observed. Such specific carotenoid composition and spectroscopic results strongly suggest that this organism optimized carotenoid composition in the light-harvesting complex 2 in order to maximize photoprotective capabilities of carotenoids but subsequently drastically suppressed their supporting role in light-harvesting process.

  2. Spectroscopic properties of the carotenoid 3´-hydroxyechinenone in the orange carotenoid protein from the cyanobacterium Arthrospira maxima

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Kerfeld, C.A.; Pascher, T.; Sundström, V.

    2007-01-01

    Roč. 44, č. 10 (2007), s. 3994-4003. ISSN 0006-2960 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * Spectroscopic properties Subject RIV: CE - Biochemistry Impact factor: 3.368, year: 2007

  3. The mechanisms of radical formation in L-α-alanine

    International Nuclear Information System (INIS)

    Modeling of radical transformations in L-α-alanine after irradiation was performed for isolated radicals and for clusters. Special attention was devoted to the explanation of the experimental results concerning selective proton transfer and behavior of cation-radicals because a unique interpretation of the corresponding experiments is very difficult. Both semi-empirical and ab initio methods were used depending on the size of system under investigation. The results obtained show the usefulness of the computer simulation for processes in rather complex materials used in dosimetry

  4. The mechanisms of radical formation in L-{alpha}-alanine

    Energy Technology Data Exchange (ETDEWEB)

    Bugay, A.A.; Onischuk, V.A.; Petrenko, T.L.; Teslenko, V.V

    2000-05-15

    Modeling of radical transformations in L-{alpha}-alanine after irradiation was performed for isolated radicals and for clusters. Special attention was devoted to the explanation of the experimental results concerning selective proton transfer and behavior of cation-radicals because a unique interpretation of the corresponding experiments is very difficult. Both semi-empirical and ab initio methods were used depending on the size of system under investigation. The results obtained show the usefulness of the computer simulation for processes in rather complex materials used in dosimetry.

  5. Radical theory of rings

    CERN Document Server

    Gardner, JW

    2003-01-01

    Radical Theory of Rings distills the most noteworthy present-day theoretical topics, gives a unified account of the classical structure theorems for rings, and deepens understanding of key aspects of ring theory via ring and radical constructions. Assimilating radical theory's evolution in the decades since the last major work on rings and radicals was published, the authors deal with some distinctive features of the radical theory of nonassociative rings, associative rings with involution, and near-rings. Written in clear algebraic terms by globally acknowledged authorities, the presentation

  6. Diversity, physiology, and evolution of avian plumage carotenoids and the role of carotenoid-protein interactions in plumage color appearance.

    Science.gov (United States)

    LaFountain, Amy M; Prum, Richard O; Frank, Harry A

    2015-04-15

    The diversity of vibrant plumage colors in birds has evolved as a direct result of social and environmental pressures. To fully understand these underlying pressures it is necessary to elucidate the mechanisms for the creation of novel plumage colors which include the metabolic transformations of dietary carotenoids and spectral tuning of the molecules within the feather protein environment. Recent advances in this field have greatly expanded the number and breadth of avian species for which plumage pigmentation has been characterized, making it possible to reconstruct the phylogenetic history of carotenoid usage in plumage. Resonance Raman and classical Raman spectroscopic techniques have been employed with great effect in the study of carotenoids in situ. The application of these methods have two benefits: to identify carotenoids in feathers that are unavailable for destructive sampling; and to study the spectral tuning resulting from the interaction between the carotenoids and the proteins to which they are bound. This review presents a summary of recent advances in the understanding of the molecular factors controlling the coloration of avian carotenoid plumage obtained through the application of both bioanalytical and spectroscopic methodologies. PMID:25637658

  7. Validation model for Raman based skin carotenoid detection.

    Science.gov (United States)

    Ermakov, Igor V; Gellermann, Werner

    2010-12-01

    Raman spectroscopy holds promise as a rapid objective non-invasive optical method for the detection of carotenoid compounds in human tissue in vivo. Carotenoids are of interest due to their functions as antioxidants and/or optical absorbers of phototoxic light at deep blue and near UV wavelengths. In the macular region of the human retina, carotenoids may prevent or delay the onset of age-related tissue degeneration. In human skin, they may help prevent premature skin aging, and are possibly involved in the prevention of certain skin cancers. Furthermore, since carotenoids exist in high concentrations in a wide variety of fruits and vegetables, and are routinely taken up by the human body through the diet, skin carotenoid levels may serve as an objective biomarker for fruit and vegetable intake. Before the Raman method can be accepted as a widespread optical alternative for carotenoid measurements, direct validation studies are needed to compare it with the gold standard of high performance liquid chromatography. This is because the tissue Raman response is in general accompanied by a host of other optical processes which have to be taken into account. In skin, the most prominent is strongly diffusive, non-Raman scattering, leading to relatively shallow light penetration of the blue/green excitation light required for resonant Raman detection of carotenoids. Also, sizable light attenuation exists due to the combined absorption from collagen, porphyrin, hemoglobin, and melanin chromophores, and additional fluorescence is generated by collagen and porphyrins. In this study, we investigate for the first time the direct correlation of in vivo skin tissue carotenoid Raman measurements with subsequent chromatography derived carotenoid concentrations. As tissue site we use heel skin, in which the stratum corneum layer thickness exceeds the light penetration depth, which is free of optically confounding chromophores, which can be easily optically accessed for in vivo RRS

  8. Carotenoids: Actual knowledge on food sources, intakes, stability and bioavailability and their protective role in humans

    DEFF Research Database (Denmark)

    Maiani, Giuseppe; Castón, María Jesús Periago; Catasta, Giovina;

    2009-01-01

    Carotenoids are one of the major food micronutrients in human diets and the overall objective of this review is to re-examine the role of carotenoids in human nutrition. We have emphasized the attention on the following carotenoids present in food and human tissues: -carotene, -cryptoxanthin......, -carotene, lycopene, lutein and zeaxanthin; we have reported the major food sources and dietary intake of these compounds. We have tried to summarize positive and negative effects of food processing, storage, cooking on carotenoid content and carotenoid bioavailability. In particular, we have evidenced...... the possibility to improve carotenoids bioavailability in accordance with changes and variations of technology procedures....

  9. Relative yields of radicals produced in deuterated methanol by irradiation

    Science.gov (United States)

    Nakagawa, Seiko

    2016-05-01

    The relative yields of radicals produced in four kinds of methanols; i.e., CH3OH, CH3OD, CD3OH and CD3OD, by γ-irradiation have been studied using ESR spin trapping with PBN. Both PBN-H and PBN-D were produced from CH3OD and CD3OH. This means that the proton transfer to the neutral methanol from the cationic one is one of the processes to produce both the methoxy and hydoxy-methyl radicals. The yield of the methoxy radical adduct relative to the hydroxy-methyl radical adduct decreased in the order CD3OH>CD3OD>CH3OH>CH3OD. The difference in the rates of the proton transfer and hydrogen abstraction reactions by substitution with deuterium is the reason for the variation in the relative radical yield.

  10. Treating ballast water with hydroxyl radical on introduced organisms

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    With physical method of micro-gap gas discharge, a large amount of hydroxyl radical can be produced in 20t/h pilot-scale system using the ionization of O2 and H2O. In this paper, the effect of biochemistry of hydroxyl radicals on introduced organisms in ballast water was experimentally investigated. The results indicate that the contents of chlorophyl-a, chlorophyl-b, chlorophyl-c and carotenoid are decreased by 35%-64% within 8.0s and further to the lowest limit of test 5 minutes. In addition, the main reasons of cell death are the lipid peroxidation, the strong destruction to the monose, amylose, protein, DNA and RNA of cell, and damage in CAT, POD and SOD of antioxidant enzyme system.

  11. Improving carotenoid extraction from tomato waste by pulsed electric fields.

    Directory of Open Access Journals (Sweden)

    JavierRaso

    2014-08-01

    Full Text Available In this investigation, the influence of the application of Pulsed Electric Fields (PEF of different intensities (3-7 kV/cm and 0-300 μs on the carotenoid extraction from tomato peel and pulp in a mixture of hexane:acetone:ethanol was studied with the aim of increasing extraction yield or reducing the percentage of the less green solvents in the extraction medium. According to the cellular disintegration index, the optimum treatment time for the permeabilization of tomato peel and pulp at different electric field strengths was 90 µs. The PEF permeabilization of tomato pulp did not significantly increase the carotenoid extraction. However, a PEF-treatment at 5 kV/cm improved the carotenoid extraction from tomato peel by 39 % as compared with the control in a mixture of hexane:ethanol:acetone (50:25:25. Further increments of electric field from 5 to 7 kV/cm did not increase significantly the extraction of carotenoids. . The presence of acetone in the solvent mixture did not positively affect the carotenoid extraction when the tomato peels were PEF-treated. Response surface methodology was used to determine the potential of PEF for reducing the percentage of hexane in a hexane:ethanol mixture. The application of a PEF-treatment allowed reducing the hexane percentage from 45 to 30 % without affecting the carotenoid extraction yield. The antioxidant capacity of the extracts obtained from tomato peel was correlated with the carotenoid concentration and it was not affected by the PEF-treatment.

  12. EPR Study of Radicals in Irradiated Ionic Liquids and Implications for the Radiation Stability of Ionic Liquid-Based Extraction Systems

    CERN Document Server

    Shkrob, I A; Wishart, J F; Chemerisov, Sergey D.; Shkrob, Ilya A.; Wishart, James F.

    2007-01-01

    The radiation- and photo- chemistry of room temperature ionic liquids (ILs) composed of ammonium, phosphonium, pyrrolidinium, and imidazolium cations and bis(triflyl)amide, dicyanamide, and bis(oxalato)borate anions, have been studied using low-temperature Electron Paramagnetic Resonance (EPR). Several classes of radicals have been identified and related to reactions of the primary radiolytically generated electrons and holes. Large yields of terminal and penultimate C-centered radicals are observed in the aliphatic chains of the phosphonium, ammonium and pyrrolidinium cations, but not for imidazolium cation. This pattern can be accounted for by efficient deprotonation of a hole trapped on the cation (the radical dication) that competes with rapid charge transfer to a nearby anion. The latter leads to the formation of stable N- or O-centered radicals. The electrons either react with the protic impurity (for nonaromatic cations) yielding H atoms or the aromatic moiety (for imidazolium cations). Excitation of b...

  13. Recent patents on the extraction of carotenoids.

    Science.gov (United States)

    Riggi, Ezio

    2010-01-01

    This article reviews the patents that have been presented during the last decade related to the extraction of carotenoids from various forms of organic matter (fruit, vegetables, animals), with an emphasis on the methods and mechanisms exploited by these technologies, and on technical solutions for the practical problems related to these technologies. I present and classify 29 methods related to the extraction processes (physical, mechanical, chemical, and enzymatic). The large number of processes for extraction by means of supercritical fluids and the growing number of large-scale industrial plants suggest a positive trend towards using this technique that is currently slowed by its cost. This trend should be reinforced by growing restrictions imposed on the use of most organic solvents for extraction of food products and by increasingly strict waste management regulations that are indirectly promoting the use of extraction processes that leave the residual (post-extraction) matrix substantially free from solvents and compounds that must subsequently be removed or treated. None of the reviewed approaches is the best answer for every extractable compound and source, so each should be considered as one of several alternatives, including the use of a combination of extraction approaches. PMID:20653552

  14. [Antioxidant activity of cationic whey protein isolate].

    Science.gov (United States)

    titova, M E; Komolov, S A; Tikhomirova, N A

    2012-01-01

    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (pwhey protein isolate has an

  15. Spin-selective recombination kinetics of a carotenoid-porphyrin-fullerene radical pair

    Energy Technology Data Exchange (ETDEWEB)

    Maeda, Kiminori; Wedge, Christopher J.; Storey, Jonathan G.; Henbest, Kevin B.; Liddell, Paul A.; Kodis, Gerdenis; Gust, Devens; Hore, P. J.; Timmel, Christiane R.

    2011-01-01

    We determine the spin-selective kinetics of a carotenoid–porphyrin–fullerene triad that has previously been used to establish the principle that a photochemical reaction could form the basis of the magnetic compass sensor of migratory birds and show that its magnetic sensitivity can be understood without invoking quantum Zeno effects.

  16. Silyloxyamines as Sources of Silyl Radicals: ESR Spin Trapping, Laser Flash Photolysis Investigation and Photopolymerization Ability

    OpenAIRE

    Lalevee, Jacques

    2010-01-01

    Abstract Two original silyloxyamines derived from 8-(pentamethyldisilyloxy)-julolidine and diethyl 3-(pentamethyldisilyloxy)-aniline are proposed as new sources of silyl radicals. The decomposition mechanism, the excited state processes and the radical generation are explored by steady state photolysis, laser flash photolysis, ESR and MO calculations. The Si-Si bond cleavage is clearly demonstrated. The formation of a radical cation on the amine moiety is also observed. Moreover, t...

  17. Laparoscopic radical cystectomy

    OpenAIRE

    Fergany, Amr

    2012-01-01

    Objective Laparoscopic radical cystectomy (LRC) has emerged as a minimally invasive alternative to open radical cystectomy (ORC). This review focuses on patient selection criteria, technical aspects and postoperative outcomes of LRC. Methods Material for the review was obtained by a PubMed search over the last 10 years, using the keywords ‘laparoscopic radical cystectomy’ and ‘laparoscopic bladder cancer’ in human subjects. Results Twenty-two publications selected for relevance and content we...

  18. Laparoscopic Radical Trachelectomy

    OpenAIRE

    Rendón, Gabriel J.; Ramirez, Pedro T.; Frumovitz, Michael; Schmeler, Kathleen M.; Pareja, Rene

    2012-01-01

    Introduction: The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. Case Description: We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old fem...

  19. Carotenoid composition of strawberry tree (Arbutus unedo L.) fruits.

    Science.gov (United States)

    Delgado-Pelayo, Raúl; Gallardo-Guerrero, Lourdes; Hornero-Méndez, Dámaso

    2016-05-15

    The carotenoid composition of strawberry tree (Arbutus unedo) fruits has been characterised in detail and quantified for the first time. According to the total carotenoid content (over 340 μg/g dw), mature strawberry tree berries can be classified as fruits with very high carotenoid content (>20 μg/g dw). (all-E)-Violaxanthin and 9Z-violaxanthin were found to be the major carotenoid pigments, accounting for more than 60%, responsible for the bright colour of the flesh of ripe fruits. In addition other 5,6-epoxide carotenoids, such as (all-E)-neoxanthin, (9'Z)-neoxanthin (all-E)-antheraxanthin and lutein 5,6-epoxide, together with (all-E)-lutein, (all-E)-zeaxanthin and (all-E)-β-carotene were found at high levels (>5-20 μg/g dw). The LC-MS (APCI+) analysis of the xanthophyll fraction in their native state (direct extract) revealed that most of them (>90%) were totally esterified with saturated fatty acids (capric, lauric, myristic, palmitic and stearic). Monoesters, homodiesters and heterodiesters of (all-E)-violaxanthin and 9Z-violaxanthin were the major pigments. PMID:26775958

  20. Vibronic coupling in the excited-states of carotenoids.

    Science.gov (United States)

    Miki, Takeshi; Buckup, Tiago; Krause, Marie S; Southall, June; Cogdell, Richard J; Motzkus, Marcus

    2016-04-20

    The ultrafast femtochemistry of carotenoids is governed by the interaction between electronic excited states, which has been explained by the relaxation dynamics within a few hundred femtoseconds from the lowest optically allowed excited state S2 to the optically dark state S1. Extending this picture, some additional dark states (3A and 1B) and their interaction with the S2 state have also been suggested to play a major role in the ultrafast deactivation of carotenoids and their properties. Here, we investigate the interaction between such dark and bright electronic excited states of open chain carotenoids, particularly its dependence on the number of conjugated double bonds (N). We focus on the ultrafast wave packet motion on the excited potential surface, which is modified by the interaction between bright and dark electronic states. Such a coupling between electronic states leads to a shift of the vibrational frequency during the excited-state evolution. In this regard, pump-degenerate four-wave mixing (pump-DFWM) is applied to a series of carotenoids with different numbers of conjugated double bonds N = 9, 10, 11 and 13 (neurosporene, spheroidene, lycopene and spirilloxanthin, respectively). Moreover, we demonstrate in a closed-chain carotenoid (lutein) that the coupling strength and therefore the vibrational shift can be tailored by changing the energy degeneracy between the 1B and 1B states via solvent interaction. PMID:27055720

  1. An update on microbial carotenoid production: application of recent metabolic engineering tools.

    Science.gov (United States)

    Das, Amitabha; Yoon, Sang-Hwal; Lee, Sook-Hee; Kim, Jae-Yean; Oh, Deok-Kun; Kim, Seon-Won

    2007-12-01

    Carotenoids are ubiquitous pigments synthesized by plants, fungi, algae, and bacteria. Industrially, carotenoids are used in pharmaceuticals, neutraceuticals, and animal feed additives, as well as colorants in cosmetics and foods. Scientific interest in dietary carotenoids has increased in recent years because of their beneficial effects on human health, such as lowering the risk of cancer and enhancement of immune system function, which are attributed to their antioxidant potential. The availability of carotenoid genes from carotenogenic microbes has made possible the synthesis of carotenoids in non-carotenogenic microbes. The increasing interest in microbial sources of carotenoid is related to consumer preferences for natural additives and the potential cost effectiveness of creating carotenoids via microbial biotechnology. In this review, we will describe the recent progress made in metabolic engineering of non-carotenogenic microorganisms with particular focus on the potential of Escherichia coli for improved carotenoid productivity. PMID:17912511

  2. Near-infrared transient absorption study of the orange carotenoid protein

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Chábera, P.; Sundström, V.; Kerfeld, C.A.

    Nové Hrady : Academic and University Center, 2008. s. 34. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Keywords : carotenoids Subject RIV: BO - Biophysics

  3. Direct quantification of carotenoids in low fat babyfoods via laser photoacoustics and colorimetric index a

    NARCIS (Netherlands)

    Doka, O.; Ajtony, Z.; Bicanic, D.D.; Valinger, D.; Vegvari, G.

    2014-01-01

    Carotenoids are important antioxidants found in various foods including those for nutrition of infants. In this investigation, the total carotenoid content (TCC) of nine different commercially available baby foods was quantified using colorimetric index a * obtained via reflectance colorimetry (RC)

  4. Development of carotenoid-enriched vegetables with increased nutritional quality and visual appearance

    Science.gov (United States)

    Carotenoids are a class of red, orange and yellow pigments widely distributed in nature. Biotech approach has been proved to be effective in successfully engineering of carotenoid content in food crops with better health and visual appearance....

  5. The Or gene enhances carotenoid accumulation and stability during post-harvest storage of potato tubers

    Science.gov (United States)

    Provitamin A carotenoids in staple crops are not very stable during storage and their loss compromises nutritional quality. To elucidate the fundamental mechanisms underlying carotenoid accumulation and stability, we investigated transgenic potato tubers that express the cauliflower Orange (Or) gene...

  6. Spin-selective recombination reactions of radical pairs: Experimental test of validity of reaction operators

    Energy Technology Data Exchange (ETDEWEB)

    Maeda, Kiminori [Department of Chemistry, University of Oxford, Centre for Advanced Electron Spin Resonance, Inorganic Chemistry Laboratory, Oxford (United Kingdom); Liddell, Paul; Gust, Devens [Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona, 85287-1604 (United States); Hore, P. J. [Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, Oxford (United Kingdom)

    2013-12-21

    Spin-selective reactions of radical pairs are conventionally modelled using an approach that dates back to the 1970s [R. Haberkorn, Mol. Phys. 32, 1491 (1976)]. An alternative approach based on the theory of quantum measurements has recently been suggested [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010)]. We present here the first experimental attempt to discriminate between the two models. Pulsed electron paramagnetic resonance spectroscopy has been used to investigate intramolecular electron transfer in the radical pair form of a carotenoid-porphyrin-fullerene molecular triad. The rate of spin-spin relaxation of the fullerene radical in the triad was found to be inconsistent with the quantum measurement description of the spin-selective kinetics, and in accord with the conventional model when combined with spin-dephasing caused by rotational modulation of the anisotropic g-tensor of the fullerene radical.

  7. Carotenoid limitation of sexual coloration along an environmental gradient in guppies

    OpenAIRE

    Grether, G. F; Hudon, J; Millie, D. F.

    1999-01-01

    Carotenoids produce most of the brilliant orange and yellow colours seen in animals, but animals cannot synthesize these pigments and must rely on dietary sources. The idea that carotenoids make good signals because they are a scarce limiting resource was proposed two decades ago and has become the leading hypothesis for the role of carotenoids in animal communication. To our knowledge, until now, however, there has been no direct evidence that carotenoids are a limiting resource in nature. W...

  8. Biochemistry and Molecular Biology of Carotenoid Biosynthesis in Chili Peppers (Capsicum spp.)

    OpenAIRE

    María del Rocío Gómez-García; Neftalí Ochoa-Alejo

    2013-01-01

    Capsicum species produce fruits that synthesize and accumulate carotenoid pigments, which are responsible for the fruits’ yellow, orange and red colors. Chili peppers have been used as an experimental model for studying the biochemical and molecular aspects of carotenoid biosynthesis. Most reports refer to the characterization of carotenoids and content determination in chili pepper fruits from different species, cultivars, varieties or genotypes. The types and levels of carotenoids differ be...

  9. Enhancement of Carotenoid Biosynthesis in Transplastomic Tomatoes by Induced Lycopene-to-Provitamin A Conversion

    OpenAIRE

    Apel, W.; R. Bock

    2009-01-01

    Carotenoids are essential pigments of the photosynthetic apparatus and an indispensable component of the human diet. In addition to being potent antioxidants, they also provide the vitamin A precursor beta-carotene. In tomato (Solanum lycopersicum) fruits, carotenoids accumulate in specialized plastids, the chromoplasts. How the carotenoid biosynthetic pathway is regulated and what limits total carotenoid accumulation in fruit chromoplasts is not well understood. Here, we have introduced the ...

  10. Microscale extraction method for HPLC carotenoid analysis in vegetable matrices

    Directory of Open Access Journals (Sweden)

    Sidney Pacheco

    2014-10-01

    Full Text Available In order to generate simple, efficient analytical methods that are also fast, clean, and economical, and are capable of producing reliable results for a large number of samples, a micro scale extraction method for analysis of carotenoids in vegetable matrices was developed. The efficiency of this adapted method was checked by comparing the results obtained from vegetable matrices, based on extraction equivalence, time required and reagents. Six matrices were used: tomato (Solanum lycopersicum L., carrot (Daucus carota L., sweet potato with orange pulp (Ipomoea batatas (L. Lam., pumpkin (Cucurbita moschata Duch., watermelon (Citrullus lanatus (Thunb. Matsum. & Nakai and sweet potato (Ipomoea batatas (L. Lam. flour. Quantification of the total carotenoids was made by spectrophotometry. Quantification and determination of carotenoid profiles were formulated by High Performance Liquid Chromatography with photodiode array detection. Microscale extraction was faster, cheaper and cleaner than the commonly used one, and advantageous for analytical laboratories.

  11. Noninvasive measurements of carotenoids in bovine udder by reflection spectroscopy

    Science.gov (United States)

    Klein, Julia; Darvin, Maxim E.; Müller, Kerstin E.; Lademann, Jürgen

    2012-10-01

    For a long time, the antioxidative status in cattle has been discussed as an indicator for stress conditions resulting from disease or exertion. Until now, invasive approaches have been necessary to obtain blood samples or biopsy materials and gain insights into the antioxidative status of cattle. Due to these efforts and the costs of the analyses, serial sampling is feasible in an experimental setting, but not for measurements on a routine basis. The present study focuses on the feasibility of an innovative, noninvasive spectroscopic technique that allows in vivo measurements of carotenoids in the skin by reflection spectroscopy. To this end, in a first trial, repeated measurements of the carotenoid concentration of the udder skin were performed on 25 healthy cattle from different breeds. Carotenoid concentrations showed highly significant differences between individual animals (Ptest) differed significantly (P<0.005), with higher concentrations observed in robust cows.

  12. Evaluation of Extraction Methods for the Analysis of Carotenoids for Different Vegetable Matrix

    OpenAIRE

    Stancuta Scrob; Sevastita Muste; Crina Muresan; Anca Farcas; Sonia Socaci; Romina Vlaic

    2013-01-01

    In this study, different solvents were used to achieve the maximum extractibility of total carotenoids. The extracted total carotenoids were estimated using UV- visible spectrophotometer. Carotenoids from vegetable matrix can be used as a food colorant, food additive, cosmetics, antioxidants and nutraceuticals.

  13. The contribution of various foods to intake of vitamin A and carotenoids in the Netherlands

    NARCIS (Netherlands)

    Goldbohm, R.A.; Brants, H.A.M.; Hulshof, K.F.A.M.; Brandt, P.A. van den

    1998-01-01

    This study presents data on dietary intake of specific carotenoids in the Netherlands, based on a recently developed food composition database for carotenoids. Regularly eaten vegetables, the main dietary source of carotenoids, were sampled comprehensively and analysed with modern analytic methods.

  14. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  15. A covalent attraction between two molecular cation TTF·~+

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The optimized structure of the tetrathiafulvalence radical-cation dimer(TTF·+-TTF·+) with all-real frequencies is obtained at MP2/6-311G level,which exhibits the attraction between two molecular cation TTF·+.The new attraction interaction is a 20-center-2-electron intermolecular covalent π /π bonding with a telescope shape.The covalent π /π bonding has the bonding energy of about -21 kcal·mol-1 and is concealed by the Coulombic repulsion between two TTF·+ cations.This intermolecular covalent attraction also influences the structure of the TTF·+ subunit,i.e.,its molecular plane is bent by an angle θ=5.6°.This work provides new knowledge on intermolecular interaction.

  16. Estabilidad del Carotenoide Licopeno en Tomates en Conserva Lycopene Carotenoide Stability in Canned Tomatoes

    Directory of Open Access Journals (Sweden)

    Alicia L Ordóñez

    2009-01-01

    Full Text Available El objetivo de este trabajo fue determinar la estabilidad del carotenoide licopeno durante el proceso de elaboración de conservas de tomates peritas y evaluar la misma durante su almacenamiento como producto terminado. Se trabajó con muestras provenientes de elaboraciones industriales extraídas en distintos puntos del proceso: tomates frescos, en la boquilla de alimentación de la línea; tomate pelado, a la salida de la peladora termofísica y producto terminado a la salida del esterilizador-enfriador, de distintos lotes de elaboración y en tres ocasiones durante la temporada 2007. El producto terminado, envasado en hojalata, fue evaluado durante un año, cada tres meses. El licopeno fue extraído con una mezcla de hexano-acetona-etanol y determinado por espectrofotometría visible a 472nm. Los resultados se analizaron estadísticamente mostrando que la esterilización industrial produce liberación celular del licopeno.The objective of this work was to determine lycopene carotenoid stability during manufacturing process in canned peeled whole tomatoes and during its storage as final product. Samples were taken during industrial manufacturing at different process points: fresh tomatoes when they were feeding to process line, peeled tomatoes from thermophysical peeler and finished product after it passed the cooker-cooler. Samples were obtained from different manufacturing lots at three times during the 2007 harvesting season. Canned tomatoes were analyzed every three months, during one year. Lycopene was extracted with hexane-acetone-ethyl alcohol and measured by spectrophotometry at 472 nm. Statistical analysis of the results shows that industrial sterilization produces cell release of lycopene.

  17. Cationic Antimicrobial Peptide Cytotoxicity

    OpenAIRE

    Laverty, Garry; Gilmore, Brendan

    2014-01-01

    Fluorescence microscopy serves as a valuable tool for assessing the structural integrity and viability of eukaryotic cells. Through the use of calcein AM and the DNA stain 4,6-diamidino-2 phenylindole (DAPI), cell viability and membrane integrity can be qualified. Our group has previously shown the ultra-short cationic antimicrobial peptide H-OOWW-NH2; the amphibian derived 27-mer peptide Maximin-4and the ultra-short lipopeptide C12-OOWW-NH2 to be effective against a range of bacterial biofil...

  18. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

    Energy Technology Data Exchange (ETDEWEB)

    Shirani, Hossein, E-mail: shiranihossein@gmail.com [Young Researchers Club, Islamic Azad University, Toyserkan Branch, Toyserkan (Iran, Islamic Republic of); Jameh-Bozorghi, Saeed [Department of Chemistry, Islamic Azad University, Arak Branch, Arak (Iran, Islamic Republic of); Yousefi, Ali [Department of Computer Engineering, Islamic Azad University, Hamedan Branch, Hamedan (Iran, Islamic Republic of)

    2015-01-22

    In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

  19. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

    International Nuclear Information System (INIS)

    In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed

  20. Quenching Capabilities of Long-Chain Carotenoids in Light-Harvesting-2 Complexes from Rhodobacter sphaeroides with an Engineered Carotenoid Synthesis Pathway

    Science.gov (United States)

    2016-01-01

    Six light-harvesting-2 complexes (LH2) from genetically modified strains of the purple photosynthetic bacterium Rhodobacter (Rb.) sphaeroides were studied using static and ultrafast optical methods and resonance Raman spectroscopy. These strains were engineered to incorporate carotenoids for which the number of conjugated groups (N = NC=C + NC=O) varies from 9 to 15. The Rb. sphaeroides strains incorporate their native carotenoids spheroidene (N = 10) and spheroidenone (N = 11), as well as longer-chain analogues including spirilloxanthin (N = 13) and diketospirilloxantion (N = 15) normally found in Rhodospirillum rubrum. Measurements of the properties of the carotenoid first singlet excited state (S1) in antennas from the Rb. sphaeroides set show that carotenoid-bacteriochlorophyll a (BChl a) interactions are similar to those in LH2 complexes from various other bacterial species and thus are not significantly impacted by differences in polypeptide composition. Instead, variations in carotenoid-to-BChl a energy transfer are primarily regulated by the N-determined energy of the carotenoid S1 excited state, which for long-chain (N ≥ 13) carotenoids is not involved in energy transfer. Furthermore, the role of the long-chain carotenoids switches from a light-harvesting supporter (via energy transfer to BChl a) to a quencher of the BChl a S1 excited state B850*. This quenching is manifested as a substantial (∼2-fold) reduction of the B850* lifetime and the B850* fluorescence quantum yield for LH2 housing the longest carotenoids. PMID:27285777

  1. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  2. Molecular Factors Controlling Photosynthetic Light Harvesting by Carotenoids

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Frank, H.A.

    2010-01-01

    Roč. 43, č. 8 (2010), s. 1125-1134. ISSN 0001-4842 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * energy transfer * photosynthesis * light-harvesting Subject RIV: BO - Biophysics Impact factor: 21.840, year: 2010

  3. Dark excited states of carotenoids: Consensus and controversy

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Sundström, V.

    2009-01-01

    Roč. 477, 1-3 (2009), s. 1-11. ISSN 0009-2614 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids * excited states * relaxation pathways * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 2.291, year: 2009

  4. Femtosecond carotenoid to retinal energy transfer in xanthorhodopsin

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Balashov, S.P.; Chábera, P.; Imasheva, E.S.; Yartsev, A.; Sundström, V.; Lanyi, J.K.

    2009-01-01

    Roč. 96, č. 6 (2009), s. 2268-2277. ISSN 0006-3495 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : energy transfer * carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.390, year: 2009

  5. Photon echo spectroscopy reveals structure-dynamics relationships in carotenoids

    Czech Academy of Sciences Publication Activity Database

    Christensson, N.; Polívka, Tomáš; Yartsev, A.; Pullerits, T.

    2009-01-01

    Roč. 79, č. 24 (2009), s. 1-14. ISSN 1098-0121 Institutional research plan: CEZ:AV0Z50510513 Keywords : electron correlations * energy gap * excited states * carotenoids Subject RIV: BO - Biophysics Impact factor: 3.475, year: 2009

  6. Excited State Structural Dynamics of Carotenoids and Charge Transfer Systems

    International Nuclear Information System (INIS)

    This dissertation describes the development and implementation of a visible/near infrared pump/mid-infrared probe apparatus. Chapter 1 describes the background and motivation of investigating optically induced structural dynamics, paying specific attention to solvation and the excitation selection rules of highly symmetric molecules such as carotenoids. Chapter 2 describes the development and construction of the experimental apparatus used throughout the remainder of this dissertation. Chapter 3 will discuss the investigation of DCM, a laser dye with a fluorescence signal resulting from a charge transfer state. By studying the dynamics of DCM and of its methyl deuterated isotopomer (an otherwise identical molecule), we are able to investigate the origins of the charge transfer state and provide evidence that it is of the controversial twisted intramolecular (TICT) type. Chapter 4 introduces the use of two-photon excitation to the S1 state, combined with one-photon excitation to the S2 state of the carotenoid beta-apo-8'-carotenal. These 2 investigations show evidence for the formation of solitons, previously unobserved in molecular systems and found only in conducting polymers Chapter 5 presents an investigation of the excited state dynamics of peridinin, the carotenoid responsible for the light harvesting of dinoflagellates. This investigation allows for a more detailed understanding of the importance of structural dynamics of carotenoids in light harvesting

  7. Carotenoids are essential for the assembly of cyanobacterial photosynthetic complexes

    Czech Academy of Sciences Publication Activity Database

    Tóth, T. N.; Chukhutsina, V.; Knoppová, Jana; Komenda, Josef; Kis, M.; Lenart, Z.; Garab, G.; Kovács, L.; Gombos, Z.; van Amerongen, H.

    2015-01-01

    Roč. 1847, č. 10 (2015), s. 1153-1165. ISSN 0005-2728 R&D Projects: GA ČR GBP501/12/G055; GA MŠk LO1416 Institutional support: RVO:61388971 Keywords : Carotenoid deficiency * Cyanobacterial photosynthesis * Phycobilisome Subject RIV: EE - Microbiology, Virology Impact factor: 5.353, year: 2014

  8. Na+-Translocating Rhodopsin from Dokdonia sp. PRO95 Does Not Contain Carotenoid Antenna.

    Science.gov (United States)

    Bertsova, Y V; Arutyunyan, A M; Bogachev, A V

    2016-04-01

    Carotenoid-binding properties of Na+-translocating rhodopsin (NaR) from Dokdonia sp. PRO95 were studied. Carotenoids were extracted from Dokdonia sp. PRO95 cells. It was found that zeaxanthin is the predominant carotenoid of this bacterium. Incubation of recombinant NaR purified from Escherichia coli cells with carotenoids from Dokdonia sp. PRO95 did not result in any changes in optical absorption or circular dichroism spectra, indicating the absence of binding of the carotenoids by NaR. The same results were obtained using salinixanthin as the carotenoid. These data along with genome analysis of Dokdonia sp. PRO95 and other flavobacteria indicate that NaR from Dokdonia sp. PRO95 and possibly the other flavobacterial Na+-translocating rhodopsins do not contain a carotenoid antenna. PMID:27293099

  9. Carotenoids of Sea Angels Clione limacina and Paedoclione doliiformis from the Perspective of the Food Chain

    Directory of Open Access Journals (Sweden)

    Takashi Maoka

    2014-03-01

    Full Text Available Sea angels, Clione limacina and Paedoclione doliiformis, are small, floating sea slugs belonging to Gastropoda, and their gonads are a bright orange-red color. Sea angels feed exclusively on a small herbivorous sea snail, Limacina helicina. Carotenoids in C. limacina, P. doliiformis, and L. helicina were investigated for comparative biochemical points of view. β-Carotene, zeaxanthin, and diatoxanthin were found to be major carotenoids in L. helicina. L. helicina accumulated dietary algal carotenoids without modification. On the other hand, keto-carotenoids, such as pectenolone, 7,8-didehydroastaxanthin, and adonixanthin were identified as major carotenoids in the sea angels C. limacina and P. doliiformis. Sea angels oxidatively metabolize dietary carotenoids and accumulate them in their gonads. Carotenoids in the gonads of sea angels might protect against oxidative stress and enhance reproduction.

  10. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  11. Testing the carotenoid trade-off hypothesis in the polychromatic Midas cichlid, Amphilophus citrinellus.

    Science.gov (United States)

    Lin, Susan M; Nieves-Puigdoller, Katherine; Brown, Alexandria C; McGraw, Kevin J; Clotfelter, Ethan D

    2010-01-01

    Many animals use carotenoid pigments derived from their diet for coloration and immunity. The carotenoid trade-off hypothesis predicts that, under conditions of carotenoid scarcity, individuals may be forced to allocate limited carotenoids to either coloration or immunity. In polychromatic species, the pattern of allocation may differ among individuals. We tested the carotenoid trade-off hypothesis in the Midas cichlid, Amphilophus citrinellus, a species with two ontogenetic color morphs, barred and gold, the latter of which is the result of carotenoid expression. We performed a diet-supplementation experiment in which cichlids of both color morphs were assigned to one of two diet treatments that differed only in carotenoid content (beta-carotene, lutein, and zeaxanthin). We measured integument color using spectrometry, quantified carotenoid concentrations in tissue and plasma, and assessed innate immunity using lysozyme activity and alternative complement pathway assays. In both color morphs, dietary carotenoid supplementation elevated plasma carotenoid circulation but failed to affect skin coloration. Consistent with observable differences in integument coloration, we found that gold fish sequestered more carotenoids in skin tissue than barred fish, but barred fish had higher concentrations of carotenoids in plasma than gold fish. Neither measure of innate immunity differed between gold and barred fish, or as a function of dietary carotenoid supplementation. Lysozyme activity, but not complement activity, was strongly affected by body condition. Our data show that a diet low in carotenoids is sufficient to maintain both coloration and innate immunity in Midas cichlids. Our data also suggest that the developmental transition from the barred to gold morph is not accompanied by a decrease in innate immunity in this species. PMID:20151818

  12. Evaluation of carotenoid contents in irradiated buriti (Mauritia flexuosa L.)

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Jaqueline M. da; Coelho, Maysa J.; Lima, Keila S.C.; Lima, Antonio L.S. [Instituto Militar de Engenharia (IME), Rio de Janeiro, RJ (Brazil). Secao de Engenharia Nuclear]. E-mail: maysa@ime.eb.br; Godoy, Ronoel L.O.; Pacheco, Sidney [EMBRAPA Agroindustria de Alimentos, Rio de Janeiro, RJ (Brazil)]. E-mail: ronoel@ctaa.embrapa.br; Ferreira, Rubemar S. [Centro Regional de Ciencias Nucleares do Centro-Oeste CRCN-CO/CNEN, Abadia de Goias, GO (Brazil); E-mail: rferreira@cnen.gov.br

    2007-07-01

    Buriti (Mauritia flexuosa L.), a typical Brazilian fruit, can be found at north, northeast and center-west regions in Brazil. It has a high nutritional value and is considered an excellent source of vitamin A precursors, called carotenoids, showing a majority of {beta}-carotene. It can be used in many regional dishes. In this study, Buriti in natura was treated with gamma irradiation, deriving from a cavity type research irradiator which has a Cs-137 radiation source, with the doses of 0.5 and 1.0 kGy. The objective is to evaluate the irradiation effects on nutritional quality maintenance and conservation of Buriti, focusing in optimizer the processing conditions and increase consumption as a way to fight vitamin A deficiency. Clinical, biological and dietetic studies have indicated that the lack of vitamin A is the main cause of night blindness and xerophthalmia. The use of food irradiation is growing and represents an economic benefit to the agriculture through the reduction of post harvesting losses. The irradiated fruits and the control group were evaluated through the total carotenoids analysis, by spectrophotometry, and the carotenoids (a and b-carotene and luteine) determined by High Performance Liquid Chromatography (HPLC). ANOVA was used to treat the results. The results show that buriti is an excellent source of total carotenoids, with a concentration of 44500 {mu}g/100 g in the pulp (70% of {beta}-carotene). The reduction of carotenoids contents due to the irradiation process does not compromise its nutritional quality that is still very above of recommendations, being the dose of 0.5 kGy more appropriate. (author)

  13. Evaluation of carotenoid contents in irradiated buriti (Mauritia flexuosa L.)

    International Nuclear Information System (INIS)

    Buriti (Mauritia flexuosa L.), a typical Brazilian fruit, can be found at north, northeast and center-west regions in Brazil. It has a high nutritional value and is considered an excellent source of vitamin A precursors, called carotenoids, showing a majority of β-carotene. It can be used in many regional dishes. In this study, Buriti in natura was treated with gamma irradiation, deriving from a cavity type research irradiator which has a Cs-137 radiation source, with the doses of 0.5 and 1.0 kGy. The objective is to evaluate the irradiation effects on nutritional quality maintenance and conservation of Buriti, focusing in optimizer the processing conditions and increase consumption as a way to fight vitamin A deficiency. Clinical, biological and dietetic studies have indicated that the lack of vitamin A is the main cause of night blindness and xerophthalmia. The use of food irradiation is growing and represents an economic benefit to the agriculture through the reduction of post harvesting losses. The irradiated fruits and the control group were evaluated through the total carotenoids analysis, by spectrophotometry, and the carotenoids (a and b-carotene and luteine) determined by High Performance Liquid Chromatography (HPLC). ANOVA was used to treat the results. The results show that buriti is an excellent source of total carotenoids, with a concentration of 44500 μg/100 g in the pulp (70% of β-carotene). The reduction of carotenoids contents due to the irradiation process does not compromise its nutritional quality that is still very above of recommendations, being the dose of 0.5 kGy more appropriate. (author)

  14. Recent Applications of the (TMS3SiH Radical-Based Reagent

    Directory of Open Access Journals (Sweden)

    Chryssostomos Chatgilialoglu

    2012-01-01

    Full Text Available This review article focuses on the recent applications of tris(trimethylsilylsilane as a radical-based reagent in organic chemistry. Numerous examples of the successful use of (TMS3SiH in radical reductions, hydrosilylation and consecutive radical reactions are given. The use of (TMS3SiH allows reactions to be carried out under mild conditions with excellent yields of products and remarkable chemo-, regio-, and stereoselectivity. The strategic role of (TMS3SiH in polymerization is underlined with emphasis on the photo-induced radical polymerization of olefins and photo-promoted cationic polymerization of epoxides.

  15. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro

    2013-05-01

    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  16. Radical cystectomy in eldery

    OpenAIRE

    Bančević Vladimir; Aleksić Predrag; Milović Novak; Spasić Aleksandar; Kovačević Božidar; Toševski Perica; Čampara Zoran; Milošević Radovan; Cerović Snežana

    2015-01-01

    Background/Aim. Radical cystectomy is the method of choice for the treatment of muscle invasive bladder cancer. This major surgery is associated with many complications, especially in older patients. The aim of this study was to analyze preoperative comorbidity, and intraoperative and postoperative complicatons in patients older than 75 years. Methods. This clinical, retrospective study included 46 patients over 75 years, who underwent radical cystectomy. I...

  17. Potential of Dietary Non-Provitamin A Carotenoids in the Prevention and Treatment of Diabetic Microvascular Complications.

    Science.gov (United States)

    Murillo, Ana Gabriela; Fernandez, Maria Luz

    2016-01-01

    Diabetes is a chronic metabolic disease that affects a substantial part of the population around the world. Whether type I or type II, this disease has serious macro- and microvascular complications that constitute the primary cause of death in diabetic patients. Microvascular complications include diabetic retinopathy, nephropathy, and neuropathy. Although these complications are clinically and etiologically diverse, they share a common factor: glucose-induced damage. In the progression of diabetic complications, oxidative stress, inflammation, and the formation of glycation end products play an important role. Previous studies have shown that a healthy diet is vital in preventing these complications; in particular, the intake of antioxidants has been studied for their potential effect in ameliorating hyperglycemic injuries. Carotenoids are lipid-soluble pigments synthesized by plants, bacteria, and some kinds of algae that are responsible for the yellow, red, and orange colors in food. These compounds are part of the antioxidant machinery in plants and have also shown their efficacy in quenching free radicals, scavenging reactive oxygen species, modulating gene expression, and reducing inflammation in vitro and in vivo, showing that they can potentially be used as part of a preventive strategy for metabolic disorders, including diabetes and its related complications. This review highlights the potential protective effects of 4 non-provitamin A carotenoids-lutein, zeaxanthin, lycopene, and astaxanthin-in the development and progression of diabetic microvascular complications. PMID:26773012

  18. Study of 'Redhaven' peach and its white-fleshed mutant suggests a key role of CCD4 carotenoid dioxygenase in carotenoid and norisoprenoid volatile metabolism

    Directory of Open Access Journals (Sweden)

    Tartarini Stefano

    2011-01-01

    Full Text Available Abstract Background Carotenoids are plant metabolites which are not only essential in photosynthesis but also important quality factors in determining the pigmentation and aroma of flowers and fruits. To investigate the regulation of carotenoid metabolism, as related to norisoprenoids and other volatile compounds in peach (Prunus persica L. Batsch., and the role of carotenoid dioxygenases in determining differences in flesh color phenotype and volatile composition, the expression patterns of relevant carotenoid genes and metabolites were studied during fruit development along with volatile compound content. Two contrasted cultivars, the yellow-fleshed 'Redhaven' (RH and its white-fleshed mutant 'Redhaven Bianca' (RHB were examined. Results The two genotypes displayed marked differences in the accumulation of carotenoid pigments in mesocarp tissues. Lower carotenoid levels and higher levels of norisoprenoid volatiles were observed in RHB, which might be explained by differential activity of carotenoid cleavage dioxygenase (CCD enzymes. In fact, the ccd4 transcript levels were dramatically higher at late ripening stages in RHB with respect to RH. The two genotypes also showed differences in the expression patterns of several carotenoid and isoprenoid transcripts, compatible with a feed-back regulation of these transcripts. Abamine SG - an inhibitor of CCD enzymes - decreased the levels of both isoprenoid and non-isoprenoid volatiles in RHB fruits, indicating a complex regulation of volatile production. Conclusions Differential expression of ccd4 is likely to be the major determinant in the accumulation of carotenoids and carotenoid-derived volatiles in peach fruit flesh. More in general, dioxygenases appear to be key factors controlling volatile composition in peach fruit, since abamine SG-treated 'Redhaven Bianca' fruits had strongly reduced levels of norisoprenoids and other volatile classes. Comparative functional studies of peach carotenoid

  19. On the Route to the Photogeneration of Heteroaryl Cations. The Case of Halothiophenes.

    Science.gov (United States)

    Raviola, Carlotta; Chiesa, Francesco; Protti, Stefano; Albini, Angelo; Fagnoni, Maurizio

    2016-08-01

    2-Chloro-, 2-bromo-, and 2-iodothiophenes undergo photochemical dehalogenation via the triplet state. In the presence of suitable π-bond nucleophiles, thienylation occurs with modest yield from chloro and bromo derivatives (via photogenerated triplet 2-thienyl cation). Specific trapping by using oxygen along with computational analysis carried out by means of a density functional method support that, in the case of iodo derivatives, homolytic thienyl-I bond fragmentation occurs first and heteroaryl cations are formed by electron transfer within the triplet radical pair, thus opening an indirect access to such cations. PMID:27383725

  20. Free Radical Reactions in Food.

    Science.gov (United States)

    Taub, Irwin A.

    1984-01-01

    Discusses reactions of free radicals that determine the chemistry of many fresh, processed, and stored foods. Focuses on reactions involving ascorbic acid, myoglobin, and palmitate radicals as representative radicals derived from a vitamin, metallo-protein, and saturated lipid. Basic concepts related to free radical structure, formation, and…

  1. Accumulation of carotenoids and expression of carotenogenic genes in peach fruit.

    Science.gov (United States)

    Cao, Shifeng; Liang, Minhua; Shi, Liyu; Shao, Jiarong; Song, Chunbo; Bian, Kun; Chen, Wei; Yang, Zhenfeng

    2017-01-01

    To understand better the regulatory mechanism of the carotenoid accumulation, the expression profile of relevant carotenoid genes and metabolites were compared between two peach cultivars with different colors during fruit development. Meanwhile, the change pattern of carotenoid content and expression of carotenoid metabolic genes in peaches after harvest in response to blue light were also investigated. As compared to the yellow fleshed-cultivar 'Jinli', lower carotenoid levels were observed in skin and pulp in white peach cultivar 'Hujing', which might be explained by differentially expression of PpCCD4 gene. With respect to 'Jinli', the carotenoid accumulation during fruit development in fruit skin was partially linked with the transcriptional regulation of PpFPPS, PpGGPS, PpLCYB and PpCHYB. However, in the pulp, the accumulation might be also associated with the increased transcriptions of PpPDS, along with the above four genes. Blue light treatment induced carotenoid accumulation in 'Jinli' peaches during storage. In addition, the treated-fruit displayed higher expression of all the eight genes analysed with a lesser extent on PpCCD4, which suggested that the much more increased carotenoid synthesis rate could result in the higher carotenoid content in blue light-treated fruit. The results presented herein contribute to further elucidating the regulatory mechanism of carotenoid accumulation in peach fruit. PMID:27507458

  2. Utilization of Microemulsions from Rhinacanthus nasutus (L.) Kurz to Improve Carotenoid Bioavailability.

    Science.gov (United States)

    Ho, Nai-Hsing; Inbaraj, Baskaran Stephen; Chen, Bing-Huei

    2016-01-01

    Carotenoids have been known to reduce the risk of several diseases including cancer and cardiovascular. However, carotenoids are unstable and susceptible to degradation. Rhinacanthus nasutus (L.) Kurz (R. nasutus), a Chinese medicinal herb rich in carotenoids, was reported to possess vital biological activities such as anti-cancer. This study intends to isolate carotenoids from R. nasutus by column chromatography, identify and quantify by HPLC-MS, and prepare carotenoid microemulsions for determination of absolute bioavailability in rats. Initially, carotenoid fraction was isolated using 250 mL ethyl acetate poured into an open-column packed with magnesium oxide-diatomaceous earth (1:3, w/w). Fourteen carotenoids including internal standard β-apo-8'-carotenal were resolved within 62 min by a YMC C30 column and gradient mobile phase of methanol-acetonitrile-water (82:14:4, v/v/v) and methylene chloride. Highly stable carotenoid microemulsions were prepared using a mixture of Capryol(TM)90, Transcutol®HP, Tween 80 and deionized water, with the mean particle being 10.4 nm for oral administration and 10.7 nm for intravenous injection. Pharmacokinetic study revealed that the absolute bioavailability of carotenoids in microemulsions and dispersion was 0.45% and 0.11%, respectively, while a much higher value of 6.25% and 1.57% were shown for lutein, demonstrating 4-fold enhancement in bioavailability upon incorporation of R. nasutus carotenoids into a microemulsion system. PMID:27150134

  3. Carotenoids and amphibians: effects on life history and susceptibility to the infectious pathogen, Batrachochytrium dendrobatidis.

    Science.gov (United States)

    Cothran, Rickey D; Gervasi, Stephanie S; Murray, Cindy; French, Beverly J; Bradley, Paul W; Urbina, Jenny; Blaustein, Andrew R; Relyea, Rick A

    2015-01-01

    Carotenoids are considered beneficial nutrients because they provide increased immune capacity. Although carotenoid research has been conducted in many vertebrates, little research has been done in amphibians, a group that is experiencing global population declines from numerous causes, including disease. We raised two amphibian species through metamorphosis on three carotenoid diets to quantify the effects on life-history traits and post-metamorphic susceptibility to a fungal pathogen (Batrachochytrium dendrobatidis; Bd). Increased carotenoids had no effect on survival to metamorphosis in gray treefrogs (Hyla versicolor) but caused lower survival to metamorphosis in wood frogs [Lithobates sylvaticus (Rana sylvatica)]. Increased carotenoids caused both species to experience slower development and growth. When exposed to Bd after metamorphosis, wood frogs experienced high mortality, and the carotenoid diets had no mitigating effects. Gray treefrogs were less susceptible to Bd, which prevented an assessment of whether carotenoids could mitigate the effects of Bd. Moreover, carotenoids had no effect on pathogen load. As one of only a few studies examining the effects of carotenoids on amphibians and the first to examine potential interactions with Bd, our results suggest that carotenoids do not always serve amphibians in the many positive ways that have become the paradigm in other vertebrates. PMID:27293690

  4. The Or gene enhances carotenoid accumulation and stability during post-harvest storage of potato tubers.

    Science.gov (United States)

    Li, Li; Yang, Yong; Xu, Qiang; Owsiany, Katherine; Welsch, Ralf; Chitchumroonchokchai, Chureeporn; Lu, Shan; Van Eck, Joyce; Deng, Xiu-Xin; Failla, Mark; Thannhauser, Theodore W

    2012-03-01

    Provitamin A carotenoids in staple crops are not very stable during storage and their loss compromises nutritional quality. To elucidate the fundamental mechanisms underlying carotenoid accumulation and stability, we investigated transgenic potato tubers that expressed the cauliflower Orange (Or) gene. We found that the Or transgene not only promoted retention of β-carotene level, but also continuously stimulated its accumulation during 5 months of cold storage. In contrast, no increased levels of carotenoids were observed in the tubers of vector-only controls or a yellow-flesh variety during the same period of storage. The increased carotenoid accumulation was found to be associated with the formation of lipoprotein-carotenoid sequestering structures, as well as with the enhanced abundance of phytoene synthase, a key enzyme in the carotenoid biosynthetic pathway. Furthermore, the provitamin A carotenoids stored were shown to be stable during simulated digestion and accessible for uptake by human intestinal absorptive cells. Proteomic analysis identified three major functional groups of proteins (i.e. heat shock proteins, glutathione-S-transferases, and carbohydrate metabolic proteins) that are potentially important in the Or-regulated carotenoid accumulation. Our results show that regulation of carotenoid sequestration capacity is an important mechanism by which carotenoid stability is regulated. Our findings suggest that induction of a proper sink structure formation in staple crops may provide the crops with a unique ability to promote and/or stabilize provitamin A accumulation during plant growth and post-harvest storage. PMID:22155949

  5. Opposing effects of oxidative challenge and carotenoids on antioxidant status and condition-dependent sexual signalling.

    Science.gov (United States)

    Tomášek, Oldřich; Gabrielová, Barbora; Kačer, Petr; Maršík, Petr; Svobodová, Jana; Syslová, Kamila; Vinkler, Michal; Albrecht, Tomáš

    2016-01-01

    Several recent hypotheses consider oxidative stress to be a primary constraint ensuring honesty of condition-dependent carotenoid-based signalling. The key testable difference between these hypotheses is the assumed importance of carotenoids for redox homeostasis, with carotenoids being either antioxidant, pro-oxidant or unimportant. We tested the role of carotenoids in redox balance and sexual signalling by exposing adult male zebra finches (Taeniopygia guttata) to oxidative challenge (diquat dibromide) and manipulating carotenoid intake. As the current controversy over the importance of carotenoids as antioxidants could stem from the hydrophilic basis of commonly-used antioxidant assays, we used the novel measure of in vivo lipophilic antioxidant capacity. Oxidative challenge reduced beak pigmentation but elicited an increase in antioxidant capacity suggesting resource reallocation from signalling to redox homeostasis. Carotenoids counteracted the effect of oxidative challenge on lipophilic (but not hydrophilic) antioxidant capacity, thereby supporting carotenoid antioxidant function in vivo. This is inconsistent with hypotheses proposing that signalling honesty is maintained through either ROS-induced carotenoid degradation or the pro-oxidant effect of high levels of carotenoid-cleavage products acting as a physiological handicap. Our data further suggest that assessment of lipophilic antioxidant capacity is necessary to fully understand the role of redox processes in ecology and evolution. PMID:27000655

  6. Effects of experimental brood size manipulation and gender on carotenoid levels of Eurasian kestrels Falco tinnunculus.

    Directory of Open Access Journals (Sweden)

    Toni Laaksonen

    Full Text Available BACKGROUND: Animals use carotenoid-pigments for coloration, as antioxidants and as enhancers of the immune system. Carotenoid-dependent colours can thus signal individual quality and carotenoids have also been suggested to mediate life-history trade-offs. METHODOLOGY: To examine trade-offs in carotenoid allocation between parents and the young, or between skin coloration and plasma of the parents at different levels of brood demand, we manipulated brood sizes of Eurasian kestrels (Falco tinnunculus. PRINCIPAL FINDINGS: Brood size manipulation had no overall effect on plasma carotenoid levels or skin hue of parents, but female parents had twice the plasma carotenoid levels of males. Males work physically harder than females and they might thus also use more carotenoids against oxidative stress than females. Alternatively, females could be gaining back the carotenoid stores they depleted during egg-laying by eating primarily carotenoid-rich food items during the early nestling stage. Fledglings in enlarged broods had higher plasma carotenoid concentrations than those in reduced broods. This difference was not explained by diet. In light of recent evidence from other species, we suggest it might instead be due to fledglings in enlarged broods having higher testosterone levels, which in turn increased plasma carotenoid levels. The partial cross-foster design of our experiment revealed evidence for origin effects (genetic or maternal on carotenoid levels of fledglings, but no origin-environment interaction. SIGNIFICANCE: These results from wild birds differ from studies in captivity, and thus offer new insights into carotenoid physiology in relation to division of parental care and demands of the brood.

  7. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    CERN Document Server

    Lewis, Alan M; Hore, P J

    2014-01-01

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene (CPF) triad containing considerably more nu...

  8. Characterization of carotenoid-protein complexes and gene expression analysis associated with carotenoid sequestration in pigmented cassava (Manihot esculenta Crantz) storage root

    Science.gov (United States)

    Carotenoid-protein complex separation by size exclusion chromatography, protein fractionation by SDS-PAGE, and shotgun PROTEOMICS technology were used to identify and characterize carotenoid associated proteins (CAPs) of chromoplast-enriched suspensions from cassava intense yellow storage root. A no...

  9. Ion exchange behaviour of polymeric zirconium cations

    International Nuclear Information System (INIS)

    Polymeric zirconium cations formed in weakly acid solutions (pH2) are taken up strongly into macroporous cation exchange resins, while uptake into normal cation exchange resins (pore diameter about 1 nm) is low. Macroporous cation exchange resins loaded with polymeric Zr cations are shown to function as ligand exchange sorbents. (Authors)

  10. Effects of organic and conventional growth systems on the content of carotenoids in carrot roots, and on intake and plasma status of carotenoids in humans

    DEFF Research Database (Denmark)

    Søltoft, Malene; Bysted, Anette; Madsen, K. H.;

    2011-01-01

    BACKGROUND: The demand for organic food products has increased during the last decades due to their probable health effects, among others. A higher content of secondary metabolites such as carotenoids in organic food products has been claimed, though not documented, to contribute to increased...... health effects of organic foods. The aim was to study the impact of organic and conventional agricultural systems on the content of carotenoids in carrots and human diets. In addition, a human cross-over study was performed, measuring the plasma status of carotenoids in humans consuming diets made from...... crops from these agricultural systems. RESULTS: The content of carotenoids in carrot roots and human diets was not significantly affected by the agricultural production system or year, despite differences in fertilisation strategy and levels. The plasma status of carotenoids increased significantly...

  11. Effect of electron-withdrawing power of the substituted group on ${}^{\\bullet}$OH radical reaction with substituted aryl sulphides: A pulse radiolysis study

    Indian Academy of Sciences (India)

    Hari Mohan

    2002-12-01

    In neutral aqueous solution of (phenylthio)acetic acid, hydroxyl radical is observed to react with a bimolecular rate constant of 7.2 × 109 dm3 mol-1 s-1 and the transient absorption bands are assigned to ${}^{\\bullet}$OH radical addition to benzene and sulphur with a rough estimated values of 50 and 40% respectively. The reaction of the ${}^{\\bullet}$OH radical with diphenyl sulphide ( = 4.3 × 108 dm3 mol-1 s-1) is observed to take place with formation of solute radical cation, OH-adduct at sulphur and benzene with estimated values of about 12, 28 and 60% respectively. The transient absorption bands observed on reaction of ${}^{\\bullet}$OH radical, in neutral aqueous solution of 4-(methylthio) phenyl acetic acid, are assigned to solute radical cation (max = 550 and 730 nm), OH-adduct at sulphur (max = 360 nm) and addition at benzene ring (max = 320 nm). The fraction of ${}^{\\bullet}$OH radical reacting to form solute radical cation is observed to depend on the electron-withdrawing power of substituted group. In acidic solutions, depending on the concentration of acid and electron-withdrawing power, solute radical cation is the only transient species formed on reaction of ${}^{\\bullet}$OH radical with the sulphides studied.

  12. The maximin principle of pi-radical packings.

    Science.gov (United States)

    Devic, Thomas; Yuan, Min; Adams, Judy; Fredrickson, Daniel C; Lee, Stephen; Venkataraman, D

    2005-10-26

    A two-term model is proposed for hydrocarbon and N-containing pi-radicals which are in close contact with one another. The first term is attractive (due to partially occupied frontier pi-orbitals), and the second, repulsive (due to hard-core repulsion between close-lying atoms). This model is applied to dimers where intermolecular contacts are closer than maximin principle is proposed. The maximin principle states that the lowest energy conformation maximizes overlap of the frontier orbitals while simultaneously minimizing intermolecular contacts. A Hückel Hamiltonian, the mu(2)-Hamiltonian, which contains the above attractive and repulsive terms, is applied. The interaction surfaces of two pi-hydrocarbon radical cations were calculated for the three systems known crystallographically to contain cations in close contact: naphthalene, fluoranthene, and pyrene. The global minima of these surfaces correspond to the experimentally determined structures. The mu(2)-Hamiltonian energy surfaces of the naphthalene cation dimer are qualitatively similar to those calculated at the RHF/6-311G(d,p) and MP2/6-311G(d,p) levels. The maximin principle is applied to N-containing pi-radicals. Except in the case of tetracyanoethene, the maximin principle correctly predicts the most common dimer crystal packing. (MgPc)(NO(3)).0.5THF and (MgPc)(ReO(4)).1.5THF (Pc = phthalocyanine) were prepared: both new crystal structures follow the maximin principle. The maximin principle is used to suggest the dimer cation ground state of oligoacenes, cations important as organic hole-based semiconductors. PMID:16231914

  13. Gangs, Terrorism, and Radicalization

    Directory of Open Access Journals (Sweden)

    Scott Decker

    2011-01-01

    Full Text Available What can street gangs tell us about radicalization and extremist groups? At first glance, these two groups seem to push the boundaries of comparison. In this article, we examine the important similarities and differences across criminal, deviant, and extremist groups. Drawing from research on street gangs, this article explores issues such as levels of explanation,organizational structure, group process, and the increasingly important role of technology and the Internet in the context of radicalization. There are points of convergence across these groups, but it is important to understand the differences between these groups. This review finds little evidence to support the contention that American street gangs are becoming increasingly radicalized. This conclusion is based largely on organizational differences between gangs and terror groups.

  14. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Serefoglu, Ege C; Albersen, Maarten;

    2016-01-01

    INTRODUCTION: Radical prostatectomies can result in urinary incontinence and sexual dysfunction. Traditionally, these issues have been studied separately, and the sexual problem that has received the most focus has been erectile dysfunction. AIM: To summarize the literature on sexually related side...... effects and their consequences after radical prostatectomy and focus on the occurrence and management of problems beyond erectile dysfunction. METHODS: The literature on sexuality after radical prostatectomy was reviewed through a Medline search. Original research using quantitative and qualitative...... methodologies was considered. Priority was given to studies exploring aspects of sexuality other than erectile function. MAIN OUTCOME MEASURES: The prevalence, predictive factors, and management of post-prostatectomy sexual problems beyond erectile dysfunction. RESULTS: Most patients will develop urinary...

  15. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.

    2015-05-01

    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  16. Colorful World of Microbes: Carotenoids and Their Applications

    Directory of Open Access Journals (Sweden)

    Kushwaha Kirti

    2014-01-01

    Full Text Available Microbial cells accumulate pigments under certain culture conditions, which have very important industrial applications. Microorganisms can serve as sources of carotenoids, the most widespread group of naturally occurring pigments. More than 750 structurally different yellow, orange, and red colored molecules are found in both eukaryotes and prokaryotes with an estimated market of $ 919 million by 2015. Carotenoids protect cells against photooxidative damage and hence found important applications in environment, food and nutrition, disease control, and as potent antimicrobial agents. In addition to many research advances, this paper reviews concerns with recent evaluations, applications of microbial pigments, and recommendations for future researches with an understanding of evolution and biosynthetic pathways along with other relevant aspects.

  17. Resonance Raman measurements of carotenoids using light emitting diodes

    CERN Document Server

    Bergeson, S D; Eyring, N J; Fralick, J F; Stevenson, D N; Ferguson, S B

    2008-01-01

    We report on the development of a compact commercial instrument for measuring carotenoids in skin tissue. The instrument uses two light emitting diodes (LEDs) for dual-wavelength excitation and four photomultiplier tubes for multichannel detection. Bandpass filters are used to select the excitation and detection wavelengths. The f/1.3 optical system has high optical throughput and single photon sensitivity, both of which are crucial in LED-based Raman measurements. We employ a signal processing technique that compensates for detector drift and error. The sensitivity and reproducibility of the LED Raman instrument compares favorably to laser-based Raman spectrometers. This compact, portable instrument is used for non-invasive measurement of carotenoid molecules in human skin with a repeatability better than 10%.

  18. Absorption of Carotenoids and Mechanisms Involved in Their Health-Related Properties.

    Science.gov (United States)

    Cervantes-Paz, Braulio; Victoria-Campos, Claudia I; Ornelas-Paz, José de Jesús

    2016-01-01

    Carotenoids participate in the normal metabolism and function of the human body. They are involved in the prevention of several diseases, especially those related to the inflammation syndrome. Their main mechanisms of action are associated to their potent antioxidant activity and capacity to regulate the expression of specific genes and proteins. Recent findings suggest that carotenoid metabolites may explain several processes where the participation of their parent carotenoids was unclear. The health benefits of carotenoids strongly depend on their absorption and transformation during gastrointestinal digestion. The estimation of the 'bioaccessibility' of carotenoids through in vitro models have made possible the evaluation of the effect of a large number of factors on key stages of carotenoid digestion and intestinal absorption. The bioaccessibility of these compounds allows us to have a clear idea of their potential bioavailability, a term that implicitly involves the biological activity of these compounds. PMID:27485232

  19. Analysis on Carotenoids Content and Other Quality Traits of 185 Wheat Varieties

    Institute of Scientific and Technical Information of China (English)

    Jian ZHOU; Yuanyuan WU; Wenyin ZHENG; Wenming ZHANG; Wenshang GUO; Danian YAO

    2015-01-01

    In order to provide the reference of improving the nutritional quality traits in carotenoids and screening its resources of wheat varieties, 185 wheat varieties or lines were selected as materials to test the carotenoids content, lipoxygenase activ-ity, whiteness, yel owness and some other quality traits of whole mil in wheat.The results showed that there were highly significant variations in lipoxygenase activity , carotenoids content, whiteness and yel owness among those sample of wheat vari-eties; carotenoids content was significantly and positively correlated with yel owness. Cluster analysis was performed based on carotenoids content clustered al the vari-eties or lines into three major groups. Additional y, carotenoids were discussed in the application of nutritional quality improvement in wheat.

  20. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    and their families. Existing literature and ways of thinking about the social psychological process of radicalization will be reviewed, such as social identity theory and transformative learning theory, and a theoretical framework based on a focus on belonging, recognition and the sense of community......It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper aims at exploring the reasons behind this seemingly religious radicalization from the point of view of the youngsters...

  1. Microscale extraction method for HPLC carotenoid analysis in vegetable matrices

    OpenAIRE

    Sidney Pacheco; Fernanda Marques Peixoto; Renata Galhardo Borguini; Luzimar da Silva de Mattos do Nascimento; Claudio Roberto Ribeiro Bobeda; Manuela Cristina Pessanha de Araújo Santiago; Ronoel Luiz de Oliveira Godoy

    2014-01-01

    In order to generate simple, efficient analytical methods that are also fast, clean, and economical, and are capable of producing reliable results for a large number of samples, a micro scale extraction method for analysis of carotenoids in vegetable matrices was developed. The efficiency of this adapted method was checked by comparing the results obtained from vegetable matrices, based on extraction equivalence, time required and reagents. Six matrices were used: tomato (Solanum lycopersicum...

  2. Carotenoids and skin coloration in a social raptor

    OpenAIRE

    Blas, Julio; Cabezas, Sonia; Figuerola, Jordi; López, Lidia; Tanferna, Alessandro; Hiraldo, F.; Sergio, Fabrizio; Negro, Juan J.

    2013-01-01

    [IN] The outcome of social and sexual competition in animals is typically mediated through the expression of body traits. Conspicuous characters such as yellow, orange, and red colorations in skin, scales, and feathers are often posited as quality-dependent signals, because such colors are made of dietary carotenoids and their use for signaling conflicts with health functions. Raptors often lack brightly colored feathers but most diurnal species display intense orange and yellow hues in the c...

  3. Identification and Quantification of Major Carotenoids in Some Vegetables

    OpenAIRE

    Jafar M. El-Qudah

    2009-01-01

    An HPLC study of 6 raw vegetables (Okra, green beans, eggplant zucchini, carrot and tomato) most frequently consumed worldwide was carried out to determine their carotenoid composition. The samples were purchased from supermarket in the city of Boston, USA. Neoxanthin, violaxanthin and lutein were contained in all samples except tomato for neoxanthin, carrot and tomato for violaxanthin and carrot for lutein. β-carotene was contained in all samples while α-carotene was contained only...

  4. Resonance Raman detection of carotenoid antioxidants in living human tissue

    OpenAIRE

    Ermakov, Igor V.; M Sharifzadeh; Ermakova, Maia; Gellermann, W.

    2005-01-01

    Increasing evidence points to the beneficial effects of carotenoid antioxidants in the human body. Several studies, for example, support the protective role of lutein and zeaxanthin in the prevention of age-related eye diseases. If present in high concentrations in the macular region of the retina, lutein and zeaxanthin provide pigmentation in this most light sensitive retinal spot, and as a result of light filtering and/or antioxidant action, delay the onset of macular degeneration with incr...

  5. Structures and Properties of Stabilized Vitamin and Carotenoid Dry Powders

    OpenAIRE

    Colombo, Victor E.; Gerber, Francoise

    1991-01-01

    The development of special formulated forms of vitamin and carotenoid dry powders solved most of the technical problems encountered in handling the original pure crystalline or oily compounds. Various procedures to obtain stabilized products have been introduced on an industrial scale for feed , food and pharmaceutical purposes. Proven modes of manufacture of formulated dry powders includes the numerous spraying processes for emulsions, dispersions or solutions, and the production of adsorbat...

  6. Study of RP HPLC Retention Behaviours in Analysis of Carotenoids.

    Science.gov (United States)

    Ligor, M; Kováčová, J; Gadzała-Kopciuch, R M; Studzińska, S; Bocian, Sz; Lehotay, J; Buszewski, B

    2014-01-01

    For determination of selected carotenoids, various types of columns for high-performance liquid chromatography (HPLC) with different properties have been used. The characteristics of the laboratory-used packing material containing monomeric alkyl-bonded phases (C18, C30) and phenyl as well as phenyl-hexyl stationary phases were studied. The retention data of the examined compounds were used to determine the hydrophobicity and silanol activity of stationary phases applied in the study. The presence of the polar and carboxyl groups in the structure of the bonded ligand strongly influences the polarity of the stationary phase. Columns were compared according to methylene selectivity using a series of benzene homologues. The measurements were done using a methanol-water mobile phase. Knowledge of the properties of the applied stationary phase provided the possibility to predict the RP HPLC retention behaviours in analysis of carotenoids including lutein, lycopene and β-carotene. The composition of the mobile phase, the addition of triethylamine and the type of stationary phase had been taken into account in designing the method of carotenoid identification. Also a monolithic column characterised by low hydrodynamic resistance, high porosity and high permeability was applied. The presented results show that the coverage density of the bonded ligands on silica gel packings and length of the linkage strongly influence the carotenoid retention behaviours. In our study, the highest retention parameters for lutein, lycopene and β-carotene were observed for C30 and C18 stationary phase. This effect corresponds with pore size of column packing greater than 100 Å and carbon content higher than 11 %. PMID:25089049

  7. THE CAROTENOID BIOSYNTHETIC PATHWAY: THINKING IN ALL DIMENSIONS

    OpenAIRE

    Shumskaya, Maria; Wurtzel, Eleanore T.

    2013-01-01

    The carotenoid biosynthetic pathway serves manifold roles in plants related to photosynthesis, photoprotection, development, stress hormones, and various volatiles and signalling apocarotenoids. The pathway also produces compounds that impact human nutrition and metabolic products that contribute to fragrance and flavour of food and non-food crops. It is no surprise that the pathway has been a target of metabolic engineering, most prominently in the case of Golden Rice. The future success and...

  8. Fast atom bombardment tandem mass spectrometry of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    van Breeman, R.B. [Univ. of Illinois, Chicago, IL (United States); Schmitz, H.H.; Schwartz, S.J. [North Carolina State Univ., Raleigh, NC (United States)

    1995-02-01

    Positive ion fast atom bombardment (FAB) tandem mass spectrometry (MS-MS) using a double-focusing mass spectrometer with linked scanning at constant B/E and high-energy collisionally activated dissociation (CAD) was used to differentiate 17 different cartenoids, including {beta}-apo-8{prime}- carotenal, astaxanthin, {alpha}-carotene, {beta}-carotene, {gamma}-carotene, {zeta}-carotene, canthaxanthin, {beta}-cryptoxanthin, isozeaxanthin bis (pelargonate), neoxanthin, neurosporene, nonaprene, lutein, lycopene, phytoene, phytofluene, and zeaxanthin. The carotenoids were either synthetic or isolated from plant tissues. The use of FAB ionization minimized degradation or rearrangement of the carotenoid structures due to the inherent thermal instability generally ascribed to these compounds. Instead of protonated molecules, both polar xanthophylls and nonpolar carotenes formed molecular ions, M{sup {center_dot}+}, during FAB ionization. Following collisionally activated dissociation, fragment ions of selected molecular ion precursors showed structural features indicative of the presence of hydroxyl groups, ring systems, ester groups, and aldehyde groups and the extent of aliphatic polyene conjugation. The fragmentation patterns observed in the mass spectra herein may be used as a reference for the structural determination of carotenoids isolated from plant and animal tissues. 18 refs., 4 figs.

  9. Spectroscopic characterization of mechanisms of oxidation of Phe by SO4- radical: A pulse radiolysis study

    Institute of Scientific and Technical Information of China (English)

    储高升; 韩镇辉; 都志文; 张淑娟; 姚思德; 张志成

    2002-01-01

    By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal that attack of the oxidizing SO4- radical on Phe leads directlyto the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes -COOH and -NH2 and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.

  10. Spectroscopic characterization of mechanisms of oxidation of Phe by SO.-4 radical: A pulse radiolysis study

    Institute of Scientific and Technical Information of China (English)

    储高升; 张淑娟; 姚思德; 韩镇辉; 都志文; 张志成

    2002-01-01

    By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by radical has been investigated both in aqueous and water/acetonitrile mixed solutions. The results reveal that attack of the oxidizing SO4-radical on Phe leads directly to the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes -COOH and -NH2 and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.

  11. Nematode parasites reduce carotenoid-based signalling in male red grouse

    OpenAIRE

    Martínez-Padilla, Jesús; Mougeot, François; Pérez-Rodríguez, Lorenzo; Gary R. Bortolotti

    2007-01-01

    Carotenoids determine the yellow–red colours of many ornaments, which often function as signals of quality. Carotenoid-based signalling may reliably advertise health and should be particularly sensitive to parasite infections. Nematodes are among the commonest parasites of vertebrates, with well-documented negative effects on their hosts. However, to date, little is known about the effects that these parasites may have on carotenoid-based signalling. Tetraonid birds (grouse) exhibit supra-orb...

  12. Carotenoids in Eggs and Plasma of Red-Legged Partridges: Effects of Diet and Reproductive Output

    OpenAIRE

    Bortolotti, Gary R.; Negro, Juan J.; Surai, Peter F; Prieto, Paloma

    2003-01-01

    Carotenoids are important dietary constituents in birds. They serve as pigments and play numerous physiological roles in both the laying hen and developing embryo. However, factors determining the absorption of carotenoids and their allocation to different functions are numerous and complex, and causal relationships are generally poorly known. Our objective was to determine the degree to which carotenoid levels in egg yolks and the plasma of hens were influenced by differences in diet and ...

  13. Theoretical studies of the electrochromic response of carotenoids in photosynthetic membranes.

    OpenAIRE

    Kakitani, T; Honig, B.; Crofts, A R

    1982-01-01

    Molecular orbital calculations are carried out on a number of carotenoids in the presence of an external charge and a constant electric field. The external charge is used to represent the strong permanent field that is believed to polarize carotenoids in photosynthetic membranes and thus to account for their linear response to the transmembrane potential. Our calculations show that the in vitro leads to in vivo spectral shifts of carotenoids (approximately 25 nm) can be produced by a charge i...

  14. The nature and the content of carotenoid pigments from faded leaves of Aesculus hippocastanum L.

    OpenAIRE

    Gino ROSCA; Sanda CRAPATUREANU; Socaciu, Carmen; Gavrila NEAMTU

    1995-01-01

    Faded leaves of Aesculus hippocastanum L. harvested in October and November have a high and various content of carotenoids. The content of lutein and zeaxanthin is much higher in faded leaves than in the green ones, that is why they are recommended as an important natural source for extraction (at an industrial level) of the mentioned carotenoids. Faded leaves have a low biological value, because they have a low content of provitaminic A carotenoids. They have also a low content of hydrocarbo...

  15. Studies on carotenoids and oxidative stability of winter squash seed and soybean oils

    OpenAIRE

    Helmy, H. E.

    1992-01-01

    Winter squash seed and soybean oils were extracted with commercial hexane. Carotenoids and other pigments m the oils were studied using spectrophotometric and thin layer chromatographic analysis. Three types of pigments were identified: carotenoids. mainly lutein and β-carotene, chlorophyll and some unidentified pigments. Carotenoids content were 70, 60, 0 ppm in crude, refined and bleached winter squash seed oil, and 80, 65, 0 ppm in crude, refined and bleached soybean oil respectively. ...

  16. Plasma carotenoid levels in passerines are related to infection by (some parasites

    Directory of Open Access Journals (Sweden)

    JordiFiguerola

    2014-08-01

    Full Text Available Plumage coloration plays an important role in intra and inter-sexual competition in birds. Many of the yellow, orange or red colours present in birds are carotenoid dependent. Carotenoids can not be synthetized de novo by birds and consequently should be obtained through their diet, and access to carotenoids may differ between individuals and species. In addition to ornamentation, carotenoids are important for bird physiology and it has been proposed that a trade-off in their allocation to these two functions occurs. Under this scenario parasites may play a central role in maintaining the honesty of plumage as a signaling system by increasing the demands for carotenoids for infection or damage control and/or by reducing carotenoid absorption in the intestines. We analyzed the relationship between (1 carotenoid concentrations in plasma and (2 blood and intestinal parasite richness and abundance in 22 species of passerines sampled in spring. Loads of different groups of parasites were unrelated so conclusions drawn from examining a particular group of parasites cannot be extrapolated to the whole community of pathogens and parasites inhabiting a host. At intraspecific level plasma carotenoid concentration was negatively related to the richness of intestinal parasites and the abundance of some groups of intestinal parasites, at interspecific level plasma carotenoid concentration was negatively related with the abundance of intestinal parasites. No relationship at intra- nor interpecific level was found between carotenoids and blood parasites. The results suggest that intestinal parasites play an important role in the evolution and maintenance of carotenoid-derived sexually selected ornamentations probably through a negative impact on the uptake of carotenoids at the gut.

  17. Absorption of Vitamin A and Carotenoids by the Enterocyte: Focus on Transport Proteins

    OpenAIRE

    Emmanuelle Reboul

    2013-01-01

    Vitamin A deficiency is a public health problem in most developing countries, especially in children and pregnant women. It is thus a priority in health policy to improve preformed vitamin A and/or provitamin A carotenoid status in these individuals. A more accurate understanding of the molecular mechanisms of intestinal vitamin A absorption is a key step in this direction. It was long thought that β-carotene (the main provitamin A carotenoid in human diet), and thus all carotenoids, were abs...

  18. Potential Role of Carotenoids as Antioxidants in Human Health and Disease

    OpenAIRE

    Joanna Fiedor; Květoslava Burda

    2014-01-01

    Carotenoids constitute a ubiquitous group of isoprenoid pigments. They are very efficient physical quenchers of singlet oxygen and scavengers of other reactive oxygen species. Carotenoids can also act as chemical quenchers undergoing irreversible oxygenation. The molecular mechanisms underlying these reactions are still not fully understood, especially in the context of the anti- and pro-oxidant activity of carotenoids, which, although not synthesized by humans and animals, are also present i...

  19. Serum Carotenoids Reduce Progression of Early Atherosclerosis in the Carotid Artery Wall among Eastern Finnish Men

    OpenAIRE

    Jouni Karppi; Sudhir Kurl; Kimmo Ronkainen; Jussi Kauhanen; Laukkanen, Jari A.

    2013-01-01

    BACKGROUND: Several previous epidemiologic studies have shown that high blood levels of carotenoids may be protective against early atherosclerosis, but results have been inconsistent. We assessed the association between atherosclerotic progression, measured by intima-media thickness of the common carotid artery wall, and serum levels of carotenoids. METHODS: We studied the effect of carotenoids on progression of early atherosclerosis in a population-based study. The association between conce...

  20. Conserved enzymes mediate the early reactions of carotenoid biosynthesis in nonphotosynthetic and photosynthetic prokaryotes.

    OpenAIRE

    G. A. Armstrong; Alberti, M; Hearst, J E

    1990-01-01

    Carotenoids comprise one of the most widespread classes of pigments found in nature. The first reactions of C40 carotenoid biosynthesis proceed through common intermediates in all organisms, suggesting the evolutionary conservation of early enzymes from this pathway. We report here the nucleotide sequence of three genes from the carotenoid biosynthesis gene cluster of Erwinia herbicola, a nonphotosynthetic epiphytic bacterium, which encode homologs of the CrtB, CrtE, and CrtI proteins of Rhod...

  1. Investigations of carotenoids in fungi. III. Fructifications of some species from the genus Suillus

    Directory of Open Access Journals (Sweden)

    Bazyli Czeczuga

    2014-11-01

    Full Text Available Using column and thin-layer chromatography the occurrence of carotenoids and their content was determined in fructifications of 5 species from the genus Suillus. 21 carotenoids were found, among them 3 which had not hitherto been detected in fungi (auroxanthin, 3,4-dihydroxy-α-carotene and myxoxantophyll. Moreover quantitative and qualitative differences were found in the content of carotenoids in fructifications of Boletus luteus which may be of importance in their taxonomy.

  2. Investigations on carotenoids in lichens. XXXII. Carotenoids occurring in the thalli of lichens from Kenya (Equatorial Africa

    Directory of Open Access Journals (Sweden)

    Bazyli Czeczuga

    2014-02-01

    Full Text Available The presence of cartenoids in nineteen species of lichens from Kenya (Equatorial Africa was studied by column and thinlayer chromatography. This investigations revealed the presence of the following carotenoids: neurosporene, α-carotene, β-carotene, rubixanthin, α-cryptoxanthin, β-cryptoxanthin, zeaxanthin, lutein, 3'-epilutein, torularhodin, diatoxanthin, neoxanthin, echinenone, 3'-hydroxyechinenone, canthaxanthin, α-doradexanthin, astaxanthin, β-carotene epoxide, antheraxanthin, lutein epoxide, violaxanthin, mutatoxanthin, flavoxanthin, capsochrome, β-apo-8'-carotenal, β-apo-10'-carotenal and apo-12'-violaxanthal. Five of these, torularhodin, 3'-hydroxyechinenone, capsochrome, β-apo-8'-carotenal and β-apo-10'-carotenal, are reported for the first time from lichens. The total carotenoid content of the material ranged from 15.88 (Pyxine cocoes to 135.44 µg g-1 dry weight (Telaschistes chrysophthalmus.

  3. Resonant Raman detectors for noninvasive assessment of carotenoid antioxidants in human tissue

    Science.gov (United States)

    Gellermann, Werner; Sharifzadeh, Mohsen; Ermakova, Maia R.; Ermakov, Igor V.; Bernstein, P. S.

    2003-07-01

    Carotenoid antioxidants form an important part of the human body's anti-oxidant system and are thought to play an important role in disease prevention. Studies have shown an inverse correlation between high dietary intake of carotenoids and risk of certain cancers, heart disease and degenerative diseases. For example, the carotenoids lutein and zeaxanthin, which are present in high concentrations in the human retina, are thought to prevent age-related macular degeneration, the leading cause of blindness in the elderly in the Western world. We have developed various clinical prototype instruments, based on resonance Raman spectroscopy, that are able to measure carotenoid levels directly in the tissue of interest. At present we use the Raman technology to quantify carotenoid levels in the human retina, in skin, and in the oral cavity. We use resonant excitation of the π-conjugated molecules in the visible wavelength range and detect the molecules' carbon-carbon stretch frequencies. The spectral properties of the various carotenoids can be explored to selectively measure in some cases individual carotenoid species linked ot the prevention of cancer, in human skin. The instrumentation involves home-built, compact, high-throughput Raman systems capable of measuring physiological carotenoid concentrations in human subjects rapidly and quantitatively. The instruments have been demonstrated for field use and screening of tissue carotenoid status in large populations. In Epidemiology, the technology holds promise as a novel, noninvasive and objective biomarker of fruit and vegetable uptake.

  4. The nature and the content of carotenoid pigments from faded leaves of Aesculus hippocastanum L.

    Directory of Open Access Journals (Sweden)

    Gino ROSCA

    1995-08-01

    Full Text Available Faded leaves of Aesculus hippocastanum L. harvested in October and November have a high and various content of carotenoids. The content of lutein and zeaxanthin is much higher in faded leaves than in the green ones, that is why they are recommended as an important natural source for extraction (at an industrial level of the mentioned carotenoids. Faded leaves have a low biological value, because they have a low content of provitaminic A carotenoids. They have also a low content of hydrocarbon carotenoids, but a high hydroxylic and epoxydic content.

  5. Biochemistry and molecular biology of carotenoid biosynthesis in chili peppers (Capsicum spp.).

    Science.gov (United States)

    Gómez-García, María del Rocío; Ochoa-Alejo, Neftalí

    2013-01-01

    Capsicum species produce fruits that synthesize and accumulate carotenoid pigments, which are responsible for the fruits' yellow, orange and red colors. Chili peppers have been used as an experimental model for studying the biochemical and molecular aspects of carotenoid biosynthesis. Most reports refer to the characterization of carotenoids and content determination in chili pepper fruits from different species, cultivars, varieties or genotypes. The types and levels of carotenoids differ between different chili pepper fruits, and they are also influenced by environmental conditions. Yellow-orange colors of chili pepper fruits are mainly due to the accumulation of α- and β-carotene, zeaxanthin, lutein and β-cryptoxanthin. Carotenoids such as capsanthin, capsorubin and capsanthin-5,6-epoxide confer the red colors. Chromoplasts are the sites of carotenoid pigment synthesis and storage. According to the most accepted theory, the synthesis of carotenoids in chili peppers is controlled by three loci: c1, c2 and y. Several enzymes participating in carotenoid biosynthesis in chili pepper fruits have been isolated and characterized, and the corresponding gene sequences have been reported. However, there is currently limited information on the molecular mechanisms that regulate this biosynthetic pathway. Approaches to gain more knowledge of the regulation of carotenoid biosynthesis are discussed. PMID:24065101

  6. Biochemistry and Molecular Biology of Carotenoid Biosynthesis in Chili Peppers (Capsicum spp.

    Directory of Open Access Journals (Sweden)

    María del Rocío Gómez-García

    2013-09-01

    Full Text Available Capsicum species produce fruits that synthesize and accumulate carotenoid pigments, which are responsible for the fruits’ yellow, orange and red colors. Chili peppers have been used as an experimental model for studying the biochemical and molecular aspects of carotenoid biosynthesis. Most reports refer to the characterization of carotenoids and content determination in chili pepper fruits from different species, cultivars, varieties or genotypes. The types and levels of carotenoids differ between different chili pepper fruits, and they are also influenced by environmental conditions. Yellow-orange colors of chili pepper fruits are mainly due to the accumulation of α- and β-carotene, zeaxanthin, lutein and β-cryptoxanthin. Carotenoids such as capsanthin, capsorubin and capsanthin-5,6-epoxide confer the red colors. Chromoplasts are the sites of carotenoid pigment synthesis and storage. According to the most accepted theory, the synthesis of carotenoids in chili peppers is controlled by three loci: c1, c2 and y. Several enzymes participating in carotenoid biosynthesis in chili pepper fruits have been isolated and characterized, and the corresponding gene sequences have been reported. However, there is currently limited information on the molecular mechanisms that regulate this biosynthetic pathway. Approaches to gain more knowledge of the regulation of carotenoid biosynthesis are discussed.

  7. Enhancement of carotenoid biosynthesis in transplastomic tomatoes by induced lycopene-to-provitamin A conversion.

    Science.gov (United States)

    Apel, Wiebke; Bock, Ralph

    2009-09-01

    Carotenoids are essential pigments of the photosynthetic apparatus and an indispensable component of the human diet. In addition to being potent antioxidants, they also provide the vitamin A precursor beta-carotene. In tomato (Solanum lycopersicum) fruits, carotenoids accumulate in specialized plastids, the chromoplasts. How the carotenoid biosynthetic pathway is regulated and what limits total carotenoid accumulation in fruit chromoplasts is not well understood. Here, we have introduced the lycopene beta-cyclase genes from the eubacterium Erwinia herbicola and the higher plant daffodil (Narcissus pseudonarcissus) into the tomato plastid genome. While expression of the bacterial enzyme did not strongly alter carotenoid composition, expression of the plant enzyme efficiently converted lycopene, the major storage carotenoid of the tomato fruit, into provitamin A (beta-carotene). In green leaves of the transplastomic tomato plants, more lycopene was channeled into the beta-branch of carotenoid biosynthesis, resulting in increased accumulation of xanthophyll cycle pigments and correspondingly reduced accumulation of the alpha-branch xanthophyll lutein. In fruits, most of the lycopene was converted into beta-carotene with provitamin A levels reaching 1 mg per g dry weight. Unexpectedly, transplastomic tomatoes also showed a >50% increase in total carotenoid accumulation, indicating that lycopene beta-cyclase expression enhanced the flux through the pathway in chromoplasts. Our results provide new insights into the regulation of carotenoid biosynthesis and demonstrate the potential of plastids genome engineering for the nutritional enhancement of food crops. PMID:19587100

  8. Evaluation of antigenotoxic effects of carotenoids from green algae Chlorococcum humicola using human lymphocytes

    Institute of Scientific and Technical Information of China (English)

    Bhagavathy S; Sumathi P

    2012-01-01

    Objective:To identify the available phytochemicals and carotenoids in the selected green algae and evaluate the potential genotoxic/antigenotoxic effect using lymphocytes. Methods:Organic solvent extracts of Chlorococcum humicola (C. humicola) were used for the phytochemical analysis. The available carotenoids were assessed by HPLC, and LC-MS analysis. The genotoxicity was induced by the benzo(a)pyrene in the lymphocyte culture, the genotoxic and antigenotoxic effects of algal carotenoids with and without genotoxic inducer were evaluated by chromosomal aberration (CA), sister chromatid exchange (SCE) and micronucleus assay (MN). Results: The results of the analysis showed that the algae were rich in carotenoids and fatty acids. In the total carotenoids lutein,β-carotene and α-carotene were found to be present in higher concentration. The frequency of CA and SCE increased by benzo(a)pyrene were significantly decreased by the carotenoids (P<0.05 for CA, P<0.001 for SCE). The MN frequencies of the cells were significantly decreased by the treatment with carotenoids when compared with the positive controls (P<0.05). Conclusions:The findings of the present study demonstrate that, the green algae C. humicola is a rich source of bioactive compounds especially carotenoids which effectively fight against environmental genotoxic agents, the carotenoids itself is not a genotoxic substance and should be further considered for its beneficial effects.

  9. An R2R3-MYB transcription factor regulates carotenoid pigmentation in Mimulus lewisii flowers.

    Science.gov (United States)

    Sagawa, Janelle M; Stanley, Lauren E; LaFountain, Amy M; Frank, Harry A; Liu, Chang; Yuan, Yao-Wu

    2016-02-01

    Carotenoids are yellow, orange, and red pigments that contribute to the beautiful colors and nutritive value of many flowers and fruits. The structural genes in the highly conserved carotenoid biosynthetic pathway have been well characterized in multiple plant systems, but little is known about the transcription factors that control the expression of these structural genes. By analyzing a chemically induced mutant of Mimulus lewisii through bulk segregant analysis and transgenic experiments, we have identified an R2R3-MYB, Reduced Carotenoid Pigmentation 1 (RCP1), as the first transcription factor that positively regulates carotenoid biosynthesis during flower development. Loss-of-function mutations in RCP1 lead to down-regulation of all carotenoid biosynthetic genes and reduced carotenoid content in M. lewisii flowers, a phenotype recapitulated by RNA interference in the wild-type background. Overexpression of this gene in the rcp1 mutant background restores carotenoid production and, unexpectedly, results in simultaneous decrease of anthocyanin production in some transgenic lines by down-regulating the expression of an activator of anthocyanin biosynthesis. Identification of transcriptional regulators of carotenoid biosynthesis provides the 'toolbox' genes for understanding the molecular basis of flower color diversification in nature and for potential enhancement of carotenoid production in crop plants via genetic engineering. PMID:26377817

  10. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...

  11. Radical School Reform.

    Science.gov (United States)

    Gross, Beatrice, Ed.; Gross, Ronald, Ed.

    This book provides a comprehensive examination of the nature of the school crisis and the ways in which radical thinkers and educators are dealing with it. Excerpts from the writings of Jonathan Kozol, John Holt, Kenneth Clark, and others are concerned with the realities of education in ghettos and suburbs. Paul Goodman, Marshall McLuhan, Sylvia…

  12. On Radical Feminism

    Institute of Scientific and Technical Information of China (English)

    翟良锴

    2015-01-01

    <正>All men are created equal.For centuries,human have been struggling for their rights.Women,as a special social force,are fighting vigorously for their equal rights with men.According to an introduction to feminism,there are three main types of feminism:socialist,reformist and radical(Feminism 101).In order

  13. Radical Financial Innovation

    OpenAIRE

    Robert J. Shiller

    2004-01-01

    Radical financial innovation is the development of new institutions and methods that permit risk management to be extended far beyond its former realm, covering important new classes of risks. This paper compares past such innovation with potential future innovation, looking at the process that produced past success and the possibilities for future financial innovation.

  14. OH radicals in the troposphere

    International Nuclear Information System (INIS)

    OH radicals are radicals which determine the photochemistry of the troposphere. The reactivity of OH radicals to organic substances is one of the fundamental criteria for the evaluation of abiotic decomposition. Details are given about the photochemical formation and reaction of OH radicals, the decomposition reactions of organic compounds in the gaseous phase, the determination of the specific rates of OH radical decomposition reactions, measuring methods for the determination of OH radical concentrations in the troposphere, selected results, OH concentration distributions obtained from model calculations, and the influence of trace gases on OH concentrations. A summary, conclusions, and research proposals are attached. (orig./BBR)

  15. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N2O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO2-elimination. This prevents a scission of the polymer chain in the

  16. Capturing Polyradical Protein Cations after an Electron Capture Event: Evidence for their Stable Distonic Structures in the Gas Phase

    Science.gov (United States)

    Baba, Takashi; Campbell, J. Larry

    2015-08-01

    We report on the formation and "capture" of polyradical protein cations after an electron capture event. Performed in a unique electron-capture dissociation (ECD) instrument, these experiments can generate reduced forms of multiply protonated proteins by sequential charge reduction using electrons with ~1 eV. The true structures of these possible polyradicals is considered: Do the introduced unpaired electrons recombine quickly to form a new two-electron bond, or do these unpaired electrons exist as radical sites with appropriate chemical reactivity? Using an established chemical probe—radical quenching with molecular oxygen—we demonstrate that these charge-reduced protein cations are indeed polyradicals that form adducts with up to three molecules of oxygen (i.e., tri-radical protein cations) that are stable for at least 100 ms.

  17. Carotenoids production: microorganisms as source of natural dyes Produção de carotenoides: microrganismos como fonte de pigmentos naturais

    Directory of Open Access Journals (Sweden)

    Eunice Valduga

    2009-01-01

    Full Text Available Carotenoids are natural dyes synthesized by plants, algae and microorganisms. Application in many sectors can be found, as food dyeing and supplementation, pharmaceuticals, cosmetics and animal feed. Recent investigations have shown their ability to reduce the risks for many degenerative diseases like cancer, heart diseases, cataract and macular degeneration. An advantage of microbial carotenoids is the fact that the cultivation in controlled conditions is not dependent of climate, season or soil composition. In this review the advances in bio-production of carotenoids are presented, discussing the main factors that influence the microbial production of these dyes in different systems.

  18. Cloning and comparative analysis of carotenoid β-hydroxylase genes provides new insights into carotenoid metabolism in tetraploid (Triticum turgidum ssp. durum) and hexaploid (Triticum aestivum) wheat grains

    OpenAIRE

    Qin, X.; Zhang, W.; Dubcovsky, J; Tian, L.

    2012-01-01

    Carotenoid β-hydroxylases attach hydroxyl groups to the β-ionone rings (β-rings) of carotenoid substrates, resulting in modified structures and functions of carotenoid molecules. We cloned and characterized two genes (each with three homeologs), HYD1 and HYD2, which encode β-hydroxylases in wheat. The results from bioinformatic and nested degenerate PCR analyses collectively suggest that HYD1 and HYD2 may represent the entire complement of non-heme di-iron β-hydroxylases in wheat. The homeolo...

  19. Composição de carotenoides em canistel (Pouteria campechiana (Kunth Baehni Carotenoids composition of canistel (Pouteria campechiana (Kunth Baehni

    Directory of Open Access Journals (Sweden)

    Tânia da Silveira Agostini Costa

    2010-09-01

    Full Text Available O canistel (P. campechiana é uma fruta nativa da América Central e México, ainda pouco conhecida no Brasil. Apresenta uma polpa amarelo-alaranjada, rica em carotenoides, que tem despertado interesse como potencial de vitamina A. O objetivo deste trabalho foi determinar o teor de carotenoides e o valor provitamina A na polpa de canistel, assim como os teores de umidade e lipídeos na polpa e na semente. Os carotenoides foram separados por cromatografia em coluna aberta. O conteúdo de carotenoides totais foi de 226 ± 4 μg/g. Violaxantina e neoxantina foram os carotenóides predominantes, somando 196 ± 5 μg/g. seguidos por zetacaroteno, betacaroteno 5,6-epóxido, betacaroteno e fitoflueno. A semente foi a parte do fruto que apresentou maior teor de lipídeos totais, com 4,6 ± 0,2 %, e a polpa, 0,61 ± 0,03 %. Os resultados indicam que o canistel apresenta teores de carotenóides totais muito elevados e pode ser considerado uma boa fonte de provitamina A (59 ± 6 RAE/100g, se comparado com outras frutas normalmente consumidas. No entanto, os principais carotenoides encontrados em sua polpa são destituídos de atividade provitamina A.Canistel (Pouteria campechiana is a native fruit from Central America and Mexico. This fruit still not known in Brazil, presents an orange-yellow pulp rich in carotenoids, which has attracted interest as a potential source of vitamin A. The purpose of this study was to determine the carotenoids content and pro-vitamin A values in the pulp of canistel, as well as the percentage of moisture and lipids in the pulp and seeds. Carotenoids were separated by open column chromatography. The content of total carotenoids was 226 ± 4 μg/g. Violaxantin and neoxantin were the predominant carotenoids with 196 ± 5 μg/g followed by zeta-carotene, beta-carotene 5,6-epoxide, beta-carotene and phytofluene. The seeds presented higher levels of total lipids with 4.6 ± 0.2 %, while pulp had 0.61 ± 0.03 % of total lipid. These

  20. Composição de carotenoides em canistel (Pouteria campechiana (Kunth) Baehni) Carotenoids composition of canistel (Pouteria campechiana (Kunth) Baehni)

    OpenAIRE

    Tânia da Silveira Agostini Costa; Daniele Cristina Wondracek; Renata Miranda Lopes; Roberto Fontes Vieira; Francisco Ricardo Ferreira

    2010-01-01

    O canistel (P. campechiana) é uma fruta nativa da América Central e México, ainda pouco conhecida no Brasil. Apresenta uma polpa amarelo-alaranjada, rica em carotenoides, que tem despertado interesse como potencial de vitamina A. O objetivo deste trabalho foi determinar o teor de carotenoides e o valor provitamina A na polpa de canistel, assim como os teores de umidade e lipídeos na polpa e na semente. Os carotenoides foram separados por cromatografia em coluna aberta. O conteúdo de carotenoi...

  1. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J. [Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ (United Kingdom)

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a “proof of principle” for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C{sup ·+}PF{sup ·−} radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.

  2. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions.

    Science.gov (United States)

    Lewis, Alan M; Manolopoulos, David E; Hore, P J

    2014-07-28

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a "proof of principle" for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C(·+)PF(·-) radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical. PMID:25084885

  3. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    International Nuclear Information System (INIS)

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a “proof of principle” for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C·+PF·− radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical

  4. Phylogenetic and evolutionary patterns in microbial carotenoid biosynthesis are revealed by comparative genomics.

    Directory of Open Access Journals (Sweden)

    Jonathan L Klassen

    Full Text Available BACKGROUND: Carotenoids are multifunctional, taxonomically widespread and biotechnologically important pigments. Their biosynthesis serves as a model system for understanding the evolution of secondary metabolism. Microbial carotenoid diversity and evolution has hitherto been analyzed primarily from structural and biosynthetic perspectives, with the few phylogenetic analyses of microbial carotenoid biosynthetic proteins using either used limited datasets or lacking methodological rigor. Given the recent accumulation of microbial genome sequences, a reappraisal of microbial carotenoid biosynthetic diversity and evolution from the perspective of comparative genomics is warranted to validate and complement models of microbial carotenoid diversity and evolution based upon structural and biosynthetic data. METHODOLOGY/PRINCIPAL FINDINGS: Comparative genomics were used to identify and analyze in silico microbial carotenoid biosynthetic pathways. Four major phylogenetic lineages of carotenoid biosynthesis are suggested composed of: (i Proteobacteria; (ii Firmicutes; (iii Chlorobi, Cyanobacteria and photosynthetic eukaryotes; and (iv Archaea, Bacteroidetes and two separate sub-lineages of Actinobacteria. Using this phylogenetic framework, specific evolutionary mechanisms are proposed for carotenoid desaturase CrtI-family enzymes and carotenoid cyclases. Several phylogenetic lineage-specific evolutionary mechanisms are also suggested, including: (i horizontal gene transfer; (ii gene acquisition followed by differential gene loss; (iii co-evolution with other biochemical structures such as proteorhodopsins; and (iv positive selection. CONCLUSIONS/SIGNIFICANCE: Comparative genomics analyses of microbial carotenoid biosynthetic proteins indicate a much greater taxonomic diversity then that identified based on structural and biosynthetic data, and divides microbial carotenoid biosynthesis into several, well-supported phylogenetic lineages not evident

  5. Age-Related Relationships between Innate Immunity and Plasma Carotenoids in an Obligate Avian Scavenger

    Science.gov (United States)

    López-Rull, Isabel; Hornero-Méndez, Dámaso; Frías, Óscar; Blanco, Guillermo

    2015-01-01

    Variation in immunity is influenced by allocation trade-offs that are expected to change between age-classes as a result of the different environmental and physiological conditions that individuals encounter over their lifetime. One such trade-off occurs with carotenoids, which must be acquired with food and are involved in a variety of physiological functions. Nonetheless, relationships between immunity and carotenoids in species where these micronutrients are scarce due to diet are poorly studied. Among birds, vultures show the lowest concentrations of plasma carotenoids due to a diet based on carrion. Here, we investigated variations in the relationships between innate immunity (hemagglutination by natural antibodies and hemolysis by complement proteins), pathogen infection and plasma carotenoids in nestling and adult griffon vultures (Gyps fulvus) in the wild. Nestlings showed lower hemolysis, higher total carotenoid concentration and higher pathogen infection than adults. Hemolysis was negatively related to carotenoid concentration only in nestlings. A differential carotenoid allocation to immunity due to the incomplete development of the immune system of nestlings compared with adults is suggested linked to, or regardless of, potential differences in parasite infection, which requires experimental testing. We also found that individuals with more severe pathogen infections showed lower hemagglutination than those with a lower intensity infection irrespective of their age and carotenoid level. These results are consistent with the idea that intraspecific relationships between innate immunity and carotenoids may change across ontogeny, even in species lacking carotenoid-based coloration. Thus, even low concentrations of plasma carotenoids due to a scavenger diet can be essential to the development and activation of the immune system in growing birds. PMID:26544885

  6. KAROTENOID DARI MAKROALGAE DAN MIKROALGAE: POTENSI KESEHATAN APLIKASI DAN BIOTEKNOLOGI [Carotenoids from Macroalgae and Microalgae: Health Potential, Application and Biotechnology

    Directory of Open Access Journals (Sweden)

    Leenawaty Limantara3

    2012-12-01

    Full Text Available Algae, both micro and macroalgae, is one of the largest producers of carotenoids. The major composition of carotenoid on algae are β-carotene, astaxanthin, luthein, zeaxanthin, cryptoxanthin, and fucoxanthin which have important roles for human health. Carotenoids were produced by several microalgae species such as Dunaliella sallina, Haemotococcus pluvialis, Chlorella pyrenoidosa, Spirulina platensis, Nannnochloropsis oculata, and also from some macroalgae species such as Kappaphycus alvarezii, Sargassum sp, and Caulerpa sp. Carotenoids from algae has been proven as a powerful antioxidant and may prevent some degenerative diseases, cardiovascular, and cancer. Carotenoid also has been applied as a natural dye and dietary supplements. Biotechnology has been developed to increase the production of carotenoids from micro- and macroalgae. The large-scale cultivation of microalgae, either in open or closed system are shown to increase carotenoid production. During cultivation, some stress conditions can be specifically manipulated to optimize carotenoid production from microalgae.

  7. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl-, NO3-, C2O42-) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu2+, Zn2+, UO22+, Fe3+, Nd3+, Eu3+, Th4+) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author)

  8. Toward Radicalizing Community Service Learning

    Science.gov (United States)

    Sheffield, Eric C.

    2015-01-01

    This article advocates a radicalized theoretical construction of community service learning. To accomplish this radicalization, I initially take up a discussion of traditional understandings of CSL rooted in pragmatic/progressive thought. I then suggest that this traditional structural foundation can be radicalized by incorporating Deborah…

  9. Oligorotaxane Radicals under Orders

    OpenAIRE

    WANG, YUPING; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S.; Botros, Youssry Y.; Goddard, William A.; Wasielewski, Michael R.; Stoddart, J. Fraser

    2016-01-01

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY2+) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT4+) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations sugge...

  10. Oligorotaxane Radicals under Orders

    OpenAIRE

    WANG, YUPING; Frasconi, Marco; Liu, Wei-Guang; Sun, Junling; Wu, Yilei; Nassar, Majed S.; Botros, Youssry Y.; Goddard, William A.; Wasielewski, Michael R.; Stoddart, J. Fraser

    2016-01-01

    A strategy for creating foldameric oligorotaxanes composed of only positively charged components is reported. Threadlike components—namely oligoviologens—in which different numbers of 4,4′-bipyridinium (BIPY^(2+)) subunits are linked by p-xylylene bridges, are shown to be capable of being threaded by cyclobis(paraquat-p-phenylene) (CBPQT^(4+)) rings following the introduction of radical-pairing interactions under reducing conditions. UV/vis/NIR spectroscopic and electrochemical investigations...

  11. Carotenoides bixina e norbixina extraídos do urucum (Bixa orellana L. como antioxidantes em produtos cárneos Carotenoids bixin and norbixin from annatto (Bixa orellana L. as antioxidants in meat products

    Directory of Open Access Journals (Sweden)

    Carlos Eduardo Rocha Garcia

    2012-08-01

    of this reaction. Antioxidants are substances used to inhibit or retard oxidative rancidity. However the use of these compounds has been drawing the attention of consumers and regulatory agencies about the safety of synthetic additives consumption. This study aimed to evaluate the use of carotenoids bixin and norbixin as antioxidants in meat products by review of the chemical characteristics, methods of production, toxicity and technological applications. These pigments are extracted from annatto (Bixa orellana L. using organic solvents, supercritical extraction or microwaves. In Brazil, the use of these substances is forecast by law as food colorant, however, this carotenoids show a large unsaturated carbon chains that allow the addition of free radicals and enable their use as antioxidant. The structural differences between bixin and norbixin result in distinct polarity, solubility and coloration, and consequently in different technological applications. At concentrations established by regulatory agencies, the use of these compounds is safe and, in addition to applications such as dyes, can be used by industries as natural antioxidants, which is an alternative capable of replace or minimize the use of synthetic additives in meat products.

  12. Relationship between Carotenoids, Retinol, and Estradiol Levels in Older Women

    Directory of Open Access Journals (Sweden)

    Marcello Maggio

    2015-08-01

    Full Text Available Background. In vitro evidence suggests anti-estrogenic properties for retinol and carotenoids, supporting a chemo-preventive role of these phytochemicals in estrogen-dependent cancers. During aging there are significant reductions in retinol and carotenoid concentrations, whereas estradiol levels decline during menopause and progressively increase from the age of 65. We aimed to investigate the hypothesis of a potential relationship between circulating levels of retinol, carotenoids, and estradiol (E2 in a cohort of late post-menopausal women. Methods. We examined 512 women ≥ 65 years from the InCHIANTI study. Retinol, α-caroten, β-caroten, β-criptoxantin, lutein, zeaxanthin, and lycopene levels were assayed at enrollment (1998–2000 by High-Performance Liquid Chromatography. Estradiol and testosterone (T levels were assessed by Radioimmunometry (RIA and testosterone-to-estradiol ratio (T/E2, as a proxy of aromatase activity, was also calculated. General linear models adjusted for age (Model 1 and further adjusted for other confounders including Body Mass Index (BMI BMI, smoking, intake of energy, lipids, and vitamin A; C-Reactive Protein, insulin, total cholesterol, liver function, and testosterone (Model 2 were used to investigate the relationship between retinol, carotenoids, and E2 levels. To address the independent relationship between carotenoids and E2 levels, factors significantly associated with E2 in Model 2 were also included in a fully adjusted Model 3. Results. After adjustment for age, α-carotene (β ± SE = −0.01 ± 0.004, p = 0.02 and β-carotene (β ± SE = −0.07 ± 0.02, p = 0.0007 were significantly and inversely associated with E2 levels. α-Carotene was also significantly and positively associated with T/E2 ratio (β ± SE = 0.07 ± 0.03, p = 0.01. After adjustment for other confounders (Model 2, the inverse relationship between α-carotene (β ± SE = −1.59 ± 0.61, p = 0.01, β-carotene (β ± SE = −0.29

  13. Transient alkylaminium radicals in n-hexane. Condensed-phase ion-molecule reactions

    International Nuclear Information System (INIS)

    Time-resolved fluorescence detected magnetic resonance (FDMR) is used to observe alkylaminium radicals formed in n-hexane solutions by electron pulse radiolysis. The ease of observation of aminium radical FDMR signals increases with increasing alkyl substitution of the amine solutes. The results are discussed in terms of the ion-molecule reactions, such as proton transfer, which compete with the electron-transfer processes, i.e, the electron transfer from solute molecules to n-hexane radical cations and geminate recombination

  14. EXTRACTION AND IDENTIFICATION OF CAROTENOIDS IN GREEN EATABLE VEGETABLES – A PROPOSAL FOR PRACTICAL CLASSES

    Directory of Open Access Journals (Sweden)

    D.S Paiva

    2006-07-01

    β-carotene  protecting  against  low  vitamin  A  concentration  in  the  organisms  and  the  degenerative disturbs  related  to oxidative  reactions.  Finally, the students will be orientated  to correlate  the  carotenoids actions  in the prevention of diseases caused by free radicals.

  15. Dietary Carotenoids and Risk of Lung Cancer in a Pooled Analysis of Seven Cohort Studies

    NARCIS (Netherlands)

    Männistö, S.; Smith-Warner, S.A.; Spiegelman, D.; Albanes, D.; Anderson, K.; Brandt, P.A. van den; Cerhan, J.R.; Colditz, G.; Feskanich, D.; Freudenheim, J.L.; Giovannucci, E.; Goldbohm, R.A.; Graham, S.; Miller, A.B.; Rohan, T.E.; Virtamo, J.; Willett, W.C.; Hunter, D.J.

    2004-01-01

    Intervention trials with supplemental β-carotene have observed either no effect or a harmful effect on lung cancer risk. Because food composition databases for specific carotenoids have only become available recently, epidemiological evidence relating usual dietary levels of these carotenoids with l

  16. Carotenoid profile and retention in yellow-, purple- and red-fleshed potatoes after thermal processing.

    Science.gov (United States)

    Kotíková, Zora; Šulc, Miloslav; Lachman, Jaromír; Pivec, Vladimír; Orsák, Matyáš; Hamouz, Karel

    2016-04-15

    This research aimed to investigate the effect of thermal processing on carotenoid profile, quantity and stability in 22 colour-fleshed potato cultivars grown in the Czech Republic. The total of nine carotenoids was analysed by HPLC using a C30 column and PDA detection. The total carotenoid content for all cultivars ranged from 1.44 to 40.13 μg/g DM. Yellow cultivars showed a much higher average total carotenoid content (26.22 μg/g DM) when compared to red/purple-fleshed potatoes (5.69 μg/g DM). Yellow cultivars were dominated by antheraxanthin, whereas neoxanthin was the main carotenoid in red/purple cultivars. Thermal processing significantly impacted all potato cultivars. Boiling decreased the total carotenoids by 92% compared to baking (88%). Lutein was the most stable carotenoid against thermal processing (decreased by 24-43%) followed by β-carotene (decreased by 78-83%); other carotenoids were degraded nearly completely. Increased formation of (Z)-isomers by thermal processing has not been confirmed. PMID:26617045

  17. Critical assessment of three high performance liquid chromatography analytical methods for food carotenoid quantification

    NARCIS (Netherlands)

    Dias, M.G.; Oliveira, L.; Camoes, M.F.G.F.C.; Nunes, B.; Versloot, P.; Hulshof, P.J.M.

    2010-01-01

    Three sets of extraction/saponification/HPLC conditions for food carotenoid quantification were technically and economically compared. Samples were analysed for carotenoids a-carotene, ß-carotene, ß-cryptoxanthin, lutein, lycopene, and zeaxanthin. All methods demonstrated good performance in the ana

  18. CAROTENOID RETENTION IN MINIMALLY PROCESSED BIOFORTIFIED GREEN CORN STORED UNDER RETAIL MARKETING CONDITIONS

    Directory of Open Access Journals (Sweden)

    Natália Alves Barbosa

    2015-08-01

    Full Text Available Storing processed food products can cause alterations in their chemical compositions. Thus, the objective of this study was to evaluate carotenoid retention in the kernels of minimally processed normal and vitamin A precursor (proVA-biofortified green corn ears that were packaged in polystyrene trays covered with commercial film or in multilayered polynylon packaging material and were stored. Throughout the storage period, the carotenoids were extracted from the corn kernels using organic solvents and were quantified using HPLC. A completely factorial design including three factors (cultivar, packaging and storage period was applied for analysis. The green kernels of maize cultivars BRS1030 and BRS4104 exhibited similar carotenoid profiles, with zeaxanthin being the main carotenoid. Higher concentrations of the carotenoids lutein, β-cryptoxanthin, and β-carotene, the total carotenoids and the total vitamin A precursor carotenoids were detected in the green kernels of the biofortified BRS4104 maize. The packaging method did not affect carotenoid retention in the kernels of minimally processed green corn ears during the storage period.

  19. In vitro assessment of the bioaccessibility of carotenoids from sun-dried chilli peppers.

    Science.gov (United States)

    Pugliese, Alessandro; O'Callaghan, Yvonne; Tundis, Rosa; Galvin, Karen; Menichini, Francesco; O'Brien, Nora; Loizzo, Monica R

    2014-03-01

    Chilli peppers have been recognized as an excellent source of antioxidants as they are rich in bioactive phytochemicals such as carotenoids which are known to exert various beneficial effects in vivo. Absorption is an important factor in the determination of the potential biological effects of carotenoids. The bioaccessibility of a food constituent such as a carotenoid represents its potential to be absorbed in humans. There is very limited information in the literature regarding the content and bioaccessibility of carotenoids from dried peppers. Therefore, the objectives of the present study were: first, to determine the carotenoid content of 20 varieties of red, orange or yellow coloured sun-dried chilli peppers belonging to either of four Capsicum species (annuum, baccatum, chinense and chacoense); and second, to quantify the carotenoid micellarization (bioaccessibility) following an in vitro digestion procedure. Red peppers had a higher carotenoid content and bioaccessibility than either the orange peppers or yellow pepper. Xanthophylls showed greater bioaccessibility than carotenes. Our findings confirm that dried chilli peppers are a good source of carotenoids. PMID:24272195

  20. Excited-state properties of phenolic carotenoids from green sulphur bacteria

    Czech Academy of Sciences Publication Activity Database

    Fuciman, M.; Hříbek, P.; Chábera, P.; Pšenčík, J.; Župčanová, Anita; Vácha, František; Polívka, Tomáš

    Nové Hrady : Academic and University Center, 2008. s. 43. [ESF Workshop on Novel Methods in Exploring Carotenoid Excited State Dynamics. 21.09.2008-25.09.2008, Nové Hrady] Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoids Subject RIV: BO - Biophysics

  1. More than meets the eye: from carotenoid biosynthesis to new insights into apocarotenoid signaling

    Science.gov (United States)

    Carotenoids are a class of isoprenoid compounds synthesized almost exclusively in plants and are involved in a myriad of roles including the provision of flower and fruit pigmentation for the attraction of pollinators and seed dispersing organisms. While carotenoids are essential throughout plant de...

  2. Separation of the Carotenoid Bixin from Annatto Seeds Using Thin-Layer and Column Chromatography

    Science.gov (United States)

    McCullagh, James V.; Ramos, Nicholas

    2008-01-01

    In this experiment the carotenoid bixin is isolated from annatto ("Bixa orellana") seeds using column chromatography. The experiment has several key advantages over previous pigment separation experiments. First, unlike other experiments significant quantities of the carotenoid (typically 20 to 25 mg) can be isolated from small quantities of plant…

  3. Production and glucosylation of C50 and C 40 carotenoids by metabolically engineered Corynebacterium glutamicum.

    Science.gov (United States)

    Heider, Sabine A E; Peters-Wendisch, Petra; Netzer, Roman; Stafnes, Marit; Brautaset, Trygve; Wendisch, Volker F

    2014-02-01

    The yellow-pigmented soil bacterium Corynebacterium glutamicum ATCC13032 is accumulating the cyclic C50 carotenoid decaprenoxanthin and its glucosides. Carotenoid pathway engineering was previously shown to allow for efficient lycopene production. Here, engineering of C. glutamicum for production of endogenous decaprenoxanthin as well as of the heterologous C50 carotenoids C.p.450 and sarcinaxanthin is described. Plasmid-borne overexpression of genes for lycopene cyclization and hydroxylation from C. glutamicum, Dietzia sp., and Micrococcus luteus, in a lycopene-producing platform strain constructed here, resulted in accumulation of these three C50 carotenoids to concentrations of about 3-4 mg/g CDW. Chromosomal deletion of a putative carotenoid glycosyltransferase gene cg0730/crtX in these strains entailed production of non-glucosylated derivatives of decaprenoxanthin, C.p.450, and sarcinaxanthin, respectively. Upon introduction of glucosyltransferase genes from M. luteus, C. glutamicum, and Pantoea ananatis, these hydroxylated C50 carotenoids were glucosylated. We here also demonstrate production of the C40 carotenoids β-carotene and zeaxanthin in recombinant C. glutamicum strains and co-expression of the P. ananatis crtX gene was used to obtain glucosylated zeaxanthin. Together, our results show that C. glutamicum is a potentially valuable host for production of a wide range of glucosylated C40 and C50 carotenoids. PMID:24270893

  4. Regulatory control of high levels of carotenoid accumulation in potato tubers

    Science.gov (United States)

    Potato (Solanum tuberosum L.) tubers contain a wide range of carotenoid content. To decipher the key factors controlling carotenoid levels in tubers, four potato lines (Atlantic, Désirée, 91E22, and POR03) were examined by a combination of biochemical, molecular, and genomics approaches. These lines...

  5. Carotenoids located in human lymphocyte subpopulations and natural killer cells by Raman microspectroscopy

    NARCIS (Netherlands)

    Puppels, G.J.; Garritsen, H.S.P.; Kummer, J.A.; Greve, Jan

    1993-01-01

    The presence and subcellular location of carotenoids in human lymphocyte sub-populations (CD4+, CD8+, T-cell receptor-γδ+, and CD19+ ) and natural killer cells (CD16+ ) were studied by means of Raman microspectroscopy. In CD4+ lymphocytes a high concentration (10-3M) of carotenoids was found in the

  6. Context-dependent effects of carotenoid supplementation on reproduction in zebra finches

    NARCIS (Netherlands)

    Simons, Mirre J. P.; Briga, Michael; Leenknegt, Bas; Verhulst, Simon

    2014-01-01

    Carotenoid-dependent sexual coloration is one of the best-studied sexual signals, but how the honesty of such signals is maintained remains uncertain. The main hypotheses focus on acquisition limits and physiological use of carotenoids in immune function and regulating oxidative stress. A hypothesis

  7. Carotenoid pigments and the selectivity of psittacofulvin-based coloration systems in parrots.

    Science.gov (United States)

    McGraw, K J; Nogare, M C

    2004-07-01

    Carotenoid pigments are commonly used as colorants of feathers and bare parts by birds. However, parrots (Aves: Psittaciformes) use a novel class of plumage pigments (called psittacofulvins) that, like carotenoids, are lipid-soluble and red, orange, or yellow in color. To begin to understand how and why parrots use these pigments and not carotenoids in their feathers, we must first describe the distribution of these two types of pigments in the diet, tissues, and fluids of these birds. Here, we studied the carotenoid content of blood in five species of parrots with red in their plumage to see if they show the physiological ability to accumulate carotenoids in the body. Although Scarlet (Ara macao) and Greenwing Macaws (Ara chloroptera) and Eclectus (Eclectus roratus), African Gray (Psittacus erithacus) and Blue-fronted Amazon (Amazona aestiva) Parrots all use psittacofulvins to color their feathers red, we found that they also circulated high concentrations of both dietary (lutein, zeaxanthin, beta-cryptoxanthin) and metabolically derived (anhydrolutein, dehydrolutein) carotenoids through blood at the time of feather growth, at levels comparable to those found in many other carotenoid-colored birds. These results suggest that parrots have the potential to use carotenoids for plumage pigmentation, but preferentially avoid depositing them in feathers, which is likely under the control of the maturing feather follicle. As there is no evidence of psittacofulvins in parrot blood at the tune of feather growth, we presume that these pigments are locally synthesized by growing feathers within the follicular tissue. PMID:15253871

  8. Metabolic engineering of the carotenoid biosynthetic pathway in the yeast Xanthophyllomyces dendrorhous (Phaffia rhodozyma)

    NARCIS (Netherlands)

    Verdoes, J.C.; Sandmann, G.; Visser, H.; Diaz, M.; Mossel, van M.; Ooyen, van A.J.J.

    2003-01-01

    The crtYB locus was used as an integrative platform for the construction of specific carotenoid biosynthetic mutants in the astaxanthin-producing yeast Xanthophyllomyces dendrorhous. The crtYB gene of X. dendrorhous, encoding a chimeric carotenoid biosynthetic enzyme, could be inactivated by both si

  9. Chlorophyll and carotenoid pigments in solar saltern microbial mats

    Science.gov (United States)

    Villanueva, Joan; Grimalt, Joan O.; de Wit, Rutger; Keely, Brendan J.; Maxwell, James R.

    1994-11-01

    The distributions of carotenoids, chlorophylls, and their degradation products have been studied in two microbial mat systems developed in the calcite and calcite/gypsum evaporite domains of a solar saltern system. Phormidium valderianum and Microcoleus chthonoplastes are the dominant cyanobacterial species, respectively, and large amounts of Chloroflexus-like bacteria occur in the carbonate/gypsum mat. In both systems, the major pigments are chlorophyll a, zeaxanthin, β-carotene and myxoxanthophyll, which originate from these mat-building cyanobacteria. This common feature contrasts with differences in other pigments that are specific for each mat community. Thus, chlorophyll c and fucoxanthin, reflecting diatom inputs, are only found in the calcite mat, whereas the calcite/gypsum mat contains high concentrations of bacteriochlorophylls c produced by the multicellular green filamentous bacteria. In both cases, the depth concentration profiles (0-30 and 0-40 mm) show a relatively good preservation of the cyanobacterial carotenoids, zeaxanthin, β-carotene, myxoxanthophyll, and echinenone. This contrasts with the extensive biodegradation of cyanobacterial remains observed microscopically. Fucoxanthin in the calcite mat is also transformed at a faster rate than the cyanobacterial carotenoids. Chlorophyll a, the major pigment in both mats, exhibits different transformation pathways. In the calcite/gypsum mat, it is transformed via C-13 2 carbomethoxy defunctionalization prior to loss of the phytyl chain, leading to the formation of pyrophaeophytin a and, subsequently, pyrophaeophorbide a. On the other hand, the occurrence of the enzyme chlorophyllase, attributed to diatoms in the calcite mat, gives rise to extensive phytyl hydrolysis, with the formation of chlorophyllide a, pyrophaeophorbide a and, in minor proportion, phaeophorbide a. Studies of the sources of the photosynthetic pigments and of their transformation pathways in such simplified ecosystems provide a

  10. Separation of Clay Minerals from Host Sediments Using Cation Exchange Resins

    Institute of Scientific and Technical Information of China (English)

    I.S. Ismael; H.M. Baioumy

    2003-01-01

    Classic physical and chemical treatments applied to separating clay minerals from the host sediments are often difficult or aggressive for clay minerals. A technique using cation exchange resins (amberlite IRC-50H and amberlite IR-120) is used to separate clay minerals from the host sediments. The technique is based on the exchange of cations in the minerals that may be associated clay minerals in sediments,such as Ca and Mg from dolomite; Ca from calcite,gypsum and francolite with cations carried by resin radicals. The associated minerals such as gypsum,calcite,dolomite and francolite are removed in descending order. Separation of clay minerals using cation exchange resins is less aggressive than that by other classic treatments.The efficiency of amberlite IRC-50H in the removal of associated minerals is greater than that of amberlite IR-120.

  11. Chronic alcohol intake up-regulates hepatic expressions of carotenoid cleavage enzymes and peroxisomal proliferator-activated receptors in rats

    Science.gov (United States)

    Excessive and chronic alcohol intake leads to a lower hepatic vitamin A status by interfering with vitamin A metabolism.Dietary provitamin A carotenoids can be converted into vitamin A mainly by carotenoid 15,15’-monooxygenase 1 (CMO1) and, to a lesser degree, carotenoid 9910’-monooxygenase 2 (CMO2)...

  12. Arabidopsis OR proteins are the major post-transcriptional regulators of phytoene synthase in mediating carotenoid biosynthesis

    Science.gov (United States)

    Carotenoids are indispensable natural pigments to plants and humans. Phytoene synthase (PSY), the rate-limiting enzyme in carotenoid biosynthetic pathway, and ORANGE (OR), a regulator of chromoplast differentiation and enhancer of carotenoid biosynthesis, represent two key proteins that control caro...

  13. Clorofilas y carotenoides: del screening a la bioactividad tisular

    OpenAIRE

    Pérez Gálvez, Antonio

    2008-01-01

    La funcionalidad de clorofilas y carotenoides surge a partir de los efectos derivados de su función, su acción y su asociación. Con estos pigmentos fotosintéticos se ha realizado un amplio screening de sus propiedades funcionales en sistemas in vitro y condiciones modelo, destacando su capacidad antioxidante y anti-mutagénica así como la inducción de eventos ligados a la diferenciación y proliferación celular. Como con la mayoría de compuestos funcionales, el establecimiento concreto de la bi...

  14. Carotenoid and vitamin content of Karat and other Micronesian banana cultivars.

    Science.gov (United States)

    Englberger, Lois; Schierle, Joseph; Aalbersberg, William; Hofmann, Peter; Humphries, Julia; Huang, Alvin; Lorens, Adelino; Levendusky, Amy; Daniells, Jeff; Marks, Geoffrey C; Fitzgerald, Maureen H

    2006-01-01

    We previously found high carotenoid levels in Karat and other Micronesian bananas, indicating potential importance for alleviating vitamin A deficiency and other nutritionally related health problems in the Federated States of Micronesia. Past work focused on carotenoid and mineral analyses, whereas here we investigated 16 cultivars (most not previously analysed) for a broader micronutrient profile, including seven vitamins. Karat carotenoid levels were higher than in previous analyses, confirming Karat as exceptionally carotenoid-rich. We identified an additional 10 carotenoid-rich cultivars, expanding the range having potential for alleviating vitamin A deficiency. A striking finding is the high riboflavin level in Karat, including high levels of uncharacterized flavonoids. Niacin and alpha-tocopherol are at levels that may contribute importantly to dietary intake within normal patterns of consumption. These data present a more complete basis for promoting the nutritional benefits of these banana cultivars where they are consumed in the Pacific, and potential benefits for promoting elsewhere. PMID:17135031

  15. The effect of cellular carotenoid levels in micrococcus luteus on resistance to gamma radiation

    International Nuclear Information System (INIS)

    In the present study, a biological system was developed to link the cellular carotenoid levels to Gamma radiation resistance in bacteria for the frst time. thus, in a non-photosynrhetic bacterium, in Micrococcus Luteus an inverse relationship was found between the increase in diphenylamine (DPA) concentration (5.25 μg/ml culture) and the polar cellular carotenoid pigments (C-45 and C-50 carotenoids and their glucosides). It was also found that irradiation of cells with different carotenoid concentrations with doses of γ-radiation in the range of (0.2500 gray) under oxic, air and hypoxic conditions showed that carotenoid pigments offer no significant protection as they usually do in case of visible light. (author).15 refs., 5 figs., 3 tabs

  16. New and Rare Carotenoids Isolated from Marine Bacteria and Their Antioxidant Activities

    Directory of Open Access Journals (Sweden)

    Kazutoshi Shindo

    2014-03-01

    Full Text Available Marine bacteria have not been examined as extensively as land bacteria. We screened carotenoids from orange or red pigments-producing marine bacteria belonging to rare or novel species. The new acyclic carotenoids with a C30 aglycone, diapolycopenedioc acid xylosylesters A–C and methyl 5-glucosyl-5,6-dihydro-apo-4,4′-lycopenoate, were isolated from the novel Gram-negative bacterium Rubritalea squalenifaciens, which belongs to phylum Verrucomicrobia, as well as the low-GC Gram-positive bacterium Planococcus maritimus strain iso-3 belonging to the class Bacilli, phylum Firmicutes, respectively. The rare monocyclic C40 carotenoids, (3R-saproxanthin and (3R,2′S-myxol, were isolated from novel species of Gram-negative bacteria belonging to the family Flavobacteriaceae, phylum Bacteroidetes. In this review, we report the structures and antioxidant activities of these carotenoids, and consider relationships between bacterial phyla and carotenoid structures.

  17. Genetic manipulation of carotenoid biosynthesis in the green sulfur bacterium Chlorobium tepidum

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Maresca, Julia A; Yunker, Colleen E;

    2004-01-01

    The green sulfur bacterium Chlorobium tepidum is a strict anaerobe and an obligate photoautotroph. On the basis of sequence similarity with known enzymes or sequence motifs, nine open reading frames encoding putative enzymes of carotenoid biosynthesis were identified in the genome sequence of C....... tepidum, and all nine genes were inactivated. Analysis of the carotenoid composition in the resulting mutants allowed the genes encoding the following six enzymes to be identified: phytoene synthase (crtB/CT1386), phytoene desaturase (crtP/CT0807), zeta-carotene desaturase (crtQ/CT1414), gamma......-carotene desaturase (crtU/CT0323), carotenoid 1',2'-hydratase (crtC/CT0301), and carotenoid cis-trans isomerase (crtH/CT0649). Three mutants (CT0180, CT1357, and CT1416 mutants) did not exhibit a discernible phenotype. The carotenoid biosynthetic pathway in C. tepidum is similar to that in cyanobacteria and plants...

  18. Threshold photoelectron spectroscopy of the imidogen radical

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Gustavo A., E-mail: gustavo.garcia@synchrotron-soleil.fr [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Gans, Bérenger [Institut des Sciences Moléculaires d’Orsay, Univ Paris-Sud, CNRS, Bât 210, Univ Paris-Sud, 91405 Orsay Cedex (France); Tang, Xiaofeng [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Ward, Michael; Batut, Sébastien [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Nahon, Laurent [Synchrotron SOLEIL, L’Orme des Merisiers, St. Aubin, BP 48, 91192 Gif sur Yvette (France); Fittschen, Christa [PC2A, Université de Lille 1, UMR CNRS-USTL 8522, Cité Scientifique Bât. C11, F-59655 Villeneuve d’Ascq (France); Loison, Jean-Christophe [ISM, Université de Bordeaux, CNRS, 351 cours de la Libération, 33405 Talence Cedex (France)

    2015-08-15

    We present the threshold photoelectron spectroscopy of the imidogen radical (NH) recorded in the photon energy region up to 1 eV above its first ionization threshold. The radical was produced by reaction of NH{sub 3} and F in a microwave discharge flow-tube and photoionized using vacuum ultraviolet (VUV) synchrotron radiation. A double imaging coincidence spectrometer was used to record mass-selected spectra and avoid contributions from the byproducts present in the reactor and background gas. The energy region includes the ground X{sup +2}Π and first electronically excited a{sup +4}Σ{sup −} states of NH{sup +}. Strong adiabatic transitions and weak vibrational progressions up to v{sup +} = 2 are observed for both electronic states. The rotational profile seen in the origin band has been modeled using existing neutral and cationic spectroscopic constants leading to a precise determination of the adiabatic ionization energy at 13.480 ± 0.002 eV.

  19. Mechanisms of strand breaks in DNA induced by OH radicals in aqueous solution

    International Nuclear Information System (INIS)

    The gamma irradiation of N2O-saturated aqueous solutions of DNA in the absence of O2 leads to the formation of three detached altered sugars. It is predominantly OH radical which leads to the permanent and biological significant damage of DNA, and it is especially the OH radical which produces chain breaks. The OH radicals in aqueous solutions react with DNA predominantly (about 80%) by addition to the C=C bonds of the bases, and about 20% abstracts H atoms from sugar moiety. All three isolated sugars show new C=O bonds only at the position C-4. Chain-breaking reaction is identified as the heterolytic splitting of the sugar phosphoric acid ester bond, producing a cation radical of the sugar moiety and an anion of the DNA phosphoric acid ester (SN1 reaction). The formation of the observed detached and attached altered sugars as end products is explained by the reaction of the cation radical with water in which branching in the reaction occurs, and by the subsequent reaction of the radicals formed. Two important features of the Scheme I mechanism are, first, the much faster bond breaking at the position 3' as compared with that at the position 5', and secondly, the formation of not only detached altered sugars but also altered sugar end groups. Quantitative results show that a large fraction of DNA chain breaks induced by OH radicals can be accounted for by the Scheme I. (Yamashita, S.)

  20. Cationic speciation in nonaqueous media

    International Nuclear Information System (INIS)

    Electronic spectra of solutions of d transition elements in the superacids HF, H2SO4, HSO3F, and CF3SO3H and in chloroaluminate melts indicate that in acidic monaqueous media the elements are present as solvated cations, whereas in basic media the speciation is anionic, the same situation as in aqueous solutions. Further, in very highly acidic media, cations in very low oxidation states are stable (e.g., Ti2+), but these disproportionate on addition of base to the system. In this paper spectra, where available, of U, Np, and Pu in oxidation states III and IV in aqueous media, in protonic superacids, and in chloroaluminates are presented to postulate cationic speciation of these early actinides in highly acidic media

  1. The Or Gene Enhances Carotenoid Accumulation and Stability During Post-Harvest Storage of Potato Tubers

    Institute of Scientific and Technical Information of China (English)

    Li Li; Mark Failla; Theodore W.Thannhauser; Yong Yang; Qiang Xu; Katherine Owsiany; Ralf Welsch; Chureeporn Chitchumroonchokchai; Shan Lu; Joyce Van Eck; Xiu-Xin Deng

    2012-01-01

    Provitamin A carotenoids in staple crops are not very stable during storage and their loss compromises nutritional quality.To elucidate the fundamental mechanisms underlying carotenoid accumulation and stability,we investigated transgenic potato tubers that expressed the cauliflower Orange (Or) gene.We found that the Or transgene not only promoted retention of β-carotene level,but also continuously stimulated its accumulation during 5 months of cold storage.In contrast,no increased levels of carotenoids were observed in the tubers of vector-only controls or a yellowflesh variety during the same period of storage.The increased carotenoid accumulation was found to be associated with the formation of lipoprotein-carotenoid sequestering structures,as well as with the enhanced abundance of phytoene synthase,a key enzyme in the carotenoid biosynthetic pathway.Furthermore,the provitamin A carotenoids stored were shown to be stable during simulated digestion and accessible for uptake by human intestinal absorptive cells.Proteomic analysis identified three major functional groups of proteins (i.e.heat shock proteins,glutathione-S-transferases,and carbohydrate metabolic proteins) that are potentially important in the Or-regulated carotenoid accumulation.Our results show that regulation of carotenoid sequestration capacity is an important mechanism by which carotenoid stability is regulated.Our findings suggest that induction of a proper sink structure formation in staple crops may provide the crops with a unique ability to promote and/or stabilize provitamin A accumulation during plant growth and post-harvest storage.

  2. Utilization of Microemulsions from Rhinacanthus nasutus (L.) Kurz to Improve Carotenoid Bioavailability

    Science.gov (United States)

    Ho, Nai-Hsing; Inbaraj, Baskaran Stephen; Chen, Bing-Huei

    2016-01-01

    Carotenoids have been known to reduce the risk of several diseases including cancer and cardiovascular. However, carotenoids are unstable and susceptible to degradation. Rhinacanthus nasutus (L.) Kurz (R. nasutus), a Chinese medicinal herb rich in carotenoids, was reported to possess vital biological activities such as anti-cancer. This study intends to isolate carotenoids from R. nasutus by column chromatography, identify and quantify by HPLC-MS, and prepare carotenoid microemulsions for determination of absolute bioavailability in rats. Initially, carotenoid fraction was isolated using 250 mL ethyl acetate poured into an open-column packed with magnesium oxide-diatomaceous earth (1:3, w/w). Fourteen carotenoids including internal standard β-apo-8′-carotenal were resolved within 62 min by a YMC C30 column and gradient mobile phase of methanol-acetonitrile-water (82:14:4, v/v/v) and methylene chloride. Highly stable carotenoid microemulsions were prepared using a mixture of CapryolTM90, Transcutol®HP, Tween 80 and deionized water, with the mean particle being 10.4 nm for oral administration and 10.7 nm for intravenous injection. Pharmacokinetic study revealed that the absolute bioavailability of carotenoids in microemulsions and dispersion was 0.45% and 0.11%, respectively, while a much higher value of 6.25% and 1.57% were shown for lutein, demonstrating 4-fold enhancement in bioavailability upon incorporation of R. nasutus carotenoids into a microemulsion system. PMID:27150134

  3. Hydrogen Bond Formation between the Carotenoid Canthaxanthin and the Silanol Group on MCM-41 Surface.

    Science.gov (United States)

    Gao, Yunlong; Xu, Dayong; Kispert, Lowell D

    2015-08-20

    The formation of one or two hydrogen bonds (H-bonds) between canthaxanthin (CAN), a dye, and the silanol group(s) on the MCM-41 surface has been studied by density functional theory (DFT) calculations and calorimetric experiments. It was found that the formation of the H-bond(s) stabilized the CAN molecule more than its radical cation (CAN(•+)). The charge distribution, bond lengths, and the HOMO and LUMO energies of CAN are also affected. The formation of the H-bond(s) explains the lower photoinduced electron transfer efficiency of CAN imbedded in Cu-MCM-41 versus that for β-carotene (CAR) imbedded in Cu-MCM-41 where complex formation with Cu(2+) dominates. These calculations show that to achieve high electron transfer efficiency for a dye-sensitized solar cell, H-bonding between the dye and the host should be avoided. PMID:26230844

  4. Developing an emulsifier system to improve the bioaccessibility of carotenoids.

    Science.gov (United States)

    Fernández-García, Elisabet; Rincón, Francisco; Pérez-Gálvez, Antonio

    2008-11-12

    Food emulsion designs, with the aim of delivering lipophilic bioactive compounds, should include an estimate of their bioaccessibility to support the claimed effect. With this goal in mind, in vitro digestion models and experimental design of mixtures were used as analytical tools to measure this parameter and to optimize the formulation of an O/W emulsion, including carotenoids as functional ingredients. Two experimental stages were applied. First, a screening phase was completed to detect the critical factors that exerted a significant effect on the response (bioaccessibility). During this phase, we observed that the response was modified mainly by secondary effects such as synergies and antagonisms of the emulsifying mixture. A group of four emulsifiers was selected at this phase to perform the second experimental stage, the optimization phase. This allowed us to obtain the mixture that produced the maximum carotenoid bioaccessibility. This formulation had emulsifying properties of the liposugars, acyl- and polyacyl-glycerides, as well as the synergistic effect arising from the combination of materials; this maximized the response. The analytical approach applied in this work is of interest for food designers for screening and controlling the bioaccessibility of bioactive compounds in a given matrix and, consequently, selecting the formulation conditions for higher bioaccessibilities. PMID:18937490

  5. Strigolactones, a novel carotenoid-derived plant hormone

    KAUST Repository

    Al-Babili, Salim

    2015-04-29

    Strigolactones (SLs) are carotenoid-derived plant hormones and signaling molecules. When released into the soil, SLs indicate the presence of a host to symbiotic fungi and root parasitic plants. In planta, they regulate several developmental processes that adapt plant architecture to nutrient availability. Highly branched/tillered mutants in Arabidopsis, pea, and rice have enabled the identification of four SL biosynthetic enzymes: a cis/trans-carotene isomerase, two carotenoid cleavage dioxygenases, and a cytochrome P450 (MAX1). In vitro and in vivo enzyme assays and analysis of mutants have shown that the pathway involves a combination of new reactions leading to carlactone, which is converted by a rice MAX1 homolog into an SL parent molecule with a tricyclic lactone moiety. In this review, we focus on SL biosynthesis, describe the hormonal and environmental factors that determine this process, and discuss SL transport and downstream signaling as well as the role of SLs in regulating plant development. ©2015 by Annual Reviews. All rights reserved.

  6. Theoretical Study of the Benzene Cation%苯分子离子的理论研究

    Institute of Scientific and Technical Information of China (English)

    刘亚军; 邝平先; 黄明宝

    2001-01-01

    The Jahn-Teller distorted states, 2B2g and 2B1g of the benzene radical cation have been studied by using ab initio MPn and SDCI methods. The calculations indicate that 2B2g is the ground state of the benzene cation and that 2B1g is higher in energy than 2B2g and represents a saddle point. The calculated isotropic and anisotropic hyperfine coupling constants for the 2B2g state are in excellent agreement with those obtained from the ESR experiments. It is concluded that the benzene cation is in the 2B2g Jahn-Teller distorted state.

  7. A radical publishing collective: the Journal of Radical Librarianship

    OpenAIRE

    Simon Barron

    2015-01-01

    The Journal of Radical Librarianship is a new open-access journal publishing scholarly work in the field of radical librarianship. The focus on critical approaches to librarianship and anti-marketisation of information is reflected not only in our subject matter but in our publishing model, our licensing model, and our organisational practices. We hope to foster open and engaging discussions about radical approaches to librarianship and information studies.

  8. π-Radical to σ-Radical Tautomerization in One-Electron-Oxidized 1-Methylcytosine and Its Analogs.

    Science.gov (United States)

    Adhikary, Amitava; Kumar, Anil; Bishop, Casandra T; Wiegand, Tyler J; Hindi, Ragda M; Adhikary, Ananya; Sevilla, Michael D

    2015-09-01

    In this work, iminyl σ-radical formation in several one-electron-oxidized cytosine analogs, including 1-MeC, cidofovir, 2'-deoxycytidine (dCyd), and 2'-deoxycytidine 5'-monophosphate (5'-dCMP), were investigated in homogeneous, aqueous (D2O or H2O) glassy solutions at low temperatures by employing electron spin resonance (ESR) spectroscopy. Upon employing density functional theory (DFT) (DFT/B3LYP/6-31G* method), the calculated hyperfine coupling constant (HFCC) values of iminyl σ-radical agree quite well with the experimentally observed ones, thus confirming its assignment. ESR and DFT studies show that the cytosine iminyl σ-radical is a tautomer of the deprotonated cytosine π-cation radical [cytosine π-aminyl radical, C(N4-H)(•)]. Employing 1-MeC samples at various pHs ranging from ca. 8 to 11, ESR studies show that the tautomeric equilibrium between C(N4-H)(•) and the iminyl σ-radical at low temperature is too slow to be established without added base. ESR and DFT studies agree that, in the iminyl σ-radical, the unpaired spin is localized on the exocyclic nitrogen (N4) in an in-plane pure p-orbital. This gives rise to an anisotropic nitrogen hyperfine coupling (Azz = 40 G) from N4 and a near isotropic β-nitrogen coupling of 9.7 G from the cytosine ring nitrogen at N3. Iminyl σ-radical should exist in its N3-protonated form, as the N3-protonated iminyl σ-radical is stabilized in solution by over 30 kcal/mol (ΔG = -32 kcal/mol) over its conjugate base, the N3-deprotonated form. This is the first observation of an isotropic β-hyperfine ring nitrogen coupling in an N-centered DNA radical. Our theoretical calculations predict that the cytosine iminyl σ-radical can be formed in double-stranded DNA by a radiation-induced ionization-deprotonation process that is only 10 kcal/mol above the lowest energy path. PMID:26237072

  9. Bursectomy at radical gastrectomy

    Institute of Scientific and Technical Information of China (English)

    Cuneyt; Kayaalp

    2015-01-01

    Radical gastrectomy with extended lymph node dissec tion and prophylactic resection of the omentum, peri toneum over the posterior lesser sac, pancreas and/o spleen was advocated at the beginning of the 1960 s in Japan. In time, prophylactic routine resections of the pancreas and/or spleen were abandoned because of the high incidence of postoperative complications. However omentectomy and bursectomy continued to be standard parts of traditional radical gastrectomy. The bursaomentalis was thought to be a natural barrier against invasion of cancer cells into the posterior part of the stomach. The theoretical rationale for bursectomy was to reduce the risk of peritoneal recurrences by eliminating the peritoneum over the lesser sac, which might include free cancer cells or micrometastases. Over time, the indication for bursectomy was gradually reduced to only patients with posterior gastric wall tumors penetrating the serosa. Despite its theoretical advantages, its benefit for recurrence or survival has not been proven yet. The possible reasons for this inconsistency are discussed in this review. In conclusion, the value of bursectomy in the treatment of gastric cancer is still under debate and large-scale randomized studies are necessary. Until clear evidence of patient benefit is obtained, its routine use cannot be recommended.

  10. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.

  11. Carotenoid-based coloration, condition, and immune responsiveness in the nestlings of a sexually dimorphic bird of prey.

    Science.gov (United States)

    Sternalski, Audrey; Mougeot, François; Pérez-Rodríguez, Lorenzo; Bretagnolle, Vincent

    2012-01-01

    In many birds, nestlings exhibit brightly colored traits that are pigmented by carotenoids. Carotenoids are diet limited and also serve important health-related physiological functions. The proximate mechanisms behind the expression of these carotenoid-pigmented traits are still poorly known, especially in nestlings with sexual size dimorphism. In these nestlings, intrabrood competition levels and growth strategies likely differ between sexes, and this may in turn influence carotenoid allocation rules. We used dietary carotenoid supplementation to test whether wild marsh harrier (Circus aeruginosus) nestlings were carotenoid limited and whether carotenoid allocation strategies varied between sexes, which differ in their size and growth strategies. When supplemented, nestlings used the supplemental carotenoids to increase their coloration independently of their sex. We showed that the condition dependence of the carotenoid level and the response to an immune challenge (phytohemagglutinin test) differed between sexes, possibly because sexual size dimorphism influences growth strategies and/or intrabrood competition levels and access to different types of food. In this species, which often feeds on mammals, a trade-off likely exists between food quantity (energy) and quality (carotenoid content). Finally, carotenoid-based coloration expressed in marsh harrier nestlings appeared to be indicative of immune responsiveness rather than condition, therefore potentially advertising to parents nestling quality or value rather than nutritional need. PMID:22705486

  12. Antioxidant Activity of Carotenoids from Rhodobacter sphaeroides%类球红细菌类胡萝卜素抗氧化活性研究

    Institute of Scientific and Technical Information of China (English)

    安君; 李祖明; 张静; 白志辉; 杨卫东; 王栋

    2015-01-01

    The effects of grinding, ultrasonic, ultrasonic assisted with acidolysis and thallus concentration on antioxi-dant activity of carotenoids from Rhodobacter sphaeroides were studied in this paper.The results showed that the carot-enoids extracted with different methods and solid-liquid proportion from R.sphaeroides 3757 possessed activities of scavenging DPPH free radicals, reducing power and resistance against lipid peroxidation.Carotenoids extracted by ul-trasonic assisted with acidolysis from R.sphaeroides 3757 has the highest production rate and the best antioxidant ac-tivities.Caratenoids from R.sphaeroides possessed a certain antioxidant activities, and the antioxidant activities in-creased as the thallus concentration increased.%研究了研磨法、超声波法、酸溶辅助超声波法和菌体浓度对类球红细菌类胡萝卜素抗氧化活性的影响。结果表明,不同提取方法和固液比条件下,类球红细菌类胡萝卜素均具有清除DPPH自由基能力、抗脂质过氧化能力和还原能力。酸溶辅助超声波法提取的类胡萝卜素产率最高、抗氧化活性最好。类球红细菌类胡萝卜素具有一定的抗氧化活性,其抗氧化活性随菌体浓度的增加而增加。

  13. Liquid-solid extraction of metallic cations by cationic amphiphiles

    International Nuclear Information System (INIS)

    In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

  14. Absorption of Vitamin A and Carotenoids by the Enterocyte: Focus on Transport Proteins

    Directory of Open Access Journals (Sweden)

    Emmanuelle Reboul

    2013-09-01

    Full Text Available Vitamin A deficiency is a public health problem in most developing countries, especially in children and pregnant women. It is thus a priority in health policy to improve preformed vitamin A and/or provitamin A carotenoid status in these individuals. A more accurate understanding of the molecular mechanisms of intestinal vitamin A absorption is a key step in this direction. It was long thought that β-carotene (the main provitamin A carotenoid in human diet, and thus all carotenoids, were absorbed by a passive diffusion process, and that preformed vitamin A (retinol absorption occurred via an unidentified energy-dependent transporter. The discovery of proteins able to facilitate carotenoid uptake and secretion by the enterocyte during the past decade has challenged established assumptions, and the elucidation of the mechanisms of retinol intestinal absorption is in progress. After an overview of vitamin A and carotenoid fate during gastro-duodenal digestion, our focus will be directed to the putative or identified proteins participating in the intestinal membrane and cellular transport of vitamin A and carotenoids across the enterocyte (i.e., Scavenger Receptors or Cellular Retinol Binding Proteins, among others. Further progress in the identification of the proteins involved in intestinal transport of vitamin A and carotenoids across the enterocyte is of major importance for optimizing their bioavailability.

  15. Pressurized Hot Ethanol Extraction of Carotenoids from Carrot By-Products

    Directory of Open Access Journals (Sweden)

    Charlotta Turner

    2012-02-01

    Full Text Available Carotenoids are known for their antioxidant activity and health promoting effects. One of the richest sources of carotenoids are carrots. However, about 25% of the annual production is regarded as by-products due to strict market policies. The aim of this study was to extract carotenoids from those by-products. Conventional carotenoid extraction methods require the use of organic solvents, which are costly, environmentally hazardous, and require expensive disposal procedures. Pressurized liquid extraction (PLE utilizes conventional solvents at elevated temperatures and pressure, and it requires less solvent and shorter extraction times. The extraction solvent of choice in this study was ethanol, which is a solvent generally recognized as safe (GRAS. The extraction procedure was optimized by varying the extraction time (2–10 min and the temperature (60–180 °C. β-Carotene was used as an indicator for carotenoids content in the carrots. The results showed that time and temperatures of extraction have significant effect on the yield of carotenoids. Increasing the flush volume during extraction did not improve the extractability of carotenoids, indicating that the extraction method was mainly desorption/diffusion controlled. Use of a dispersing agent that absorbs the moisture content was important for the efficiency of extraction. Analysing the content of β-carotene at the different length of extraction cycles showed that about 80% was recovered after around 20 min of extraction.

  16. Statistical optimisation of cell growth and carotenoid production by Rhodotorula mucilaginosa

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    Iriani R. Maldonade

    2012-03-01

    Full Text Available Sequential statistical methods were used to maximise carotenoid production by a strain of Rhodotorula mucilaginosa, isolated from the Brazilian ecosystem. Initially, a factorial 2(5-1 experimental design was used, and the variables were pH and the levels of glucose, yeast extract, MgSO4.7H2O and KH2PO4. The nitrogen source (yeast extract was the most important variable in enhancing carotenoid production; MgSO4.7H2O and KH2PO4 had a negative influence. The initial pH had no significant effect on carotenoid and cell productions. We further investigated the effects of glucose and yeast extract effects, using a second-order central composite design (CCD to optimise carotenoid production, which was adequately approximated with a full quadratic equation obtained from a two-factor-2-level design. The analysis of quadratic surfaces showed that after 5 days of cultivation at 25ºC, the maximum carotenoid concentration (745 µg l-1 was obtained with 15 g l-1 of yeast extract and 20 g l-1 of glucose. The maximum carotenoid production (152 µg g-1 was obtained with 5 g l-1 yeast extract and 10 g l-1 glucose. Carotenoid formation was more sensitive to changes in yeast extract concentration than to changes in glucose concentration. Maximum cell production was achieved with 15-17 g l-1 of yeast extract and 15-20 g l-1 of glucose.

  17. Carotenoids play a positive role in the degradation of heterocycles by Sphingobium yanoikuyae.

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    Xiaorui Liu

    Full Text Available BACKGROUND: Microbial oxidative degradation is a potential way of removing pollutants such as heterocycles from the environment. During this process, reactive oxygen species or other oxidants are inevitably produced, and may cause damage to DNA, proteins, and membranes, thereby decreasing the degradation rate. Carotenoids can serve as membrane-integrated antioxidants, protecting cells from oxidative stress. FINDINGS: Several genes involved in the carotenoid biosynthetic pathway were cloned and characterized from a carbazole-degrading bacterium Sphingobium yanoikuyae XLDN2-5. In addition, a yellow-pigmented carotenoid synthesized by strain XLDN2-5 was identified as zeaxanthin that was synthesized from β-carotene through β-cryptoxanthin. The amounts of zeaxanthin and hydrogen peroxide produced were significantly and simultaneously enhanced during the biodegradation of heterocycles (carbazole < carbazole + benzothiophene < carbazole + dibenzothiophene. These higher production levels were consistent with the transcriptional increase of the gene encoding phytoene desaturase, one of the key enzymes for carotenoid biosynthesis. CONCLUSIONS/SIGNIFICANCE: Sphingobium yanoikuyae XLDN2-5 can enhance the synthesis of zeaxanthin, one of the carotenoids, which may modulate membrane fluidity and defense against intracellular oxidative stress. To our knowledge, this is the first report on the positive role of carotenoids in the biodegradation of heterocycles, while elucidating the carotenoid biosynthetic pathway in the Sphingobium genus.

  18. Increase in β-ionone, a carotenoid-derived volatile in zeaxanthin-biofortified sweet corn.

    Science.gov (United States)

    Gallon, Camilla Z; Fuller, Steven C; Fanning, Kent J; Smyth, Heather E; Pun, Sharon; Martin, Ian F; O'Hare, Timothy J

    2013-07-31

    Carotenoids are responsible for the yellow color of sweet corn (Zea mays var. saccharata), but are also potentially the source of flavor compounds from the cleavage of carotenoid molecules. The carotenoid-derived volatile, β-ionone, was identified in both standard yellow sweet corn ('Hybrix5') and a zeaxanthin-enhanced experimental variety ('HZ') designed for sufferers of macular degeneration. As β-ionone is highly perceivable at extremely low concentration by humans, it was important to confirm if alterations in carotenoid profile may also affect flavor volatiles. The concentration of β-ionone was most strongly correlated (R(2) > 0.94) with the β-arm carotenoids, β-carotene, β-cryptoxanthin, and zeaxanthin, and to a lesser degree (R(2) = 0.90) with the α-arm carotenoid, zeinoxanthin. No correlation existed with either lutein (R(2) = 0.06) or antheraxanthin (R(2) = 0.10). Delaying harvest of cobs resulted in a significant increase of both carotenoid and β-ionone concentrations, producing a 6-fold increase of β-ionone in 'HZ' and a 2-fold increase in 'Hybrix5', reaching a maximum of 62 μg/kg FW and 24 μg/kg FW, respectively. PMID:23767984

  19. Comparative carotenoid compositions during maturation and their antioxidative capacities of three citrus varieties.

    Science.gov (United States)

    Yoo, Kyung-Mi; Moon, BoKyung

    2016-04-01

    This study investigated total carotenoid content, comparative carotenoid composition, vitamin C content, and total antioxidant capacity of three citrus varieties which are Yuza (Citrus junos Sieb ex Tabaka), Kjool (Citrus unshiu Marcow), and Dangyooja (Citrus grandis Osbeck). Seven carotenoids were identified, with β-cryptoxanthin, astaxanthin, and zeaxanthin being predominant in citrus varieties. Ripening increased the total carotenoid in three citrus varieties. Individual carotenoid of canthaxanthin, astaxanthin, and α-carotene in citrus varieties decreased with maturation, whereas the others increased with ripening. Yuza exhibited the highest total antioxidant capacity in 2,2'-azino-bis-3-ethylbenzthiazoline-6-sulfonic acid (ABTS) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) assays, with VCEAC values of 582.9 mg/100 g and 451.5 mg/100g, respectively. The relative VCEAC values were vitamin C (1.00)>lycopene (0.375), α-carotene (0.304), β-carotene (0.289), β-cryptoxanthin (0.242), and zeaxanthin (0.099). These results indicate that Yuza contains higher amounts of total carotenoids, individual carotenoids, and vitamin C than other Korean citrus varieties. PMID:26593526

  20. Carotenoids from Foods of Plant, Animal and Marine Origin: An Efficient HPLC-DAD Separation Method

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    Irini F. Strati

    2012-12-01

    Full Text Available Carotenoids are important antioxidant compounds, present in many foods of plant, animal and marine origin. The aim of the present study was to describe the carotenoid composition of tomato waste, prawn muscle and cephalothorax and avian (duck and goose egg yolks through the use of a modified gradient elution HPLC method with a C30 reversed-phase column for the efficient separation and analysis of carotenoids and their cis-isomers. Elution time was reduced from 60 to 45 min without affecting the separation efficiency. All-trans lycopene predominated in tomato waste, followed by all-trans-β-carotene, 13-cis-lutein and all-trans lutein, while minor amounts of 9-cis-lutein, 13-cis-β-carotene and 9-cis-β-carotene were also detected. Considering the above findings, tomato waste is confirmed to be an excellent source of recovering carotenoids, especially all-trans lycopene, for commercial use. Xanthophylls were the major carotenoids of avian egg yolks, all-trans lutein and all-trans zeaxanthin in duck and goose egg yolk, respectively. In the Penaeus kerathurus prawn, several carotenoids (zeaxanthin, all-trans-lutein, canthaxanthin, cryptoxanthin, optical and geometrical astaxanthin isomers were identified in considerable amounts by the same method. A major advantage of this HPLC method was the efficient separation of carotenoids and their cis-isomers, originating from a wide range of matrices.

  1. Spectroscopic Studies of Carotenoid-to-Bacteriochlorophyll Energy Transfer in LHRC Photosynthetic Complex from Roseiflexus castenholzii

    Energy Technology Data Exchange (ETDEWEB)

    Niedzwiedzki, Dariusz [Washington Univ., St. Louis, MO (United States); Collins, Aaron M. [Washington Univ., St. Louis, MO (United States); LaFountain, Amy M. [Univ. of Connecticut, Storrs, CT (United States); Enriquez, Miriam M. [Univ. of Connecticut, Storrs, CT (United States); Frank, Harry A. [Washington Univ., St. Louis, MO (United States); Blankenship, R. E. [Washington Univ., St. Louis, MO (United States)

    2010-06-14

    Carotenoids present in the photosynthetic light-harvesting reaction center (LHRC) complex from chlorosome lacking filamentous anoxygenic phototroph, Roseiflexus castenholzii were purified and characterized for their photochemical properties. The LHRC from anaerobically grown cells contains five different carotenoids, methoxy-keto-myxocoxanthin, γ-carotene, and its three derivatives, whereas the LHRC from aerobically grown cells contains only three carotenoid pigments with methoxy-keto-myxocoxanthin being the dominant one. The spectroscopic properties and dynamics of excited singlet states of the carotenoids were studied by steady-state absorption, fluorescence and ultrafast time-resolved optical spectroscopy in organic solvent and in the intact LHRC complex. Time-resolved transient absorption spectroscopy performed in the near-infrared (NIR) on purified carotenoids combined with steady-state absorption spectroscopy led to the precise determination of values of the energies of the S1(21Ag-) excited state. Global and single wavelength fitting of the ultrafast spectral and temporal data sets of the carotenoids in solvents and in the LHRC revealed the pathways of de-excitation of the carotenoid excited states.

  2. Outdoor cultivation of microalgae for carotenoid production: current state and perspectives.

    Science.gov (United States)

    Del Campo, José A; García-González, Mercedes; Guerrero, Miguel G

    2007-04-01

    Microalgae are a major natural source for a vast array of valuable compounds, including a diversity of pigments, for which these photosynthetic microorganisms represent an almost exclusive biological resource. Yellow, orange, and red carotenoids have an industrial use in food products and cosmetics as vitamin supplements and health food products and as feed additives for poultry, livestock, fish, and crustaceans. The growing worldwide market value of carotenoids is projected to reach over US$1,000 million by the end of the decade. The nutraceutical boom has also integrated carotenoids mainly on the claim of their proven antioxidant properties. Recently established benefits in human health open new uses for some carotenoids, especially lutein, an effective agent for the prevention and treatment of a variety of degenerative diseases. Consumers' demand for natural products favors development of pigments from biological sources, thus increasing opportunities for microalgae. The biotechnology of microalgae has gained considerable progress and relevance in recent decades, with carotenoid production representing one of its most successful domains. In this paper, we review the most relevant features of microalgal biotechnology related to the production of different carotenoids outdoors, with a main focus on beta-carotene from Dunaliella, astaxanthin from Haematococcus, and lutein from chlorophycean strains. We compare the current state of the corresponding production technologies, based on either open-pond systems or closed photobioreactors. The potential of scientific and technological advances for improvements in yield and reduction in production costs for carotenoids from microalgae is also discussed. PMID:17277962

  3. Serum carotenoids reduce progression of early atherosclerosis in the carotid artery wall among Eastern Finnish men.

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    Jouni Karppi

    Full Text Available BACKGROUND: Several previous epidemiologic studies have shown that high blood levels of carotenoids may be protective against early atherosclerosis, but results have been inconsistent. We assessed the association between atherosclerotic progression, measured by intima-media thickness of the common carotid artery wall, and serum levels of carotenoids. METHODS: We studied the effect of carotenoids on progression of early atherosclerosis in a population-based study. The association between concentrations of serum carotenoids, and intima-media thickness of the common carotid artery wall was explored in 840 middle-aged men (aged 46-65 years from Eastern Finland. Ultrasonography of the common carotid arteries were performed at baseline and 7-year follow-up. Serum levels of carotenoids were analyzed at baseline. Changes in mean and maximum intima media thickness of carotid artery wall were related to baseline serum carotenoid levels in covariance analyses adjusted for covariates. RESULTS: In a covariance analysis with adjustment for age, ultrasound sonographer, maximum intima media thickness, examination year, body mass index, systolic blood pressure, smoking, physical activity, serum LDL cholesterol, family history of coronary heart disease, antihypertensive medication and serum high sensitivity C-reactive protein, 7-year change in maximum intima media thickness was inversely associated with lycopene (p = 0.005, α-carotene (p = 0.002 and β-carotene (p = 0.019, respectively. CONCLUSIONS: The present study shows that high serum concentrations of carotenoids may be protective against early atherosclerosis.

  4. ESR/ENDOR study of the guanine cation: Secondary product in 5' -dGMP

    International Nuclear Information System (INIS)

    Previous ESR studies by Voit and Huttermann of x-irradiated single crystals of 2' deoxyguanosine-5'-monophosphate have indicated the presence of a radical thought to be formed by deprotonation of the primary base cation at N1. In this study the authors report results of a detailed ESR and ENDOR experiment at 10 K which conflict with the results cited above. One of the radicals detected inhibited two α-proton type couplings. The data analysis shows that one coupling is due to the proton on the extra annular NH/sub 2/ group, while the other is due to the proton bonded to C8

  5. Validating Resonance Raman Spectroscopy: a Non-invasive Assessment of Skin Carotenoids as a Biomarker of Fruit and Vegetable Intake in Children

    OpenAIRE

    Aguilar, Sheryl Swain

    2013-01-01

    Background: Adult studies have found a strong correlation between serum carotenoids and skin carotenoids measured by resonance Raman spectroscopy (RRS). No published studies have examined correlations between skin and serum carotenoids among children. Objectives: (1) To validate skin RRS methodology against serum carotenoid measurements by high-performance liquid chromatography and (2) to determine if RRS skin carotenoids can be used as a valid biomarker of total fruit and vegetable (FV) inta...

  6. Content of carotenoids in roots of seventeen cultivars of Daucus carota L.

    Science.gov (United States)

    Mech-Nowak, Aleksandra; Swiderski, Adam; Kruczek, Michał; Luczak, Irena; Kostecka-Gugała, Anna

    2012-01-01

    The aim of this study was to compare the content of carotenoids in seventeen cultivars of carrots grown in Poland. Conventional orange cultivars with rarely grown were compared: white, yellow and purple with yellow core cultivars. To determine the content of carotenoids, extracts from lyophilized carrot roots were prepared and analyzed by spectrophotometric as well as HPLC methods with DAD detector. The highest content of carotenoids was found in cultivars: 'Korund F(1)' (48 mg/100g of fresh weight) and 'Salsa F(1)' (36 mg/100g of fresh weight). The antioxidant properties of selected cultivars were compared using the DPPH method. PMID:22428130

  7. Noninvasive laser Raman detection of carotenoid antioxidants in living human skin

    Science.gov (United States)

    Gellermann, Werner; Ermakov, Igor V.; Ermakova, Maia R.; McClane, Robert W.

    2001-05-01

    We have used resonance Raman scattering as a novel non- invasive optical technology to measure carotenoid antioxidants in human skin of healthy volunteers. Using blue-green laser excitation, clearly distinguishable carotenoid Raman spectra are obtained which are superimposed on a large skin autofluorescence background. The Raman spectra are obtained rapidly, i.e. within about 30 seconds, and the required laser light exposure levels are well within safety standards. Our technique can be used for rapid screening of carotenoid antioxidant levels in large populations and may have applications for assessing the risk for cutaneous diseases.

  8. Carotenoid crystal formation in Arabidopsis and carrot roots caused by increased phytoene synthase protein levels.

    Directory of Open Access Journals (Sweden)

    Dirk Maass

    Full Text Available BACKGROUND: As the first pathway-specific enzyme in carotenoid biosynthesis, phytoene synthase (PSY is a prime regulatory target. This includes a number of biotechnological approaches that have successfully increased the carotenoid content in agronomically relevant non-green plant tissues through tissue-specific PSY overexpression. We investigated the differential effects of constitutive AtPSY overexpression in green and non-green cells of transgenic Arabidopsis lines. This revealed striking similarities to the situation found in orange carrot roots with respect to carotenoid amounts and sequestration mechanism. METHODOLOGY/PRINCIPAL FINDINGS: In Arabidopsis seedlings, carotenoid content remained unaffected by increased AtPSY levels although the protein was almost quantitatively imported into plastids, as shown by western blot analyses. In contrast, non-photosynthetic calli and roots overexpressing AtPSY accumulated carotenoids 10 and 100-fold above the corresponding wild-type tissues and contained 1800 and 500 microg carotenoids per g dry weight, respectively. This increase coincided with a change of the pattern of accumulated carotenoids, as xanthophylls decreased relative to beta-carotene and carotene intermediates accumulated. As shown by polarization microscopy, carotenoids were found deposited in crystals, similar to crystalline-type chromoplasts of non-green tissues present in several other taxa. In fact, orange-colored carrots showed a similar situation with increased PSY protein as well as carotenoid levels and accumulation patterns whereas wild white-rooted carrots were similar to Arabidopsis wild type roots in this respect. Initiation of carotenoid crystal formation by increased PSY protein amounts was further confirmed by overexpressing crtB, a bacterial PSY gene, in white carrots, resulting in increased carotenoid amounts deposited in crystals. CONCLUSIONS: The sequestration of carotenoids into crystals can be driven by the

  9. Investigations on carotenoids in lichens. XII. Some species from the Pyrenean Peninsula

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    Bazyli Czeczuga

    2014-02-01

    Full Text Available By means of column and thin-layer chromatography, the authors investigated the presence of various carotenoids in thalli of 12 species of lichens from the Pyrenean Peninsula. The following carotenoids were found: lycophyll, lycoxanthin, β-carotene, α-, β-cryptoxanthin, lutein, lutein epoxide, zeaxanthin, antheraxanthin, canthaxanthin, phoenicoxanthin, adonixanthin, α-doradexanthin, astaxanthin, diatoxanthin, neoxanthin, violaxanthin, mutatochrome, mutatoxanthin and rhodoxanthin. The total content of carotenoids ranged from 2.299 (Cetraria cucullata to 39.402 mg•g-1 dry weight (Pseudoevernia furfuraceae.

  10. Radical cystectomy in eldery

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    Bančević Vladimir

    2015-01-01

    Full Text Available Background/Aim. Radical cystectomy is the method of choice for the treatment of muscle invasive bladder cancer. This major surgery is associated with many complications, especially in older patients. The aim of this study was to analyze preoperative comorbidity, and intraoperative and postoperative complicatons in patients older than 75 years. Methods. This clinical, retrospective study included 46 patients over 75 years, who underwent radical cystectomy. Indications for surgery, and complications during and after the surgery were followed up. Results. Preoperatively, anemia caused by hematuria was registered in 76% of the patients. In 52% of the patients urine derivation was performed by ileal conduit, in 35% by ureterocutaneostomy and in 13% orthotopic ileal neobladder was created. The average duration of surgery was 190 (120-300 min. A total of 76% of the patients were treated by blood supstitution intraoperatively, average 630 (310-1230 mL. Concerning pathological stage of transitional cell carcinoma of urinary bladder, 26% of the patients had T2, 4% T3a, 52% T3b, and 14% T4a stage. In one case, planocellular carcinoma was diagnosed by patohistological examination, and in 2 cases prostate carcinoma was incidentally found. The average duration of hospitalization was 16 (8-35 days. Conclusion. The main reason for cystectomy in patients over 70 and 80 years was gross hematuria caused by bladder cancer, with consecutive anemia which could not be solved using endoscopic treatment or blood supstitution. As expected, a prolonged stay in hospital after cystectomy, and a higher rate of complications were recorded in this population.

  11. Polyelectrolyte Condensation Induced by Linear Cations

    OpenAIRE

    Guáqueta, Camilo; Luijten, Erik

    2007-01-01

    We examine the role of the condensing agent in the formation of polyelectrolyte bundles, via grand-canonical Monte Carlo simulations. Following recent experiments we use linear, rigid divalent cations of various lengths to induce condensation. Our results clarify and explain the experimental results for short cations. For longer cations we observe novel condensation behavior owing to alignment of the cations. We also study the role of the polyelectrolyte surface charge density, and find a non...

  12. Functional assembly of the foreign carotenoid lycopene into the photosynthetic apparatus of Rhodobacter sphaeroides, achieved by replacement of the native 3-step phytoene desaturase with its 4-step counterpart from Erwinia herbicola.

    Science.gov (United States)

    Garcia-Asua, Guillermo; Cogdell, Richard J; Hunter, C Neil

    2002-04-01

    Photosynthetic organisms synthesize a diverse range of carotenoids. These pigments are important for the assembly, function and stability of photosynthetic pigment-protein complexes, and they are used to quench harmful radicals. The photosynthetic bacterium Rhodobacter sphaeroides was used as a model system to explore the origin of carotenoid diversity. Replacing the native 3-step phytoene desaturase (CrtI) with the 4-step enzyme from Erwinia herbicola results in significant flux down the spirilloxanthin pathway for the first time in Rb. sphaeroides. In Rb. sphaeroides, the completion of four desaturations to lycopene by the Erwinia CrtI appears to require the absence of CrtC and, in a crtC background, even the native 3-step enzyme can synthesize a significant amount (13%) of lycopene, in addition to the expected neurosporene. We suggest that the CrtC hydroxylase can intervene in the sequence of reactions catalyzed by phytoene desaturase. We investigated the properties of the lycopene-synthesizing strain of Rb. sphaeroides. In the LH2 light-harvesting complex, lycopene transfers absorbed light energy to the bacteriochlorophylls with an efficiency of 54%, which compares favourably with other LH2 complexes that contain carotenoids with 11 conjugated double bonds. Thus, lycopene can join the assembly pathway for photosynthetic complexes in Rb. sphaeroides, and can perform its role as an energy donor to bacteriochlorophylls. PMID:11967082

  13. The New Carotenoid Pigment Moraxanthin Is Associated with Toxic Microalgae

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    Alfonso Mangoni

    2011-02-01

    Full Text Available The new pigment “moraxanthin” was found in natural samples from a fish mortality site in the Inland Bays of Delaware, USA. Pure cultures of the species, tentatively named Chattonella cf. verruculosa, and natural samples contained this pigment as a dominant carotenoid. The pigment, obtained from a 10 L culture of C. cf. verruculosa, was isolated and harvested by HPLC and its structure determined from MS and 1D- and 2D-NMR. The data identified this pigment as a new acylated form of vaucheriaxanthin called moraxanthin after the berry like algal cell. Its presence in pure cultures and in natural bloom samples indicates that moraxanthin is specific to C. cf. verruculosa and can be used as a marker of its presence when HPLC is used to analyze natural blooms samples.

  14. Cationic electrodepositable coating composition comprising lignin

    Science.gov (United States)

    Fenn, David; Bowman, Mark P; Zawacky, Steven R; Van Buskirk, Ellor J; Kamarchik, Peter

    2013-07-30

    A cationic electrodepositable coating composition is disclosed. The present invention in directed to a cationic electrodepositable coating composition comprising a lignin-containing cationic salt resin, that comprises (A) the reaction product of: lignin, an amine, and a carbonyl compound; (B) the reaction product of lignin, epichlorohydrin, and an amine; or (C) combinations thereof.

  15. Anti-obesity activity of the marine carotenoid fucoxanthin.

    Science.gov (United States)

    Gammone, Maria Alessandra; D'Orazio, Nicolantonio

    2015-04-01

    Nowadays the global tendency towards physical activity reduction and an augmented dietary intake of fats, sugars and calories is leading to a growing propagation of overweight, obesity and lifestyle-related diseases, such diabetes, hypertension, dyslipidemia and metabolic syndrome. In particular, obesity, characterized as a state of low-level inflammation, is a powerful determinant both in the development of insulin resistance and in the progression to type 2 diabetes. A few molecular targets offer hope for anti-obesity therapeutics. One of the keys to success could be the induction of uncoupling protein 1 (UCP1) in abdominal white adipose tissue (WAT) and the regulation of cytokine secretions from both abdominal adipose cells and macrophage cells infiltrated into adipose tissue. Anti-obesity effects of fucoxanthin, a characteristic carotenoid, exactly belonging to xanthophylls, have been reported. Nutrigenomic studies reveal that fucoxanthin induces UCP1 in abdominal WAT mitochondria, leading to the oxidation of fatty acids and heat production in WAT. Fucoxanthin improves insulin resistance and decreases blood glucose levels through the regulation of cytokine secretions from WAT. The key structure of anti-obesity effect is suggested to be the carotenoid end of the polyene chromophore, which contains an allenic bond and two hydroxyl groups. Fucoxanthin, which can be isolated from edible brown seaweeds, recently displayed its many physiological functions and biological properties. We reviewed recent studies and this article aims to explain essential background of fucoxanthin, focusing on its promising potential anti-obesity effects. In this respect, fucoxanthin can be developed into promising marine drugs and nutritional products, in order to become a helpful functional food. PMID:25871295

  16. Anti-Obesity Activity of the Marine Carotenoid Fucoxanthin

    Directory of Open Access Journals (Sweden)

    Maria Alessandra Gammone

    2015-04-01

    Full Text Available Nowadays the global tendency towards physical activity reduction and an augmented dietary intake of fats, sugars and calories is leading to a growing propagation of overweight, obesity and lifestyle-related diseases, such diabetes, hypertension, dyslipidemia and metabolic syndrome. In particular, obesity, characterized as a state of low-level inflammation, is a powerful determinant both in the development of insulin resistance and in the progression to type 2 diabetes. A few molecular targets offer hope for anti-obesity therapeutics. One of the keys to success could be the induction of uncoupling protein 1 (UCP1 in abdominal white adipose tissue (WAT and the regulation of cytokine secretions from both abdominal adipose cells and macrophage cells infiltrated into adipose tissue. Anti-obesity effects of fucoxanthin, a characteristic carotenoid, exactly belonging to xanthophylls, have been reported. Nutrigenomic studies reveal that fucoxanthin induces UCP1 in abdominal WAT mitochondria, leading to the oxidation of fatty acids and heat production in WAT. Fucoxanthin improves insulin resistance and decreases blood glucose levels through the regulation of cytokine secretions from WAT. The key structure of anti-obesity effect is suggested to be the carotenoid end of the polyene chromophore, which contains an allenic bond and two hydroxyl groups. Fucoxanthin, which can be isolated from edible brown seaweeds, recently displayed its many physiological functions and biological properties. We reviewed recent studies and this article aims to explain essential background of fucoxanthin, focusing on its promising potential anti-obesity effects. In this respect, fucoxanthin can be developed into promising marine drugs and nutritional products, in order to become a helpful functional food.

  17. Organometallic cation-exchanged phyllosilicates

    OpenAIRE

    Fleming, Shay

    1991-01-01

    Organotin (IV) complexes formed between 0 01 M dimethyltin dichloride solutions prepared at pH 2 6 and 4 0, and trimethyltin chloride prepared at pH 3 4, with Na- 119 montmori 1lonite clay have been characterised using Sn Mflssbauer spectroscopy, X-ray diffraction, thermogravimetric analysis and water sorption isotherms Following cation exchange, Mttssbauer spectroscopy identified two tin species in the dimethyltin (IV)-exchanged clay prepared at pH 2 6 A cis specie...

  18. Reactions of aliphatic free radicals with transition metal complexes

    International Nuclear Information System (INIS)

    A pulse radiolytic study of the reactions of copper ions with free aliphatic radicals was carried out. It was found that all the aliphatic radicals studied react with Cusub(aq)sup(+) and Cusub(aq)sup(2+), forming an unstable compound, with a carbon-copper σ bond, according to the reaction Mnsub(aq)sup(n+)+ . CR1R2R3 → M-CR1R2Rsub(3)sup(n+). It was also found that the rates of formation of the intermediate compounds, their half-lives and their decomposition mechanism depend on the properties of the radical and the cation. Experiments for the determination of the influence of macrocyclic ligands of the Curtis type on the stability of intermediate compounds failed because of insufficient concentrations of these ligands. The processes of ligand hydridization, isomerization and decomposition for the macrocylic complexes Cusup(I)L were also studied. These complexes, which are unstable, are formed as a result of the reaction of the stable Cusup(II)L complexes with certain free aliphatic radicals

  19. Qualitative analysis of phytochemicals, and comparative superoxide radical scavenging along with reducing potency of Solanum nigrum using various solvent extracts

    Directory of Open Access Journals (Sweden)

    A Thenmozhi

    2011-01-01

    Full Text Available An attempt has been made to screen the phytochemicals, comparative superoxide radical scavenging and reducing potency of Solanum nigrum using various solvent extracts. The herbal powder obtained from plant part-dry leaves were extracted with various solvents. The extracts were analysed for phytochemicals and antioxidants-carotenoids, ascorbic acid, tocopherol, total phenol, proteins, reducing sugars and sterols. Free radical scavenging capacity was analysed in terms of superoxide radial scavenging assay and reducing power assay. Phytochemical characterization of the different extracts revealed the presence of the phytochemicals-alkaloids, phenols, flavonoids, sterol, saponin glycosides, reducing sugars, proteins, cardio active aglycones and cardinolides. Excellent Superoxide Radical scavenging ability found in almost all extracts of S. nigrum. In the present study superoxide radical reduces nitro blue tetrazolium (NBT to a blue coloured formazan that is measured at 560 nm. Antioxidant activity has been reported to be concomitant with development of reducing power. This shows that extracts might contain reductones like ascorbic acid, reducing sugar, thiol group containing protein which could react with free radicals to stabilize and terminate radical chain reaction. These findings suggest that the promising phytonutrients of the plant could be exploited against oxidative stress, cancer, ageing, Ischemic heart disease in dissolving thrombus, microbial infections and hormone replacement therapy (HRT justifying their use in traditional medicine as nutraceuticals.

  20. Carotenoid content of commonly consumed herbs and assessment of their bioaccessibility using an in vitro digestion model.

    Science.gov (United States)

    Daly, Trevor; Jiwan, Marvin A; O'Brien, Nora M; Aherne, S Aisling

    2010-06-01

    Herbs are a rich source of bioactive phytochemicals such as carotenoids, which are known to exert various positive biological effects. However, there is very limited information in the literature regarding the content and bioavailability of carotenoids from commonly consumed herbs. Therefore, the objectives of the present study were first, to determine the carotenoid content of eight herbs namely basil (Ocimum basilicum), coriander (Coriandrum sativum), dill (Anethum graveolens), mint (Metha L.), parsley (Petroselinum crispum), rosemary (Rosmarinus officinalis), sage (Salvia officinalis), and tarragon (Artemisia dracunculus L.); and second, to assess carotenoid bioaccessibility from these herbs using a simulated human in vitro digestion model. Carotenoid bioaccessibility is defined as the amount of carotenoids transferred to micelles after digestion when compared with the original amount present in the food. The content of individual carotenoids varied significantly among the herbs tested. Carotenoid bioaccessibility varied from 0 to 42.8%. Basil and coriander, and their respective micelles, contained the highest levels of beta-carotene, beta-cryptoxanthin, and lutein + zeaxanthin. Our findings show that herbs are rich sources of carotenoids and that these foods can significantly contribute to the intake of bioaccessible carotenoids. PMID:20443063