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Sample records for carotenoid radical cations

  1. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    Energy Technology Data Exchange (ETDEWEB)

    Kispert, Lowell D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Focsan, A Ligia [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Konovalova, Tatyana A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence, Jesse [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Bowman, Michael K [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Molnar, Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Deli, Jozsef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2007-06-11

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car•+) but also neutral radicals (#Car•) by proton loss from the methyl groups at positions 5 or 5', and possibly 9 or 9' and 13 or 13'. Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car•+ which agree with the ENDOR for carotenoid α-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity [Lycopene (III) versus 8'-apo-β-caroten-8'-al (IV)]; hydrogen bonding [Lutein (V) versus III]; host [silica-alumina versus MCM-41 molecular sieve]; and substituted metal in MCM-41. Loss of H+ from the 5(5'), 9(9') or 13(13') methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I •+…Chl•-), lower in energy than 1Chl*. Formation of I •+ results in bond

  2. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    International Nuclear Information System (INIS)

    Kispert, Lowell D.; Focsan, A. Ligia; Konovalova, Tatyana A.; Lawrence, Jesse; Bowman, Michael K.; Dixon, David A.; Molnar, Peter; Deli, Jozsef

    2007-01-01

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car ·+ ) but also neutral radicals ((number s ign)Car · ) by proton loss from the methyl groups at positions 5 or 5(prime), and possibly 9 or 9(prime) and 13 or 13(prime). Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car # center d ot# + which agree with the ENDOR for carotenoid π-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity (Lycopene (III) versus 8(prime)-apo-β-caroten-8(prime)-al (IV)); hydrogen bonding (Lutein (V) versus III); host (silica-alumina versus MCM-41 molecular sieve); and substituted metal in MCM-41. Loss of H + from the 5(5(prime)), 9(9(prime)) or 13(13(prime)) methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1 Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I # center d ot# + ...Chl # center d ot# - ), lower in

  3. Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

    International Nuclear Information System (INIS)

    Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

    1989-01-01

    Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

  4. Photolysis of carotenoids in chloroform: enhanced yields of carotenoid radical cations in the presence of a tryptophan ester

    International Nuclear Information System (INIS)

    El-Agamey, Ali; Burke, Marc; Edge, Ruth; Land, Edward J.; McGarvey, David J.; Truscott, T. George

    2005-01-01

    The presence of an acetyl tryptophan ester gives rise to enhanced yields of carotenoid radical cations in chloroform following 355 nm laser excitation of the carotenoid, even though the tryptophan does not absorb at this wavelength. The increase is attributed to positive charge transfer from semi-oxidized tryptophan itself generated by light absorbed by the carotenoid. The mechanism of these radical processes has been elucidated by pulse radiolysis studies

  5. Electron transfer from plant phenolates to carotenoid radical cations. Antioxidant interaction entering the Marcus theory inverted region.

    Science.gov (United States)

    Cheng, Hong; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2014-01-29

    β-Carotene, lycopene, and zeaxanthin are maximally regenerated by plant phenolates from their radical cations formed during laser flash photolysis in 9:1 (v/v) chloroform/methanol for a driving force corresponding to the reorganization energy according to the Marcus theory. For β-carotene, the reorganization energy has values of 0.41 ± 0.04 and 0.40 ± 0.04 eV for the plant phenols in the presence of 1 and 2 equiv of base, respectively, at 23 °C. For a driving force lower than the reorganization energy, regeneration of the carotenoids is less efficient as is seen for m-hydroxybenzoic acid, vanillic acid, and p-coumaric acid. For a driving force above the maximum rate as determined to have kET = 6.3 × 10(9) L·mol(-1)·s(-1) for syringic acid and β-carotene, the reaction becomes gradually slower and regeneration less efficient as is seen for the more reducing caffeic acid, rutin, and quercetin corresponding to an inverted region for the rate of electron transfer. Lycopene and zeaxanthin show a similar behavior for the same series of plant phenols with slightly lower reorganization energy, in agreement with the lower reduction potential of their radical cations, while, for the ketocarotenoids astaxanthin and canthaxanthin, fast reactions with a solvent of radical cations inhibit regeneration from being detected. Intermediate reducing plant phenols accordingly yield maximal protection of carotenoids against photobleaching in foods and beverages.

  6. Detection of Anisotropic Hyperfine Components of Chemically Prepared Carotenoid Radical Cations:1D and 2D ESEEM and Pulsed ENDOR Study

    International Nuclear Information System (INIS)

    Konovalova, Tatyana A.; Dikanov, Sergei A.; Bowman, Michael K.; Kispert, Lowell D.

    2001-01-01

    Canthaxanthin and 8'-apo-B-caroten-8'-al radical cations chemically prepared on activated silica-alumina and in CH2CI2 solution containing A1C13 were studied by pulsed EPR and ENDOR spectroscopies. Both the 1D three-pulse ESEEM and the 2D HYSCORE spectra of the carotenoid-A1C13 mixtures exhibited the 27 A1 nuclei peak at 3.75 MHz. This indicates electron-transfer interactions between carotenoids and A1III ions resulting in the formation and stabilization of carotenoid radical cations. Davies ENDOR measurements of the canthaxanthin radical cation on silica-alumina determined the hyperfine couplings of B protons belonging to three different methyl groups with ahI=2.6 MHz, aH2=8.6MHz, and ah3 ca. 13 MHz. The principal components of the proton hyperfine tensors were obtained from HYSCORE spectra in A1C13 solutions and on the solid support. Identification of the protons was made on the basis of isotropic hyperfine couplings determined by RHF-INDO/SP molecular orbital calculations. In frozen A1C13 solution, the C(7, 7')Ha and C(14, 14')-Ha a protons were observed for Canthaxanthin and the C(8 or 14')-Ha, C(15')-Ha were observed for 8'-apo-B-caroten-8'-al. On the silica-alumina support, the C(10, 10')-Ha, C(11, 11')-Ha, and C(15,15')-Ha a protons were measured for Canthaxanthin and the C(12)-Ha and C(15')-Ha were measured for 8' apo-B-caroten-8'-al. Some protons with large isotropic couplings (> 10 MHz) determined from HYSCORE analysis could be assigned to B protons, but the principal components of their hyperfine tensors are much more anisotropic than those reported previously for B protons. We suggest that cis/trans isomerization of carotenoids on silica-alumina results in stabilization of di-cis isomers with large isotropic couplings for some a protons which are comparable to those of B protons

  7. Pulsed radiation studies of carotenoid radicals and excited states

    International Nuclear Information System (INIS)

    Burke, M.

    2001-04-01

    The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of β-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar (∼1 x 10 7 M -1 s -1 ) for β-carotene and zeaxanthin and somewhat lower (∼0.5 x 10 7 M -1 s -1 ) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for β-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number of conjugated double bonds, the longer chain systems having

  8. Pulsed radiation studies of carotenoid radicals and excited states

    Energy Technology Data Exchange (ETDEWEB)

    Burke, M

    2001-04-01

    The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of {beta}-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar ({approx}1 x 10{sup 7} M{sup -1}s{sup -1}) for {beta}-carotene and zeaxanthin and somewhat lower ({approx}0.5 x 10{sup 7} M{sup -1}s{sup -1}) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for {beta}-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number

  9. DFT and ENDOR Study of Bixin Radical Cations and Neutral Radicals on Silica-Alumina.

    Science.gov (United States)

    Tay-Agbozo, Sefadzi S; Krzyaniak, Matthew D; Bowman, Michael K; Street, Shane; Kispert, Lowell D

    2015-06-18

    Bixin, a carotenoid found in annatto (Bixa orellana), is unique among natural carotenoids by being water-soluble. We stabilized free radicals from bixin on the surface of silica-alumina (Si-Al) and characterized them by pulsed electron-nuclear double resonance (ENDOR). DFT calculations of unpaired electron spin distribution for various bixin radicals predict the EPR hyperfine couplings. Least-square fitting of experimental ENDOR spectra by spectra calculated from DFT hyperfine couplings characterized the radicals trapped on Si-Al. DFT predicts that the trans bixin radical cation is more stable than the cis bixin radical cation by 1.26 kcal/mol. This small energy difference is consistent with the 26% trans and 23% cis radical cations in the ENDOR spectrum. The remainder of the ENDOR spectrum is due to several neutral radicals formed by loss of a H(+) ion from the 9, 9', 13, or 13' methyl group, a common occurrence in all water-insoluble carotenoids previously studied. Although carboxyl groups of bixin strongly affect its solubility relative to other natural carotenoids, they do not alter properties of its free radicals based on DFT calculations and EPR measurements which remain similar to typical water-insoluble carotenoids.

  10. Radical cations in condensed phases

    Energy Technology Data Exchange (ETDEWEB)

    Symons, M.C.R. (Leicester Univ. (UK). Dept. of Chemistry)

    The subject is covered in sections, entitled: introduction (scope of present Review); preparative procedures; alkane and cycloalkane cations; alkene and cyclic alkene cations; alkyl-halide cations; alcohol and ether cations; carbonyl cations (aldehyde, ketone and ester cations); sulphur-centred cations; selenium-centred cations; nitrogen-centred cations; phosphorus-centred cations; tin- and lead-centred cations; aromatic cations; five membered hetero-aromatic cations; vinyl cations; inorganic cations.

  11. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.

    2000-01-01

    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The

  12. Radical Cations and Acid Protection during Radiolysis

    International Nuclear Information System (INIS)

    Mincher, Bruce J.; Zarzana, Christopher A.; Mezyk, Stephen P.

    2016-01-01

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  13. Radical Cations and Acid Protection during Radiolysis

    Energy Technology Data Exchange (ETDEWEB)

    Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2016-09-09

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO3. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  14. Generation of carotenoid radical cation in the vicinity of a chlorophyll derivative bound to titanium oxide, upon excitation of the chlorophyll derivative to the Q y state, as identified by time-resolved absorption spectroscopy

    Science.gov (United States)

    Wang, Xiao-Feng; Kakitani, Yoshinori; Xiang, Junfeng; Koyama, Yasushi; Rondonuwu, Ferdy S.; Nagae, Hiroyoshi; Sasaki, Shin-ichi; Tamiaki, Hitoshi

    2005-12-01

    Electron injection from a chlorophyll derivative (methyl 3-carboxy-3-devinylpyropheophorobide a, abbreviated as PPB a) to TiO 2 nanoparticle took place in ≈30 fs following the decay of an excimer that was generated immediately after excitation to the Q y state (681 nm). Then, electron transfer from carotenoids (Cars) to PPB arad + took place in ≈200-240 ps. The latter observation supports the electron-transfer mechanism proposed in a previous investigation, in which Cars were added as redox spacers to the PPB a-sensitized TiO 2 solar cells to enhance their performance (X.-F. Wang, J. Xiang, P. Wang, Y. Koyama, S. Yanagida, Y. Wada, K. Hamada, S. Sasaki, H. Tamiaki, Chem. Phys. Lett. 408 (2005) 409).

  15. Isomerizations of the Nitromethane Radical Cation in the Gas Phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars; Elbel, Susanne

    1986-01-01

    The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane/aci-nitromethane tauto......The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane...

  16. 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...... and 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....

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

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    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 - sub(aq)), while superoxide anions (O 2 - ) 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)

  18. Structure and Intramolecular Proton Transfer of Alanine Radical Cations

    International Nuclear Information System (INIS)

    Lee, Gab Yong

    2012-01-01

    The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the NH 2 group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [NH 3 + -CHCH 3 -COO·], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol

  19. Renaissance of cation-radicals in mass spectrometry.

    Science.gov (United States)

    Tureček, František

    2013-01-01

    This brief overview addresses the topic that was presented in the Thomson Medal Award session at the 19th International Mass Spectrometry Conference in Kyoto, Japan. Mass spectrometry of cation-radicals has enjoyed a remarkable renaissance thanks to the development of new methods for electron attachment to multiply charged peptide ions. The charge-reduced ions that are odd-electron species exhibit interesting reactivity that is useful for peptide and protein sequencing. The paper briefly reviews the fundamental aspects of the formation, energetics, and backbone dissociations of peptide cation-radicals.

  20. The chemistry of separations ligand degradation by organic radical cations

    International Nuclear Information System (INIS)

    Mezyk, S.P.; Horne, G.P.; Mincher, B.J.; Zalupski, P.R.; Cook, A.R.; Wishart, J.F.

    2016-01-01

    Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexing agents and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R .+ ), carbon-centered radicals (R . ), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R .+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with 2 ligands: CMPO and TODGA. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved. (authors)

  1. Structure and Reactivity of the Cysteine Methyl Ester Radical Cation

    NARCIS (Netherlands)

    Osburn, S.; Steill, J. D.; Oomens, J.; O' Hair, R. A. J.; Van Stipdonk, M.; Ryzhov, V.

    2011-01-01

    The structure and reactivity of the cysteine methyl ester radical cation, CysOMe(center dot+), have been examined in the gas phase using a combination of experiment and density functional theory (DFT) calculations. CysOMe(center dot+) undergoes rapid ion molecule reactions with dimethyl disulfide,

  2. Renaissance of Cation-Radicals in Mass Spectrometry

    OpenAIRE

    Tureček, František

    2013-01-01

    This brief overview addresses the topic that was presented in the Thomson Medal Award session at the 19th International Mass Spectrometry Conference in Kyoto, Japan. Mass spectrometry of cation-radicals has enjoyed a remarkable renaissance thanks to the development of new methods for electron attachment to multiply charged peptide ions. The charge-reduced ions that are odd-electron species exhibit interesting reactivity that is useful for peptide and protein sequencing. The paper briefly revi...

  3. 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.

  4. The cysteine radical cation: structures and fragmentation pathways.

    Science.gov (United States)

    Zhao, Junfang; Siu, K W Michael; Hopkinson, Alan C

    2008-01-14

    A theoretical study on the structures, relative energies, isomerization reactions and fragmentation pathways of the cysteine radical cation, [NH(2)CH(CH(2)SH)COOH].+, is reported. Hybrid density functional theory (B3LYP) has been used in conjunction with the 6-311++G(d,p) basis set. The isomer at the global minimum, Captodative-1, has the structure NH(2)C.(CH(2)SH)C(OH)(2)+; the stability of this ion is attributed to the captodative effect in which the NH(2) functions as a powerful pi-electron donor and C(OH)(2)+ as a powerful pi-electron acceptor. Ion Distonic-S-1, H(3)N(+)CH(CH(2)S.)COOH, in which the radical is formally situated on the S atom, is higher in enthalpy (DeltaH degrees (0)) than Captodative-1 by 6.1 kcal mol(-1), but is lower in enthalpy than another isomer Distonic-C-1, H(3)N(+)C.(CH(2)SH)COOH, by 8.2 kcal mol(-1). Isomerization of the canonical radical cation of cysteine, [H(2)NCH(CH(2)SH)COOH].+, (Canonical-1), to Captodative-1 has an enthalpy of activation of 25.8 kcal mol(-1), while the barrier against isomerization of Canonical-1 to Distonic-S-1 is only 9.6 kcal mol(-1). Two additional transient tautomers, one with the radical located at C(alpha) and the charge on SH(2), and the other a carboxy radical with the charge on NH(3), are reported. Plausible fragmentation pathways (losses of small molecules, CO(2), CH(2)S, H(2)S and NH(3), and neutral radicals COOH. , HSCH(2). and NH(2).) from Canonical-1 are examined.

  5. Free Radical Exposure Creates Paler Carotenoid-Based Ornaments: A Possible Interaction in the Expression of Black and Red Traits

    Science.gov (United States)

    Alonso-Alvarez, Carlos; Galván, Ismael

    2011-01-01

    Oxidative stress could be a key selective force shaping the expression of colored traits produced by the primary animal pigments in integuments: carotenoids and melanins. However, the impact of oxidative stress on melanic ornaments has only recently been explored, whereas its role in the expression of carotenoid-based traits is not fully understood. An interesting study case is that of those animal species simultaneously expressing both kinds of ornaments, such as the red-legged partridge (Alectoris rufa). In this bird, individuals exposed to an exogenous source of free radicals (diquat) during their development produced larger eumelanin-based (black) plumage traits than controls. Here, we show that the same red-legged partridges exposed to diquat simultaneously developed paler carotenoid-based ornaments (red beak and eye rings), and carried lower circulating carotenoid levels as well as lower levels of some lipids involved in carotenoid transport in the bloodstream (i.e., cholesterol). Moreover, partridges treated with a hormone that stimulates eumelanin production (i.e., alpha-melanocyte-stimulating hormone) also increased blood carotenoid levels, but this effect was not mirrored in the expression of carotenoid-based traits. The redness of carotenoid-based ornaments and the size of a conspicuous eumelanic trait (the black bib) were negatively correlated in control birds, suggesting a physiological trade-off during development. These findings contradict recent studies questioning the sensitivity of carotenoids to oxidative stress. Nonetheless, the impact of free radicals on plasma carotenoids seems to be partially mediated by changes in cholesterol metabolism, and not by direct carotenoid destruction/consumption. The results highlight the capacity of oxidative stress to create multiple phenotypes during development through differential effects on carotenoids and melanins, raising questions about evolutionary constraints involved in the production of multiple

  6. Carotenoids

    Science.gov (United States)

    This short article indicated that greater understanding of the biological functions of carotenoids mediated via their oxidative metabolites through their effects on these important cellular pathways and molecular targets, as well as their significance to cancer prevention, is needed. In considering ...

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

    International Nuclear Information System (INIS)

    Werst, D.W.; Trifunac, A.D.

    1992-01-01

    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

  8. Resonance Raman and quantum chemical studies of short polyene radical cations

    DEFF Research Database (Denmark)

    Keszthelyi, T.; Wilbrandt, R.; Bally, T.

    1997-01-01

    The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1...... and to assist assignment of the resonance Raman spectra. A new and improved scaled quantum mechanical force field for the butadiene radical cation was also determined. The presence of more than one rotamer was observed in all the polyene radical cations we investigated. (C) 1997 Elsevier Science B.V....

  9. Formation and reactions of cation-radicals of aliphatic ketones in freon matrices at low temperatures

    International Nuclear Information System (INIS)

    Belevskii, V.N.; Belopushkin, S.I.; Fel'dman, V.I.

    1988-01-01

    In solutions of acetone and methyl ethyl ketone in CFCl 3 (0.1-22%) γ-irradiated at 77 K, monomeric and dimeric cation-radicals of the ketones, as well as RCHCOMe radicals, are stabilized with yields dependent on the ketone concentration in the CFCl 3 . On exposure to light the dimeric cation-radicals are converted to RCHCOMe while the monomers disappear without forming radicals. It is shown that different types of ion-molecule reactions occur in the solid phase in which the monomeric and dimeric cation-radicals participate

  10. Formation and transformations of radical-cations of aliphatic ketones in freon matrices at low temperatures

    International Nuclear Information System (INIS)

    Belevskij, V.N.; Belopushkin, S.I.; Fel'dman, V.I.

    1987-01-01

    Monomeric and dimeric radical-cations of ketones as well as RCHCOMe radicals which yields depend on concentrations of CFCl 3 ketones are stabilized in γ-irradiated solutions of acetone and methyl ethyl ketone in CFCl 3 (0.1-22%) at 77 K. Under light action dimeric radical-cations are transformed into RCHCOMe, and monomeric ones disappear without radical formation. Different types of ion-molecular reactions in a solid phase with monomeric and dimeric radical-cation participation are shown

  11. Carotenoid stabilized gold and silver nanoparticles derived from the Actinomycete Gordonia amicalis HS-11 as effective free radical scavengers.

    Science.gov (United States)

    Sowani, Harshada; Mohite, Pallavi; Damale, Shailesh; Kulkarni, Mohan; Zinjarde, Smita

    2016-12-01

    The Actinomycete Gordonia amicalis HS-11 produced orange pigments when cultivated on n-hexadecane as the sole carbon source. When cells of this pigmented bacterium were incubated with 1mM chloroauric acid (HAuCl 4 ) or silver nitrate (AgNO 3 ), pH 9.0, at 25°C, gold and silver nanoparticles, respectively, were obtained in a cell associated manner. It was hypothesized that the pigments present in the cells may be mediating metal reduction reactions. After solvent extraction and High Performance Liquid Chromatography, two major pigments displaying UV-vis spectra characteristic of carotenoids were isolated. These were identified on the basis of Atmospheric Pressure Chemical Ionization Mass Spectrometry (APCI-MS) in the positive mode as 1'-OH-4-keto-γ-carotene (Carotenoid K) and 1'-OH-γ-carotene (Carotenoid B). The hydroxyl groups present in the carotenoids were eliminated under alkaline conditions and provided the reducing equivalents necessary for synthesizing nanoparticles. Cell associated and carotenoid stabilized nanoparticles were characterized by different analytical techniques. In vitro free radical scavenging activities of cells (control, gold and silver nanoparticle loaded), purified carotenoids and carotenoid stabilized gold and silver nanoparticles were evaluated. Silver nanoparticle loaded cells and carotenoid stabilized silver nanoparticles exhibited improved nitric oxide (NO) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging activities compared to their control and gold counterparts. This paper thus reports cell associated nanoparticle synthesis by G. amicalis, describes for the first time the role of carotenoid pigments in metal reduction processes and demonstrates enhanced free radical scavenging activities of the carotenoid stabilized nanoparticles. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Kinetics of styrene type radical cations generated by different ionization procedures

    International Nuclear Information System (INIS)

    Brede, O.; David, Frank

    1996-01-01

    In this paper the results from time-resolved experiments (pulse radiolysis, laser photolysis) on the formation of radical cations derived from styrene type olefins in solvents of different polarity are presented. The free olefin radical cations formed by charge transfer (in cyclohexane), two photon ionization or one electron oxidation (in aqueous solutions) dimerize to distonic radical cations or react with nucleophiles to produce benzyl type radicals. The decay of the dimer cation Ar-C·H-CH 2 -CH 2 -C + H-Ar seems to be determined by their ionic state: cationic polymerization in the case of free radical cations (one electron transfer ionization of styrenes), and intramolecular rearrangement to molecular dimer structures in the presence of counter ions [triplet sensitized electron transfer as reported by [Schepp and Johnston (1994) J. Am. Chem. Soc. 116, 6895]. (Author)

  13. Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

    International Nuclear Information System (INIS)

    Desrosiers, M.F.; Trifunac, A.D.

    1986-01-01

    The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10 -2 M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures

  14. Formation and reactions of radical cations of substituted benzenes in aqueous media

    International Nuclear Information System (INIS)

    Holcman, J.

    1977-08-01

    Radical cations of anisole, methylated benzenes, ethylbenzene, isopropylbenzene, tert-butylbenzene and N,N-dimethylaniline were studied in aqueous media by pulse radiolytic technique. Absorption spectra and reaction kinetics of the radical cations were recorded. The radical cations are formed from the corresponding OH adducts by the elimination of OH - , either by a simple dissociation or by an acid catalyzed reaction. The rate constants of the formation of the radical cations and their reactions with water, OH - and Fe 2+ , or the reaction of a proton loss, were measured. The rate constants for the reaction with water and OH - , together with the rate constants for the dissociation of the OH adducts, are correlated with the ionization potential of the parent compound. These correlations offer a possibility of predicting the acid-base properties of radical cations of substituted benzenes, or the estimation of their ionization potential. (author)

  15. Radiation-induced polymerisation of 2,3-dihydrofuran: free-radical or cationic mechanism?

    Science.gov (United States)

    Janovský, Igor; Naumov, Sergej; Knolle, Wolfgang; Mehnert, Reiner

    2005-02-01

    Concentrated (10 mol%) solutions of 2,3-dihydrofuran in CFCl 2CF 2Cl matrix were irradiated at 77 K and several intermediates (dimer radical cation, dihydrofuryl radical, and polymer radicals) were observed by low-temperature EPR spectroscopy. The irradiated solutions yielded after melting a polymeric product, which was characterised by IR spectroscopy and gel permeation chromatography. The polydisperse polymer is assumed to be formed mainly by a cationic process initiated by a dimer carbocation. The free-radical mechanism via the dihydrofuryl radical leads to low molecular weight oligomers only. Quantum chemical calculations support the interpretation of the experimental results.

  16. Nitroxide free radicals protect macular carotenoids against chemical destruction (bleaching) during lipid peroxidation.

    Science.gov (United States)

    Zareba, M; Widomska, J; Burke, J M; Subczynski, W K

    2016-12-01

    Macular xanthophylls (MXs) lutein and zeaxanthin are dietary carotenoids that are selectively concentrated in the human eye retina, where they are thought to protect against age-related macular degeneration (AMD) by multiple mechanisms, including filtration of phototoxic blue light and quenching of singlet oxygen and triplet states of photosensitizers. These physical protective mechanisms require that MXs be in their intact structure. Here, we investigated the protection of the intact structure of zeaxanthin incorporated into model membranes subjected to oxidative modification by water- and/or membrane-soluble small nitroxide free radicals. Model membranes were formed from saturated, monounsaturated, and polyunsaturated phosphatidylcholines (PCs). Oxidative modification involved autoxidation, iron-mediated, and singlet oxygen-mediated lipid peroxidation. The extent of chemical destruction (bleaching) of zeaxanthin was evaluated from its absorption spectra and compared with the extent of lipid peroxidation evaluated using the thiobarbituric acid assay. Nitroxide free radicals with different polarity (membrane/water partition coefficients) were used. The extent of zeaxanthin bleaching increased with membrane unsaturation and correlated with the rate of PC oxidation. Protection of the intact structure of zeaxanthin by membrane-soluble nitroxides was much stronger than that by water-soluble nitroxides. The combination of zeaxanthin and lipid-soluble nitroxides exerted strong synergistic protection against singlet oxygen-induced lipid peroxidation. The synergistic effect may be explained in terms of protection of the intact zeaxanthin structure by effective scavenging of free radicals by nitroxides, therefore allowing zeaxanthin to quench the primary oxidant, singlet oxygen, effectively by the physical protective mechanism. The redox state of nitroxides was monitored using electron paramagnetic resonance spectroscopy. Both nitroxide free radicals and their reduced form

  17. Blue-Violet Light Irradiation Dose Dependently Decreases Carotenoids in Human Skin, Which Indicates the Generation of Free Radicals

    Directory of Open Access Journals (Sweden)

    Staffan Vandersee

    2015-01-01

    Full Text Available In contrast to ultraviolet and infrared irradiation, which are known to facilitate cutaneous photoaging, immunosuppression, or tumour emergence due to formation of free radicals and reactive oxygen species, potentially similar effects of visible light on the human skin are still poorly characterized. Using a blue-violet light irradiation source and aiming to characterize its potential influence on the antioxidant status of the human skin, the cutaneous carotenoid concentration was measured noninvasively in nine healthy volunteers using resonance Raman spectroscopy following irradiation. The dose-dependent significant degradation of carotenoids was measured to be 13.5% and 21.2% directly after irradiation at 50 J/cm² and 100 J/cm² (P<0.05. The irradiation intensity was 100 mW/cm². This is above natural conditions; the achieved doses, though, are acquirable under natural conditions. The corresponding restoration lasted 2 and 24 hours, respectively. The degradation of cutaneous carotenoids indirectly shows the amount of generated free radicals and especially reactive oxygen species in human skin. In all volunteers the cutaneous carotenoid concentration dropped down in a manner similar to that caused by the infrared or ultraviolet irradiations, leading to the conclusion that also blue-violet light at high doses could represent a comparably adverse factor for human skin.

  18. Glutathione radical cation in the gas phase; generation, structure and fragmentation.

    Science.gov (United States)

    Zhao, Junfang; Siu, K W Michael; Hopkinson, Alan C

    2011-11-07

    Two different chemical methods have been used to form glutathione radical cations: (1) collision-induced dissociations (CIDs) of the ternary complex [Cu(II)(tpy)(M)]˙(2+) (M = GSH, tpy = 2,2':6',2''-terpyridine) and (2) homolysis of the S-NO bond in protonated S-nitrosoglutathione. The radical cations, M˙(+), were trapped and additional CIDs were performed. They gave virtually identical CID spectra, suggesting a facile interconversion between initial structures prior to fragmentation. DFT calculations at the B3LYP/6-31++G(d,p) level of theory have been used to study interconversion between different isomers of the glutathione radical cation and to examine mechanisms by which these ions fragment. The N-terminal α-carbon-centred radical cation, strongly stabilized by the captodative effect, is at the global minimum, which is 8.5 kcal mol(-1) lower in enthalpy than the lowest energy conformer of the S-centred radical cation. The barrier against interconversion is 18.1 kcal mol(-1) above the S-centred radical.

  19. UV-Vis Action Spectroscopy Reveals a Conformational Collapse in Hydrogen-Rich Dinucleotide Cation Radicals.

    Science.gov (United States)

    Korn, Joseph A; Urban, Jan; Dang, Andy; Nguyen, Huong T H; Tureček, František

    2017-09-07

    We report the generation of deoxyriboadenosine dinucleotide cation radicals by gas-phase electron transfer to dinucleotide dications and their noncovalent complexes with crown ether ligands. Stable dinucleotide cation radicals of a novel hydrogen-rich type were generated and characterized by tandem mass spectrometry and UV-vis photodissociation (UVPD) action spectroscopy. Electron structure theory analysis indicated that upon electron attachment the dinucleotide dications underwent a conformational collapse followed by intramolecular proton migrations between the nucleobases to give species whose calculated UV-vis absorption spectra matched the UVPD action spectra. Hydrogen-rich cation radicals generated from chimeric riboadenosine 5'-diesters gave UVPD action spectra that pointed to novel zwitterionic structures consisting of aromatic π-electron anion radicals intercalated between stacked positively charged adenine rings. Analogies with DNA ionization are discussed.

  20. Formation of radical cations in a model for the metabolism of aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Lehner, Andreas F.; Horn, Jamie; Flesher, James W.

    2004-01-01

    To test the hypothesis that electrophilic radical cations are the major ultimate electrophilic and carcinogenic forms of benz[a]anthracene (BA), dibenz[a,h]anthracene (DBA), and benzo[a]pyrene (BP), we have focused on a chemical model of metabolism which parallels and duplicates known or potential metabolites of some polycyclic hydrocarbons formed in cells. Studies of this model system show that radical cations are hardly formed, if at all, in the case of BA or DBA but are definitely formed in the cases of the carcinogen BP as well as the non-carcinogenic hydrocarbons, pyrene and perylene. We conclude that the carcinogenicities of BA, DBA, BP, pyrene, and perylene are independent of one-electron oxidation to radical cation intermediates

  1. Fingerprinting DNA oxidation processes: IR characterization of the 5-methyl-2'-deoxycytidine radical cation.

    Science.gov (United States)

    Bucher, Dominik B; Pilles, Bert M; Pfaffeneder, Toni; Carell, Thomas; Zinth, Wolfgang

    2014-02-24

    Methylated cytidine plays an important role as an epigenetic signal in gene regulation. Its oxidation products are assumed to be involved in active demethylation processes but also in damaging DNA. Here, we report the photochemical production of the 5-methyl-2'-deoxycytidine radical cation via a two-photon ionization process. The radical cation is detected by time-resolved IR spectroscopy and identified by band assignment using density functional theory calculations. Two final oxidation products are characterized with liquid chromatography coupled to mass spectrometry. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Structure and Reactivity of the Glutathione Radical Cation: Radical Rearrangement from the Cysteine Sulfur to the Glutamic Acid alpha-Carbon Atom

    NARCIS (Netherlands)

    Osburn, S.; Berden, G.; Oomens, J.; Gulyuz, K.; Polfer, N.C.; O'Hair, R.A.J.; Ryzhov, V.

    2013-01-01

    A gas-phase radical rearrangement through intramolecular hydrogen-atom transfer (HAT) was studied in the glutathione radical cation, [-ECG](+.), which was generated by a homolytic cleavage of the protonated S-nitrosoglutathione. Ion-molecule reactions suggested that the radical migrates from the

  3. Resonance Raman investigation of the radical cation of 1,3,5-hexatriene

    DEFF Research Database (Denmark)

    Keszhelyi, T.; Wilbrandt, R.; Cave, R.J.

    1994-01-01

    The resonance Raman spectrum of the 1,3,5-hexatriene radical cation generated by gamma-irradiation in a Freon glass is reported. The spectrum is excited at 395 nm in resonance with the second absorption band. Identical spectra are obtained from ionized (E)- and (Z)-1,3,5-hexatriene. The presence...

  4. Cationic and radical intermediates in the acid photorelease from aryl sulfonates and phosphates.

    Science.gov (United States)

    Terpolilli, Marco; Merli, Daniele; Protti, Stefano; Dichiarante, Valentina; Fagnoni, Maurizio; Albini, Angelo

    2011-01-01

    The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly) radical with sulfonates.

  5. Resonance Raman and quantum chemical studies of short polyene radical cations

    DEFF Research Database (Denmark)

    Keszthelyi, T.; Wilbrandt, R.; Bally, T.

    1997-01-01

    ,3,5-hexatriene have been studied. The radical cations were generated radiolytically in a glassy Freon matrix and investigated by optical absorption and resonance Raman spectroscopy. Ab initio and density functional molecular-orbital calculations have been carried out to predict equilibrium structures...

  6. 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...... a much more efficient interaction between the nitrogen 'lone pairs' than in the neutral ground state....

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

    International Nuclear Information System (INIS)

    Grodkowski, J.; Bobrowski, K.; Mehnert, R.; Brede, O.

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl 4 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)

  8. Evidence for the Formation of Pyrimidine Cations from the Sequential Reactions of Hydrogen Cyanide with the Acetylene Radical Cation.

    Science.gov (United States)

    Hamid, Ahmed M; Bera, Partha P; Lee, Timothy J; Aziz, Saadullah G; Alyoubi, Abdulrahman O; El-Shall, M Samy

    2014-10-02

    Herein, we report the first direct evidence for the formation of pyrimidine ion isomers by sequential reactions of HCN with the acetylene radical cation in the gas phase at ambient temperature using the mass-selected variable temperature and pressure ion mobility technique. The formation and structures of the pyrimidine ion isomers are theoretically predicted via coupled cluster and density functional theory calculations. This ion-molecule synthesis may indicate that pyrimidine is produced in the gas phase in space environments before being incorporated into condensed-phase ices and transformed into nucleic acid bases such as uracil.

  9. 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....

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

    Science.gov (United States)

    Cheng, Hong; Liang, Ran; Han, Rui-Min; Zhang, Jian-Ping; Skibsted, Leif H

    2014-02-01

    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 k2 = 3.2 × 10(9) L mol(-1) s(-1) in 9 : 1 v/v chloroform-methanol at 23 °C, less efficiently by the anion of salicylic acid with 2.2 × 10(8) L mol(-1) s(-1), 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 rearrangements. The relative scavenging rate of the β-carotene radical cation by the three salicylates is supported by DFT-calculations.

  11. Formation and decay of the methylviologen radical cation in the solid phase

    Science.gov (United States)

    Wolszczak, M.; Stradowski, Cz.

    Absorption and emission spectra of the methylviologen (MV 2+)/ tris (2,2'-bipyridine) ruthenium(II)[Ru(bpy) 2+3 system in a variety of solid systems—ethylene glycol-water glass, polymer foil, cellulose, and wool—have been studied at 4.2, 77, and 298 K. It was found that MV 2+ always quenches the luminescence of ∗ Ru(bpy)2+3. However, the MV +. radical cation, which is generated at 298 K as a result of a quenching process, is not generated at 77 and 4.2 K. Lowering of the temperature probably prevents the diffusion of electron donor to the oxidized form of photosensitizer and enables instantaneous back reaction. The formation of the MV +. radical cation under the influence of light λ > 300 nm at low and ambient temperatures has been studied. The crucial role of water in the oxidation of MV +. was confirmed in a pulse radiolysis experiment.

  12. Are radical cation states delocalized over GG and GGG hole traps in DNA?

    Science.gov (United States)

    Voityuk, Alexander A

    2005-06-02

    Recently, Kurnikov et al. (J. Phys. Chem. B 2002, 106, 7) have shown that solvation of DNA duplexes destabilizes holes of sizes larger than three base pairs. In this paper, we consider the effects of solvation and internal reorganization on the hole charge distribution in sequences 5'-X-GG-Y-3'. Radical cation states in DNA are found to be localized to a single guanine site independent of the nature of adjacent base pairs.

  13. New electrochemical oscillator based on the cation-catalyzed reduction of nitroaromatic radical anions

    Czech Academy of Sciences Publication Activity Database

    Hromadová, Magdaléna; Pospíšil, Lubomír; Sokolová, Romana; Fanelli, N.

    2009-01-01

    Roč. 54, č. 22 (2009), s. 4991-4996 ISSN 0013-4686 R&D Projects: GA AV ČR IAA400400802; GA AV ČR IAA400400505; GA ČR GA203/08/1157; GA MŠk LC510; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : nitroaromatic radical * cationic catalysis * electrochemical impendance * oscillation Subject RIV: CG - Electrochemistry Impact factor: 3.325, year: 2009

  14. PPP and CNDO calculations on the free radical cations of styrene

    International Nuclear Information System (INIS)

    Helmstreit, W.

    1986-01-01

    Open shell calculations were carried out on the styrene monomer radical cation St/sup +./, the associated dimer radical cation St 2 /sup +./, and the covalently bonded dimer radical cation (St-St)/sup +./, using a PPP and CNDO/INDO method. St 2 /sup +./ was assumed to have a sandwich structure with different overlapping of the π-orbitals. Calculated transition energies are in agreement with the experimental data. The calculations suggest that St 2 /sup +./ has electronic transitions in the IR and UV/VIS range whereas those of (St-St)/sup +./ lie only within the UV/VIS range. The molecular diagrams of the investigated ions are discussed in the framework of general structure principles. The change of the total energy calculated for the reaction steps St/sup +./ + St → St 2 + → (St-St) + as well as the similarity of the electronic structures of St 2 /sup +./ and (St-St)/sup +./ suggest that the former is a precursor of the latter ion. (author)

  15. Synthesis of block copolymers by combination of atom transfer radical polymerization and visible light-induced free radical promoted cationic polymerization.

    Science.gov (United States)

    Kahveci, Muhammet U; Acik, Gokhan; Yagci, Yusuf

    2012-02-27

    A new synthetic approach for the preparation of block copolymers by mechanistic transformation from atom transfer radical polymerization (ATRP) to visible light-induced free radical promoted cationic polymerization is described. A series of halide end-functionalized polystyrenes with different molecular weights synthesized by ATRP were utilized as macro-coinitiators in dimanganese decacarbonyl [Mn(2) (CO)(10) ] mediated free radical promoted cationic photopolymerization of cyclohexene oxide or isobutyl vinyl ether. Precursor polymers and corresponding block copolymers were characterized by spectral, chromatographic, and thermal analyses. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. New electrochemical oscillator based on the cation-catalyzed reduction of nitroaromatic radical anions

    Energy Technology Data Exchange (ETDEWEB)

    Hromadova, Magdalena [J. Heyrovsky Institute of Physical Chemistry of ASCR, v.v.i., Dolejskova 3, CZ-18223 Prague (Czech Republic)], E-mail: hromadom@jh-inst.cas.cz; Pospisil, Lubomir [J. Heyrovsky Institute of Physical Chemistry of ASCR, v.v.i., Dolejskova 3, CZ-18223 Prague (Czech Republic)], E-mail: Lubomir.Pospisil@jh-inst.cas.cz; Sokolova, Romana [J. Heyrovsky Institute of Physical Chemistry of ASCR, v.v.i., Dolejskova 3, CZ-18223 Prague (Czech Republic); Fanelli, Nicolangelo [Istituto per i Processi Chimico-Fisici, C.N.R., via G. Moruzzi 1, I-56124 Pisa (Italy)

    2009-09-01

    Nitroaromatic compound bifenox (methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate) is used as a model system for a new NDR oscillator in the aprotic solvent acetonitrile. The reduction of bifenox yields the anion radical, which is further reduced by an overall addition of three electrons and four protons to the corresponding phenylhydroxylamine. The second reduction step is strongly influenced by the nature and concentration of the tetraalkylammonium salts used as the supporting electrolytes. At the low concentration of tetrahexylammonium hexafluorophosphate the anion radical reduction occurs at extremely negative potentials due to the double-layer effect on the negatively charged reactant. An addition of small amounts of the alkali metal cations (Li{sup +}, Na{sup +} and K{sup +}) to such a system has a remarkable acceleration effect on the electron transfer rate since these ions undergo pairing with in situ generated anion radicals and the double-layer effect on the resulting particles of a diminished charge is much weaker. At potentials where alkali metal cations are reduced to the corresponding amalgams the acceleration ceases. As a result the current-potential curves show a negative slope. Electrochemical impedance spectroscopy sensitively indicates the presence of the negative differential charge transfer resistance (NDR). The addition of a high external resistor in series with the electrochemical cell leads to the current oscillations at the stationary mercury electrode and to the current instabilities on the dropping mercury electrode. Described system is a new example of the NDR oscillator, in which the double-layer effect in connection with cationic catalysis rather than anionic catalysis plays a crucial role in the observation of NDR.

  17. Reaction of paraquat radical cations with oxygen. A pulse radiolysis and laser photolysis study

    International Nuclear Information System (INIS)

    Patterson, L.K.; Small, R.D. Jr.; Scaiano, J.C.

    1977-01-01

    The reaction of paraquat radical cations, PQ + , with oxygen has been examined in methanol-water mixtures and in a number of other alcohols. The oxidation of PQ + by oxygen follows the kinetic expression k 1 [O 2 ][PQ + ], supporting the idea that the superoxide anion is an important intermediary in the biological behavior of paraquat and related herbicides. Changes in k 1 with variations in the methanol-water solvent mixtures were found to be largely consistent with the behavior predicted by a simple electrostatic model relating rate constants of ionization to solvent dielectric constant

  18. 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.

  19. Multihydroxy-Anthraquinone Derivatives as Free Radical and Cationic Photoinitiators of Various Photopolymerizations under Green LED.

    Science.gov (United States)

    Zhang, Jing; Hill, NicholasS; Lalevée, Jacques; Fouassier, Jean-Pierre; Zhao, Jiacheng; Graff, Bernadette; Schmidt, Timothy W; Kable, Scott H; Stenzel, Martina H; Coote, Michelle L; Xiao, Pu

    2018-04-20

    Multihydroxy-anthraquinone derivatives [i.e., 1,2,4-trihydroxyanthraquinone (124-THAQ), 1,2,7-trihydroxyanthraquinone (127-THAQ), and 1,2,5,8-tetrahydroxyanthraquinone (1258-THAQ)] can interact with various additives [e.g., iodonium salt, tertiary amine, N-vinylcarbazole, and 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine] under household green LED irradiation to generate active species (cations and radicals). The relevant photochemical mechanism is investigated using quantum chemistry, fluorescence, cyclic voltammetry, laser flash photolysis, steady state photolysis, and electron spin resonance spin-trapping techniques. Furthermore, the multihydroxy-anthraquinone derivative-based photoinitiating systems are capable of initiating cationic photopolymerization of epoxides or divinyl ethers under green LED, and the relevant photoinitiation ability is consistent with the photochemical reactivity (i.e., 124-THAQ-based photoinitiating system exhibits highest reactivity and photoinitiation ability). More interestingly, multihydroxy-anthraquinone derivative-based photoinitiating systems can initiate free radical crosslinking or controlled (i.e., reversible addition-fragmentation chain transfer) photopolymerization of methacrylates under green LED. It reveals that multihydroxy-anthraquinone derivatives can be used as versatile photoinitiators for various types of photopolymerization reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Vafiadis, Anastasios P.; Bakalbassis, Evangelos G.

    2005-01-01

    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 intra s correlate reasonably with geometrical parameters for the closed-shell, neutral counterparts, in contrast with previous estimates

  1. Toward Improved Catholyte Materials for Redox Flow Batteries: What Controls Chemical Stability of Persistent Radical Cations?

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jingjing; Shkrob, Ilya A.; Assary, Rajeev S.; Tung, Siu on [Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States; Silcox, Benjamin [Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States; Curtiss, Larry A.; Thompson, Levi [Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States; Zhang, Lu

    2017-10-16

    Catholyte materials are used to store positive charge in energized fluids circulating through redox flow batteries (RFBs) for electric grid and vehicle applications. Energy-rich radical cations (RCs) are being considered for use as catholyte materials, but to be practically relevant, these RCs (that are typically unstable, reactive species) need to have long lifetimes in liquid electrolytes under the ambient conditions. Only few families of such energetic RCs possess stabilities that are suitable for their use in RFBs; currently, the derivatives of 1,4- dialkoxybenzene look the most promising. In this study, we examine factors that define the chemical and electrochemical stabilities for RCs in this family. To this end, we engineered rigid bis-annulated molecules that by design avoid the two main degradation pathways for such RCs, viz. their deprotonation and radical addition. The decay of the resulting RCs are due to the single remaining reaction: O-dealkylation. We establish the mechanism for this reaction and examine factors controlling its rate. In particular, we demonstrate that this reaction is initiated by the nucleophile attack of the counter anion on the RC partner. The reaction proceeds through the formation of the aroxyl radicals whose secondary reactions yield the corresponding quinones. The O-dealkylation accelerates considerably when the corresponding quinone has poor solubility in the electrolyte, and the rate depends strongly on the solvent polarity. Our mechanistic insights suggest new ways of improving the RC catholytes through molecular engineering and electrolyte optimization.

  2. Lifetimes and reaction pathways of guanine radical cations and neutral guanine radicals in an oligonucleotide in aqueous solutions.

    Science.gov (United States)

    Rokhlenko, Yekaterina; Geacintov, Nicholas E; Shafirovich, Vladimir

    2012-03-14

    The exposure of guanine in the oligonucleotide 5'-d(TCGCT) to one-electron oxidants leads initially to the formation of the guanine radical cation G(•+), its deptotonation product G(-H)(•), and, ultimately, various two- and four-electron oxidation products via pathways that depend on the oxidants and reaction conditions. We utilized single or successive multiple laser pulses (308 nm, 1 Hz rate) to generate the oxidants CO(3)(•-) and SO(4)(•-) (via the photolysis of S(2)O(8)(2-) in aqueous solutions in the presence and absence of bicarbonate, respectively) at concentrations/pulse that were ∼20-fold lower than the concentration of 5'-d(TCGCT). Time-resolved absorption spectroscopy measurements following single-pulse excitation show that the G(•+) radical (pK(a) = 3.9) can be observed only at low pH and is hydrated within 3 ms at pH 2.5, thus forming the two-electron oxidation product 8-oxo-7,8-dihydroguanosine (8-oxoG). At neutral pH, and single pulse excitation, the principal reactive intermediate is G(-H)(•), which, at best, reacts only slowly with H(2)O and lives for ∼70 ms in the absence of oxidants/other radicals to form base sequence-dependent intrastrand cross-links via the nucleophilic addition of N3-thymidine to C8-guanine (5'-G*CT* and 5'-T*CG*). Alternatively, G(-H)(•) can be oxidized further by reaction with CO(3)(•-), generating the two-electron oxidation products 8-oxoG (C8 addition) and 5-carboxamido-5-formamido-2-iminohydantoin (2Ih, by C5 addition). The four-electron oxidation products, guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp), appear only after a second (or more) laser pulse. The levels of all products, except 8-oxoG, which remains at a low constant value, increase with the number of laser pulses.

  3. Relative abundances of primary ion radicals in γ-irradiated DNA: Cytosine vs thymine anions and guanine vs adenine cations

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Becker, D.; Yan, Mengyao; Summerfield, S.R.

    1991-01-01

    An ESR study of the relative distribution of ion radicals formed in DNA equilibrated with D 2 O and γ-irradiated at 77 K is presented. The ESR spectra of irradiated DNA and polynucleotides (poly[dG]·poly[dC] and poly[dAdT]·poly[dAdT]) were obtained and employed in a computer-assisted analysis for the individual ion-radical distribution. Analysis of spectra as a function of power allowed the separation of the spectra of the pyrimidine anions (T sm-bullet- , C sm-bullet- ) from the spectra of the purine cations (G sm-bullet+ , A sm-bullet+ ). The spectra of the mononucleotide ion radicals, dCMP sm-bullet- , dTMP sm-bullet- , dGMP sm-bullet+ , and dAMP sm-bullet+ , were produced in 8 M LiCl glasses. In addition, the spectra of the ion radicals of all of the mononucleotide ion radicals except dAMP + were simulated by using hyperfine and g tensors from the literature. Basis spectra derived from (1) power saturation experiments, (2) polynucleotide and mononucleotide spectra, (3) spectra of mononucleotides alone, and (4) anisotropic simulations were used to fit the spectra of DNA by use of a linear least-squares analysis. Each of the four separate analyses confirms that the cytosine anion dominates the spectra of DNA at 100 K. Three analyses included the cationic composition, and they strongly favor the guanine cation over the adenine cation. An average of the authors results gives the DNA ion radicals' relative to abundances as ca. 77% C sm-bullet- , 23% T sm-bullet- for the anions and >90% G sm-bullet+ for the cations about equal amounts of anions and cations are present. No difference in results is found for DNA irradiated in frozen D 2 O solutions or simply exchanged at 100% D 2 O humidity

  4. Accidental degeneracy in the spiropyran radical cation : charge transfer between two orthogonal rings inducing ultra-efficient reactivity

    NARCIS (Netherlands)

    Mendive-Tapia, David; Kortekaas, Luuk; Steen, Jorn D.; Perrier, Aurelie; Lasorne, Benjamin; Browne, Wesley R.; Jacquemin, Denis

    2016-01-01

    Photochromism of the spiropyran radical cation to the corresponding merocyanine form is investigated by a combination of electrochemical oxidation, UV/vis absorption spectroscopy, spectroelectrochemistry and first-principles calculations (TD-DFT, CAS-SCF and CAS-PT2). First, we demonstrate that the

  5. The First Step of the Oxidation of Elemental Sulfur: Crystal Structure of the Homopolyatomic Sulfur Radical Cation [S8].

    Science.gov (United States)

    Derendorf, Janis; Jenne, Carsten; Keßler, Mathias

    2017-07-03

    The oxidation of elemental sulfur in superacidic solutions and melts is one of the oldest topics in inorganic main group chemistry. Thus far, only three homopolyatomic sulfur cations ([S 4 ] 2+ , [S 8 ] 2+ , and [S 19 ] 2+ ) have been characterized crystallographically although ESR investigations have given evidence for the presence of at least two additional homopolyatomic sulfur radical cations in solution. Herein, the crystal structure of the hitherto unknown homopolyatomic sulfur radical cation [S 8 ] .+ is presented. The radical cation [S 8 ] .+ represents the first step of the oxidation of the S 8 molecule present in elemental sulfur. It has a structure similar to the known structure of [S 8 ] 2+ , but the transannular sulfur⋅⋅⋅sulfur contact is significantly elongated. Quantum-chemical calculations help in understanding its structure and support its presence in solution as a stable compound. The existence of [S 8 ] .+ is also in accord with previous ESR investigations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Distance dependence of hole transfer rates from G radical cations to GGG traps in DNA.

    Science.gov (United States)

    Kalosakas, G; Spanou, E

    2013-10-07

    Relative reaction rates for hole transfer between G radical cations and GGG triplets in DNA, through different bridges of varying lengths, are numerically calculated and the obtained results are compared with corresponding experimental observations [Giese et al., 2001, Nature, 412, 318; Angew. Chem., Int. Ed., 1999, 38, 996]. Hole donors and acceptors are separated either by (T-A)n bridges or by N repeated barriers consisting of (T-A,T-A) double base-pairs which are connected through single G-C base-pairs. In the former case, hole transfer rates show a strong exponential decrease with the length of the bridge for short bridges, while a switching to weak distance dependence has been observed for longer bridges. In the latter case, a power law seems to better describe the distance dependence of charge transfer rates. All these experimental observations are qualitatively reproduced by our simulations without any adjustable parameter, considering only tunneling as the charge transfer mechanism. Physical insights into the mechanism providing the switching behavior in the case of (T-A)n bridges are presented through an analysis of the eigenfunctions of the system.

  7. Metal-insulator transition of alloyed radical cation salts, (MexEDO-TTF)2PF6

    Science.gov (United States)

    Murata, Tsuyoshi; Shao, Xiangfeng; Nakano, Yoshiaki; Yamochi, Hideki; Saito, Gunzi; Uruichi, Mikio; Yakushi, Kyuya; Tanaka, Koichiro

    2010-06-01

    Ternary radical cation salts containing ethylenedioxytetrathiafulvalene, its mono-methyl substituted derivative, and hexafluorophosphate, [(EDO-TTF)1-x(MeEDO-TTF)x]2PF6 (x=mole fraction of MeEDO-TTF, x=0.01-0.13) were prepared by electrooxidation. Mole fractions of EDO-TTF and MeEDO-TTF in EDO-TTF rich alloys were consistent with the donor mixing ratios in preparation. Crystal structures of these alloys at room temperature were isostructural to that of (EDO-TTF)2PF6, where the donor molecules formed a nearly uniform stacking column to give a quasi-one-dimensional Fermi surface. The alloys exhibited a metal-insulator transition with tetramerization within the donor stack and anion-ordering. Temperature-variable structural analysis and Raman spectra revealed that the charge-ordering took place in the low temperature phase of x=0.05 alloy, however, this feature vanished in the x=0.13 alloy. The phase transition temperature decreased with increasing x value from 279 K of pristine (EDO-TTF)2PF6 to 188 K of x=0.13 alloy.

  8. Modulations of exchange coupling in oxoferrylporphyrin cation radical complexes detected by Mössbauer and EPR measurements

    Science.gov (United States)

    Bill, E.; Ding, X.-Q.; Bominaar, E. L.; Butzlaff, Ch.; Trautwein, A. X.; Mandon, D.; Weiss, R.; Gold, A.

    1992-04-01

    Oxoferrylporphyrin cation radical complexes were generated using the prophyrin dianions: tetrakis 2,6-dichlorophenyl (TDCPP) and tetrakis 2,4,6-trimethoxyphenyl (TTMPP). Spin coupling between ferryl iron (S=1) and porphyrin radical S'=1/2), ligand field interaction and hyperfine parameters of iron were studied by Mössbauer and EPR measurements and corresponding spin Hamiltonian analyses. Samples of [FeIV=0 TDCPP], which had to be prepared in CH2Cl2, were “vacuum dried” in order to obtain Mössbauer spectra.

  9. 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.

  10. ESR and electronic spectra of alkane radical cations formed in γ-irradiated 3-methylpentane and 3-methylhexane glasses containing alkane solutes

    International Nuclear Information System (INIS)

    Ichikawa, T.; Ohta, N.

    1987-01-01

    Electron spin resonance (ESR) and optical difference spectra of photobleaching are measured, and the radical cations from some higher alkanes (C 9 -C 11 ) and some methyl-branched butanes are found to be trapped in 3-methylpentane or 3-methylhexane matrices at 77 K. The ESR spectra show close agreement with those of radical cations produced in CCl 2 FCClF 2 matrices. The cations of methyl-branched butanes give the absorption bands with λ/sub max/ ranging from 300 to 260 nm and the bands are attributed to σ-localized cations, while the higher alkane cation bands appearing in the near-IR region are ascribed to σ-delocalized cations. The cations of higher alkanes are found to be mobilized by light with λ > 900 nm to recombine with the negative ions formed by electron scavenging

  11. Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 2. Preparation, dissociations, and energetics of 3-hydroxyoxolan-3-yl radical and cation.

    Science.gov (United States)

    Vivekananda, Shetty; Sadílek, Martin; Chen, Xiaohong; Adams, Luke E; Turecek, Frantisek

    2004-07-01

    The title radical (1) is generated in the gas-phase by collisional neutralization of carbonyl-protonated oxolan-3-one. A 1.5% fraction of 1 does not dissociate and is detected following reionization as survivor ions. The major dissociation of 1 (approximately 56%) occurs as loss of the hydroxyl H atom forming oxolan-3-one (2). The competing ring cleavages by O[bond]C-2 and C-4[bond]C-5 bond dissociations combined account for approximately 42% of dissociation and result in the formation of formaldehyde and 2-hydroxyallyl radical. Additional ring-cleavage dissociations of 1 resulting in the formation of C(2)H(3)O and C(2)H(4)O cannot be explained as occurring competitively on the doublet ground (X) electronic state of 1, but are energetically accessible from the A and higher electronic states accessed by vertical electron transfer. Exothermic protonation of 2 also produces 3-oxo-(1H)-oxolanium cation (3(+)) which upon collisional neutralization gives hypervalent 3-oxo-(1H)-oxolanium radical (3). The latter dissociates spontaneously by ring opening and expulsion of hydroxy radical. Experiment and calculations suggest that carbohydrate radicals incorporating the 3-hydroxyoxolan-3-yl motif will prefer ring-cleavage dissociations at low internal energies or upon photoexcitation by absorbing light at approximately 590 and approximately 400 nm.

  12. Mechanisms for radiation damage in DNA constituents and DNA: reactions of the N1-substituted thymine π-cation radicals

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Engelhardt, M.L.

    1977-01-01

    Reactions of the N 1 -substituted thymine π-cation radicals were investigated by ESR in several aqueous glasses. In 8M NaOD (NaOH) spectra suggestive and OD - (OH - ) addition to position 6 in the π-cations of 1-methylthymine, and thymidine were found immediately after uv photolysis at 77 0 K. Production of the same radicals by electron attachment to 1-methyl-5-bromo-6-hydroxythymine, and 5-bromo-6-hydroxythymidine in 8M NaOD confirms the OD - addition mechanism. Results found for these brominated compounds in 12M LiCl (D 2 O) after electron attachment show that the α 6 (H) splitting was sensitive to changes in substituents at position 1 as well as changes in environment. This variation in splitting is shown to be accounted for by small conformational changes in the radicals. In 8M NaClO 4 π-cations of the substituted thymines gave evidence for both deprotonation and OD- addition

  13. Phenothiazine Radical Cation Excited States as Super-oxidants for Energy Demanding Reactions.

    Science.gov (United States)

    Christensen, Joseph A; Phelan, Brian T; Chaudhuri, Subhajyoti; Acharya, Atanu; Batista, Victor S; Wasielewski, Michael R

    2018-03-28

    We demonstrate that the 10-phenyl-10H-phenothiazine radical cation (PTZ +• ) has a manifold of excited doublet states accessible using visible and near-infrared light that can serve as super-photooxidants with excited state potentials in excess of +2.1 V vs SCE to power energy demanding oxidation reactions. Photoexcitation of PTZ +• in CH 3 CN with a 517 nm laser pulse populates a D n electronically excited doublet state that decays first to the unrelaxed lowest electronic excited state, D 1 ' (τ < 0.3 ps), followed by relaxation to D 1 (τ = 10.9 ± 0.4 ps), which finally decays to D 0 (τ = 32.3 ± 0.8 ps). D 1 ' can also be populated directly using a lower energy 900 nm laser pulse, which results in a longer D 1 ' → D 1 relaxation time (τ = 19 ± 2 ps). To probe the oxidative power of PTZ +• photoexcited doublet states, PTZ +• was covalently linked to each of three hole acceptors, perylene (Per), 9,10-diphenylanthracene (DPA), and 10-phenyl-9-anthracenecarbonitrile (ACN), which have oxidation potentials of 1.04, 1.27, and 1.6 V vs. SCE, respectively. In all three cases, photoexcitation wavelength dependent ultrafast hole transfer occurs from D n , D 1 ', or D 1 of PTZ +• to Per, DPA, and ACN. The ability to take advantage of the additional oxidative power provided by the upper excited doublet states of PTZ +• will enable applications using this chromophore as a super-oxidant for energy demanding reactions.

  14. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  15. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  16. Combining UV photodissociation action spectroscopy with electron transfer dissociation for structure analysis of gas-phase peptide cation-radicals.

    Science.gov (United States)

    Shaffer, Christopher J; Pepin, Robert; Tureček, František

    2015-12-01

    We report the first example of using ultraviolet (UV) photodissociation action spectroscopy for the investigation of gas-phase peptide cation-radicals produced by electron transfer dissociation. z-Type fragment ions (●) Gly-Gly-Lys(+), coordinated to 18-crown-6-ether (CE), are generated, selected by mass and photodissociated in the 200-400 nm region. The UVPD action spectra indicate the presence of valence-bond isomers differing in the position of the Cα radical defect, (α-Gly)-Gly-Lys(+) (CE), Gly-(α-Gly)-Lys(+) (CE) and Gly-Gly-(α-Lys(+))(CE). The isomers are readily distinguishable by UV absorption spectra obtained by time-dependent density functional theory (TD-DFT) calculations. In contrast, conformational isomers of these radical types are calculated to have similar UV spectra. UV photodissociation action spectroscopy represents a new tool for the investigation of transient intermediates of ion-electron reactions. Specifically, z-type cation radicals are shown to undergo spontaneous hydrogen atom migrations upon electron transfer dissociation. Copyright © 2015 John Wiley & Sons, Ltd.

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

    Science.gov (United States)

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

    2009-01-01

    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 experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' β-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron nuclear double resonance or high-field ESR. This approach also produces geometric parameters (dihedral angles for the β-methylene hydrogens) which should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals. PMID:18433127

  18. 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.

  19. Structure and properties of hydrocarbon radical cations in low-temperature matrices as studied by a combination of EPR and IR spectroscopy

    International Nuclear Information System (INIS)

    Feldman, V.I.

    1997-01-01

    Use of IR spectroscopy (as a supplement to EPR) may provide new insight into the problem of analysis of structure and properties of organic radical cations. In this work, the results of combined EPR/IR studies of the formation, structure and properties of hydrocarbon radical cations in halocarbon and solid rare gas matrices are discussed. Both IR and EPR studies were carried out with matrix deposited samples irradiated with fast electrons at 15 or 77 K. IR spectroscopic data were found to be helpful in three aspects: (i) characterization of the conformation and association and molecule-matrix interactions of the parent molecules; (ii) identification of diamagnetic products of the reactions of radical cations in ground and excited states; (iii) determining the characteristics of vibrational spectra of the radical cations, which are of primary interest for analysis of chemical bonding and reactivity of the radical cations. The applications of the combined approach are illustrated with examples of studies of several alkenes in Freon matrices and alkanes in solid rare gas matrices. The matrix effects on trapping and degradation of radical cations were interpreted as the result of variations in matrix electronic characteristics (IP, polarizability) and molecule-matrix interactions. (au) 48 refs

  20. Non-photochemical Fluorescence Quenching in Photosystem II Antenna Complexes by the Reaction Center Cation Radical.

    Science.gov (United States)

    Paschenko, V Z; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Ivanov, M V; Maksimov, E G; Mamedov, M D

    2016-06-01

    efficiency for non-photochemical antenna fluorescence quenching by RC cation radical in comparison to that of photochemical quenching are discussed.

  1. Cytochrome P-450-catalyzed rearrangement of a peroxyquinol derived from butylated hydroxytoluene. Involvement of radical and cationic intermediates.

    Science.gov (United States)

    Wand, M D; Thompson, J A

    1986-10-25

    The p-peroxyquinol derived from butylated hydroxytoluene, 2,6-di-t-butyl-4-hydroperoxy-4-methyl-2,5-cyclohexadienone, was degraded by the ferric form of rat liver cytochrome P-450, and the resulting products and their mechanisms of formation were investigated. Quinoxy radical BO. from homolysis of the O-O bond reacted by competing pathways; beta-scission yielded 2,6-di-t-butyl-p-benzoquinone, and rearrangement with ring-expansion produced an oxacycloheptadienone free radical (X(.)). This rearranged radical was stabilized by the captodative effect that facilitated competitive interactions with the P-450 iron-oxo complexes formed during O-O bond scission. Approximately 15% of X(.) was captured by oxygen rebound with a hydroxyl radical from the P-450 complex (FeOH)3+ to form a hemiketal, that led to the ring-contracted product 2,5-di-t-butyl-5-(2'-oxopropyl)-4-oxa-2-cyclopentenone by spontaneous rearrangement. The major fraction of X(.), however, underwent electron transfer oxidation to form the corresponding cation. Hydration of this cation produced the ring-contracted product, and proton elimination (or, alternatively, direct H(.) removal from X(.) led to the product 2,7-di-t-butyl-4-methylene-5-oxacyclohepta-2,6-dienone. The findings indicate that cytochrome P-450 intermediate complexes are mainly responsible for oxidation of X(.). The results complement our previous study with 2,6-di-t-butyl-4-hydroperoxy-4-methyl-2,5-cyclohexadienone (Thompson, J. A., and Wand, M. D. (1985) J. Biol. Chem. 260, 10637-10644), demonstrating competitive heterolytic and homolytic mechanisms of O-O bond cleavage, and competitive rebound and oxidation processes when a substrate-derived radical interacts with P-450 complexes.

  2. On the intrinsic optical absorptions by tetrathiafulvalene radical cations and isomers

    DEFF Research Database (Denmark)

    Kirketerp, Maj-Britt Suhr; Leal, Leonardo Andrés Espinosa; Varsano, Daniele

    2011-01-01

    Gas-phase action spectroscopy shows unambiguously that the low-energy absorptions by tetramethylthiotetrathiafulvalene and tetrathianaphthalene cations in solution phase are due to monomers and not π-dimers....

  3. Gas-Phase Intercluster Thiyl-Radical Induced C-H Bond Homolysis Selectively Forms Sugar C2-Radical Cations of Methyl D-Glucopyranoside: Isotopic Labeling Studies and Cleavage Reactions

    Science.gov (United States)

    Osburn, Sandra; Speciale, Gaetano; Williams, Spencer J.; O'Hair, Richard A. J.

    2017-07-01

    A suite of isotopologues of methyl D-glucopyranosides is used in conjunction with multistage mass spectrometry experiments to determine the radical site and cleavage reactions of sugar radical cations formed via a recently developed `bio-inspired' method. In the first stage of CID (MS2), collision-induced dissociation (CID) of a protonated noncovalent complex between the sugar and S-nitrosocysteamine, [H3NCH2CH2SNO + M]+, unleashes a thiyl radical via bond homolysis to give the noncovalent radical cation, [H3NCH2CH2S• + M]+. CID (MS3) of this radical cation complex results in dissociation of the noncovalent complex to generate the sugar radical cation. Replacement of all exchangeable OH and NH protons with deuterons reveals that the sugar radical cation is formed in a process involving abstraction of a hydrogen atom from a C-H bond of the sugar coupled with proton transfer to the sugar, to form [M - H• + D+]. Investigation of this process using individual C-D labeled sugars reveals that the main site of H/D abstraction is the C2 position, since only the C2-deuterium labeled sugar yields a dominant [M - D• + H+] product ion. The fragmentation reactions of the distonic sugar radical cation, [M - H•+ H+], were studied by another stage of CID (MS4). 13C-labeling studies revealed that a series of three related fragment ions each contain the C1-C3 atoms; these arise from cross-ring cleavage reactions of the sugar.

  4. Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

    Science.gov (United States)

    Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

    2011-01-01

    Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

  5. ENDOR and ESEEM of the 15N labelled radical cations of chlorophyll a and the primary donor P 700 in photosystem I

    Science.gov (United States)

    Käβ, H.; Bittersmann-Weidlich, E.; Andréasson, L.-E.; Bönigk, B.; Lubitz, W.

    1995-05-01

    The hyperfine couplings of the nitrogen nuclei in the radical cations of both 15N-labelled chlorophyll a and the primary donor P 700 in Photosystem I of Synechococcus elongatus and spinach ( Spinacea oleracea) in frozen solutions were investigated by ENDOR and, for confirmation, by two-dimensional ESEEM techniques. In addition, 1H ENDOR experiments were performed on these compounds. The experimental 15N hyperfine couplings of the chlorophyll a radical cation are compared with theoretical ones obtained by RHF-INDO/SP calculations and with the respective hyperfine couplings in the closely related 15N-bacteriochlorophyll a radical cation. Based on the observed 15N and 1H hyperfine couplings two possible models are discussed for P 700+: (a) the special pair model with a strongly asymmetric spin density distribution over the dimer halves; (b) the model of a strongly perturbed chlorophyll a monomer.

  6. Electrochemistry and electrogenerated chemiluminescence of dithienylbenzothiadiazole derivative. Differential reactivity of donor and acceptor groups and simulations of radical cation-anion and dication-radical anion annihilations.

    Science.gov (United States)

    Shen, Mei; Rodríguez-López, Joaquín; Huang, Ju; Liu, Quan; Zhu, Xu-Hui; Bard, Allen J

    2010-09-29

    We report here the electrochemistry and electrogenerated chemiluminescence (ECL) of a red-emitting dithienylbenzothiadiazole-based molecular fluorophore (4,7-bis(4-(4-sec-butoxyphenyl)-5-(3,5-di(1-naphthyl)phenyl)thiophen-2-yl)-2,1,3-benzothiadiazole, 1b). 1b contains two substituted thiophene groups as strong electron donors at the ends connected directly to a strong electron acceptor, 2,1,3-benzothiadiazole, in the center. Each thiophene moiety is substituted in position 2 by 3,5-di(1-naphthyl)phenyl and in position 3 by 4-sec-butoxyphenyl. Cyclic voltammetry of 1b, with scan rate ranging from 0.05 to 0.75 V/s, shows a single one-electron reduction wave (E°(red) = -1.18 V vs SCE) and two nernstian one-electron oxidation waves (E°(1,ox) = 1.01 V, E°(2,ox) = 1.24 V vs SCE). Reduction of the unsubstituted 2,1,3-benzothiadiazole center shows nernstian behavior with E°(red) = -1.56 V vs SCE. By comparison to a digital simulation, the heterogeneous electron-transfer rate constant for reduction, k(r)° = 1.5 × 10(-3) cm/s, is significantly smaller than those for the oxidations, k(o)° > 0.1 cm/s, possibly indicating that the two substituted end groups have a blocking effect on the reduction of the benzothiadiazole center. The ECL spectrum, produced by electron-transfer annihilation of the reduced and oxidized forms, consists of a single peak with maximum emission at about 635 nm, consistent with the fluorescence of the parent molecule. Relative ECL intensities with respect to 9,10-diphenylanthracene are 330% and 470% for the radical anion-cation and radical anion-dication annihilation, respectively. Radical anion (A(-•))-cation (A(+•)) annihilation produced by potential steps shows symmetric ECL transients during anodic and cathodic pulses, while for anion (A(-•))-dication (A(2+•)) annihilation, transient ECL shows asymmetry in which the anodic pulse is narrower than the cathodic pulse. Digital simulation of the transient ECL experiments showed that the

  7. Association of alkali and alkaline earth metal cations with radical-anions of 9-fluorenone and 9.10-anthraquinone in dimethyl formamide medium

    International Nuclear Information System (INIS)

    Karpinets, A.P.; Bezuglyj, V.D.; Svetlichnaya, T.M.

    1988-01-01

    The polarographic method is used to estimate the stability of associates formed in dimethyl formamide by the products of one-electron reduction of 9-fluorenone and 9.10-anthraquinone with cations of alkali and alkali earth metals. It is shown that the strength of 9-fluorenone and 9.10-anthraquinone radical anion associates studied increases with cation charge increase and decrease of its crystallographic radius

  8. Bleaching threshold of cationic radicals of alkanes and capture energy of the positive hole of these ions in irradiated solid matrix

    International Nuclear Information System (INIS)

    Van den Bosch, A.; Strobbe, M.; Ceulemans, J.

    1984-01-01

    Gamma irradiated Cl 3 CCF 3 shows an absorption band at about 360 nm, and another band, at 600 nm. The band at 600 nm disappears completely by irradiation with light of lambda>610 nm. Cl 3 CCF 3 containing 1% of decane irradiated at 77 K presents the some phenomena. Selective bleaching by photons of increasing energy allows the determination of the threshold for bleaching of cationic radicals of decane trapped in Cl 3 CCF 3 . Distinction between photoinduced charge transfer and photodissociation is obtained by addition of tetramethyl-p-phenylenediame. Showing that bleaching threshold corresponds to the capture energy of the positive hole on decane cationic radical [fr

  9. Acid-catalyzed disproportionation of oxoiron(IV) porphyrins to give oxoiron(IV) porphyrin radical cations.

    Science.gov (United States)

    Pan, Zhengzheng; Newcomb, Martin

    2011-06-01

    Disproportionation of oxoiron(IV) porphyrin (Compound II) to oxoiron(IV) porphyrin radical cation (Compound I) was studied in three P450 model systems with different electronic structures. Direct conversion of Compound II to Compound I has been observed for 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (TDCPP) in acid-catalyzed reactions in a mixed solvent of acetonitrile and water (1:1, v/v) containing excess m-CPBA oxidant, with a second-order rate constant of (1.3 ± 0.2) × 10(2) M(-1) s(-1). The acid-catalyzed disproportionation heavily depends on the electron demand of the substituted aryl groups on the porphyrin macrocycle. The disproportionation equilibrium constants show drastic change for the three porphyrin systems.

  10. Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

    Energy Technology Data Exchange (ETDEWEB)

    Mathavan, T., E-mail: tjmathavan@gmail.com; Divya, A.; Benial, A. Milton Franklin [PG & Research Department of Physics, N.M.S.S.Vellaichamy Nadar College, Madurai-625 019 (India); Archana, J. [Research Institute of Engineering, Shizuoka University (Japan); Ramasubbu, A. [PG & Research Department of Chemistry, Govt. Arts College, Coimbatore (India); Jothirajan, M. A. [Research Department of Physics, Arul Anandar College, Karumathur, Madurai-625 514 (India)

    2016-05-23

    Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

  11. Synthesis, Physical Properties and Reactivity of Stable Antiaromatic 1,4-DIHYDROPYRAZINES and Their Associated Radical Cations

    Science.gov (United States)

    Brook, David James Rawsthorne

    Self condensation of 3-(chloromethyl)-5,6-dihydro -5,5-dimethyl oxazin-2-one and 3-(chloromethyl)-5,6-dihydro -1,5, 5-trimethylpyrazin-2-one gave the 1,4-dihydropyrazines, 4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro- 4,4,8,8 -tetramethylanthracene-1,5,-dione (DDTTA), and 2,4,4,6,8,8-hexamethyl-2,4a,6,8a-tetraaza - 3,4,7,8-tetrahydroanthracene-1,5-dione (HTTA), respectively. Extension of this reaction to other systems resulted in failure. Thionation of DDTTA with phosphorus pentasulphide in pyridine gave mono and dithiono ester derivatives. The dihydropyrazine rings of these systems were planar and showed long wavelength pi-pi^* electronic absorption resulting in the compounds being coloured. The long wavelength band showed significant solvatochromism. NMR measurements indicated that the rings are also paratropic. DDTTA, HTTA and the thiones all showed reversible one electron oxidation to the radical cation which was characterised by electron spin resonance spectroscopy. HTTA and DDTTA also showed reversible oxidation of the radical cation to the dication. Hydrogenation of DDTTA resulted in a tetrahydropyrazine derivative, 4a,8a-diaza-2,6-dioxa -3,4,7,8,9,9a-hexahydro- 4,4,8,8-tetramethylanthracene -1,5-dione (4.5), which underwent atmospheric oxidation back to DDTTA and the alcohol 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a -hexahydro-9a-hydroxy- 4,4,8,8-tetramethylanthracene -1,5-dione (4.6). The HTTA analogue 2,4,4,6,8,8-hexamethyl -3,4,7,8,9,9a-hexahydro- 2,4a,6,8a-tetraazaanthracene -1,5-dione (4.9) is stable under the same conditions. The difference in behaviour was explained as a result of the captodative effect. DDTTA was found to undergo rapid (2 + 2) cycloaddition to the dienophile, 4-phenyl-1,2,4-triazoline -3,5-dione (PTAD). Reaction of DDTTA with ^ {3}O_{2} was found to be solvent dependent. In acetic acid the dioxetane 4a,8a-diaza-2,6-dioxa-9,9a-epidioxy-3,4,7,8,9,9a -hexahydro- 4,4,8,8-tetramethylanthracene -1,5-dione was observed; whereas, in acetonitrile

  12. Study of transitory forms of carotenoids

    International Nuclear Information System (INIS)

    Mathis, Paul

    1970-01-01

    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 3 Car. - This state (t 1/2 ∼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 3 Car 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 + (t 1/2 ∼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) [fr

  13. Infrared and electronic spectroscopy of benzene-ammonia cluster radical cations [C(6)H(6)(NH(3))(1,2)](+): observation of isolated and microsolvated σ-complexes.

    Science.gov (United States)

    Mizuse, Kenta; Hasegawa, Hayato; Mikami, Naohiko; Fujii, Asuka

    2010-10-28

    We report infrared (IR) and electronic spectra of benzene-ammonia cluster radical cations [C(6)H(6)(NH(3))(n)](+) (n = 1 and 2) in the gas phase to explore cluster structures and chemical reactivity of the simplest aromatic radical cation with base (nucleophile) molecules. The electronic spectra in the visible region indicate that these cluster cations no longer have the benzene cation chromophore as a result of an intracluster reaction. Analyses of the IR spectra, on the basis quantum chemical calculations and the vibration-internal rotation analysis, reveal that both [C(6)H(6)(NH(3))(1,2)](+) form σ-complex structures, in which the ammonia moiety is covalently bonded to the benzene moiety due to the intracluster nucleophilic addition. For [C(6)H(6)(NH(3))(2)](+), it is also shown that the second ammonia molecule solvates the σ-complex core via a N-H···N hydrogen bond. Such σ-complex structures are generally supposed to be a key intermediate of aromatic substitution reactions. The observed mass spectra and energetics calculations, however, show that [C(6)H(6)(NH(3))(n)](+) systems are inert for aromatic substitutions. The present experimental observations indicate the inherent stability of these σ-complex structures, even though they do not show the aromatic substitution reactivity.

  14. Conserving Coherence and Storing Energy during Internal Conversion: Photoinduced Dynamics of cis- and trans-Azobenzene Radical Cations

    KAUST Repository

    Munkerup, Kristin

    2017-10-24

    Light harvesting via energy storage in azobenzene has been a key topic for decades, and the process of energy distribution over the molecular degrees of freedom following photoexcitation remains to be understood. Dynamics of a photoexcited system can exhibit high degrees of non-ergodicity when it is driven by just a few degrees of freedom. Typically, an internal conversion leads to the loss of such localization of dynamics, as the intramolecular energy becomes statistically redistributed over all molecular degrees of freedom. Here, we present a unique case where the excitation energy remains localized even subsequent to internal conversion. Strong-field ionization is used to prepare cis- and trans-azobenzene radical cations on the D1 surface with little excess energy, at the equilibrium neutral geometry. These D1 ions are preferably formed because in this case D1 and D0 switch place in the presence of the strong laser field. The post-ionization dynamics is dictated by the potential energy landscape. The D1 surface is steep downhill along the cis/trans isomerization coordinate and towards a common minimum shared by the two isomers in the region of D1/D0 conical intersection. Coherent cis/trans torsional motion along this coordinate is manifested in the ion transients by a cosine modulation. In this scenario, D0 becomes populated with molecules that are energized mainly along the cis-trans isomerization coordinate, with the kinetic energy above the cis-trans inter-conversion barrier. These activated azobenzene molecules easily cycle back and forth along the D0 surface, and give rise to several periods of modulated signal before coherence is lost. This persistent localization of the internal energy during internal conversion is provided by the steep downhill potential energy surface, small initial internal energy content, and a strong hole-lone pair interaction that drives the molecule along the cis-trans isomerization coordinate to facilitate the transition between

  15. Picosecond pulse radiolysis of highly concentrated sulfuric acid solutions: evidence for the oxidation reactivity of radical cation H2O(•+).

    Science.gov (United States)

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2014-06-12

    Aqueous solution of sulfuric acid is used as a suitable system to investigate the reactivity of the short-lived radical cation H2O(•+) which is generated by radiation in water. Ten aqueous solutions containing sulfuric acid with concentration from 1 to 18 mol L(-1) are studied by picosecond pulse radiolysis. The absorbance of the secondary radical SO4(•-) (or HSO4(•)) formed within the 10 ps electron pulse is measured by a pulse-probe method in the visible range. The analysis of the kinetics show that the radicals of sulfuric acid are formed within the picosecond electron pulse via two parallel mechanisms: direct electron detachment by the electron pulse and oxidation by the radical cation of water H2O(•+). In highly concentrated solution when SO4(2-) is in contact with H2O(•+), the electron transfer becomes competitive against proton transfer with another water molecule. Therefore, H2O(•+) may act as an extremely strong oxidant. The maximum radiolytic yield of scavenged H2O(•+) is estimated to be 5.3 ± 0.1 × 10(-7) mol J(-1).

  16. A comprehensive test set of epoxidation rate constants for iron(iv)-oxo porphyrin cation radical complexes.

    Science.gov (United States)

    Sainna, Mala A; Kumar, Suresh; Kumar, Devesh; Fornarini, Simonetta; Crestoni, Maria Elisa; de Visser, Sam P

    2015-02-01

    -set of experimental reaction rates of iron(iv)-oxo porphyrin cation radical complexes, so far unprecedented in the gas-phase, providing a benchmark for calibration studies using computational techniques. Preliminary computational results presented here confirm the observed trends excellently and rationalize the reactivities within the framework of thermochemical considerations and valence bond schemes.

  17. [Carotenoids: 1. Metabolism and physiology].

    Science.gov (United States)

    Faure, H; Fayol, V; Galabert, C; Grolier, P; Le Moël, G; Steghens, J P; Van Kappel, A; Nabet, F

    1999-01-01

    Carotenoids are a family of pigments with at least 600 members. They derive from lycopene after steps of cyclisation, dehydrogenation and oxidation. It is their chemical structure that determines their physiochemical properties and, in part, their biological activities. About 50 carotenoids can be found in human diet and about 20 of them have been found in plasma and tissues. There is no RDA (Recommended Daily Allowance) for carotenoids. Quantities of carotenoids in diet are difficult to estimate, partly because methods used for the establishment of food composition tables were not specific and sensitive enough. Also, given values do not always take into account variations due to season and region of culture. Absorption of beta-carotene in humans has been the subject of numerous studies but only very little is known about other carotenoids. In general, absorption depends on bioavailability from the food matrix and solubility in micelles. After absorption through passive diffusion, carotenoids follow the chylomicrons metabolism. They are taken up by the liver and released in the blood stream in lipoproteins (VLDL). Carotenoids with no-substituted beta-ionone cycles (alpha and beta-carotene and beta-cryptoxanthin) have provitamin A activity. Highest activity has been found for all-trans beta-carotene. Not all steps of vitamin A biosynthesis and metabolism of other carotenoids have been clarified yet. Besides their provitamin A activity, carotenoids have numerous biological functions. They are efficient scavengers of free radicals, particularly of 1O2. In vitro they have been shown to protect LDL. However, results in vivo are inconsistent. Other functions include enhancement of gap junctions, immunomodulation and regulation of enzyme activity involved in carcinogenesis.

  18. A selective stepwise heme oxygenase model system: an iron(IV)-oxo porphyrin π-cation radical leads to a verdoheme-type compound via an isoporphyrin intermediate.

    Science.gov (United States)

    Garcia-Bosch, Isaac; Sharma, Savita K; Karlin, Kenneth D

    2013-11-06

    The selective oxidation of the α-position of two heme-Fe(III) tetraarylporphryinate complexes occurs when water(hydroxide) attacks their oxidized Cmpd I-type equivalents, high-valent Fe(IV)═O π-cation radical species ((P(+•))Fe(IV)═O). Stepwise intermediate formation occurs, as detected by UV-vis spectroscopic monitoring or mass spectrometric interrogation, being iron(III) isoporphyrins, iron(III) benzoyl-biliverdins, and the final verdoheme-like products. Heme oxygenase (HO) enzymes could proceed through heterolytic cleavage of an iron(III)-hydroperoxo intermediate to form a transient Cmpd I-type species.

  19. 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.

  20. Cytosine Radical Cations: A Gas-Phase Study Combining IRMPD Spectroscopy, UVPD Spectroscopy, Ion-Molecule Reactions, and Theoretical Calculations

    Czech Academy of Sciences Publication Activity Database

    Lesslie, M.; Lawler, J. T.; Dang, A.; Korn, J. A.; Bím, Daniel; Steinmetz, V.; Maitre, P.; Tureček, F.; Ryzhov, V.

    2017-01-01

    Roč. 18, č. 10 (2017), s. 1293-1301 ISSN 1439-4235 Institutional support: RVO:61388963 Keywords : ion- molecule reactions * IRMPD spectroscopy * nucleobases * radical ions * UVPD spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.075, year: 2016

  1. Oxidation of guanine in G, GG, and GGG sequence contexts by aromatic pyrenyl radical cations and carbonate radical anions: relationship between kinetics and distribution of alkali-labile lesions.

    Science.gov (United States)

    Lee, Young Ae; Durandin, Alexander; Dedon, Peter C; Geacintov, Nicholas E; Shafirovich, Vladimir

    2008-02-14

    Oxidatively generated DNA damage induced by the aromatic radical cation of the pyrene derivative 7,8,9,10-tetrahydroxytetrahydrobenzo[a]pyrene (BPT), and by carbonate radicals anions, was monitored from the initial one-electron transfer, or hole injection step, to the formation of hot alkali-labile chemical end-products monitored by gel electrophoresis. The fractions of BPT molecules bound to double-stranded 20-35-mer oligonucleotides with noncontiguous guanines G and grouped as contiguous GG and GGG sequences were determined by a fluorescence quenching method. Utilizing intense nanosecond 355 nm Nd:YAG laser pulses, the DNA-bound BPT molecules were photoionized to BPT*+ radicals by a consecutive two-photon ionization mechanism. The BPT*+ radicals thus generated within the duplexes selectively oxidize guanine by intraduplex electron-transfer reactions, and the rate constants of these reactions follow the trend 5'-..GGG.. > 5'-..GG.. > 5'-..G... In the case of CO3*- radicals, the oxidation of guanine occurs by intermolecular collision pathways, and the bimolecular rate constants are independent of base sequence context. However, the distributions of the end-products generated by CO3*- radicals, as well as by BPT*+, are base sequence context-dependent and are greater than those in isolated guanines at the 5'-G in 5'-...GG... sequences, and the first two 5'- guanines in the 5'-..GGG sequences. These results help to clarify the conditions that lead to a similar or different base sequence dependence of the initial hole injection step and the final distribution of oxidized, alkali-labile guanine products. In the case of the intermolecular one-electron oxidant CO3*-, the rate constant of hole injection is similar for contiguous and isolated guanines, but the subsequent equilibration of holes by hopping favors trapping and product formation at contiguous guanines, and the sequence dependence of these two phenomena are not correlated. In contrast, in the case of the DNA

  2. 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

    2016-02-23

    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.

  3. Nucleophilic Aromatic Addition in Ionizing Environments: Observation and Analysis of New C-N Valence Bonds in Complexes between Naphthalene Radical Cation and Pyridine.

    Science.gov (United States)

    Peverati, Roberto; Platt, Sean P; Attah, Isaac K; Aziz, Saaudallah G; El-Shall, M Samy; Head-Gordon, Martin

    2017-08-30

    Radical organic ions can be stabilized by complexation with neutral organics via interactions that can resemble chemical bonds, but with much diminished bond energies. Those interactions are a key factor in cluster growth and polymerization reactions in ionizing environments such as regions of the interstellar medium and solar nebulae. Such radical cation complexes between naphthalene (Naph) and pyridine (Pyr) are characterized using mass-selected ion mobility experiments. The measured enthalpy of binding of the Naph +• (Pyr) heterodimer (20.9 kcal/mol) exceeds that of the Naph +• (Naph) homodimer (17.8 kcal/mol). The addition of 1-3 more pyridine molecules to the Naph +• (Pyr) heterodimer gives 10-11 kcal/mol increments in binding enthalpy. A rich array of Naph +• (Pyr) isomers are characterized by electronic structure calculations. The calculated Boltzmann distribution at 400 K yields an enthalpy of binding in reasonable agreement with experiment. The global minimum is a distonic cation formed by Pyr attack on Naph +• at the α-carbon, changing its hybridization from sp 2 to distorted sp 3 . The measured collision cross section in helium for the Naph +• (Pyr) heterodimer of 84.9 ± 2.5 Å 2 at 302 K agrees well with calculated angle-averaged cross sections (83.9-85.1 Å 2 at 302 K) of the lowest energy distonic structures. A remarkable 16 kcal/mol increase in the binding energy between Naph +• (Pyr) and Bz +• (Pyr) (Bz is benzene) is understood by energy decomposition analysis. A similar increase in binding from Naph +• (NH 3 ) to Naph +• (Pyr) (as well as between Bz +• (NH 3 ) and Bz +• (Pyr)) is likewise rationalized.

  4. 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.

  5. Functional properties of carotenoids originating from algae.

    Science.gov (United States)

    Christaki, Efterpi; Bonos, Eleftherios; Giannenas, Ilias; Florou-Paneri, Panagiota

    2013-01-15

    Carotenoids are isoprenoid molecules which are synthesised de novo by photosynthetic plants, fungi and algae and are responsible for the orange, yellow and some red colours of various fruits and vegetables. Carotenoids are lipophilic compounds, some of which act as provitamins A. These compounds can be divided into xanthophylls and carotenes. Many macroalgae and microalgae are rich in carotenoids, where these compounds aid in the absorption of sunlight. Industrially, these carotenoids are used as food pigments (in dairy products, beverages, etc.), as feed additives, in cosmetics and in pharmaceuticals, especially nowadays when there is an increasing demand by consumers for natural products. Production of carotenoids from algae has many advantages compared to other sources; for example, their production is cheap, easy and environmentally friendly; their extraction is easier, with higher yields, and there is no lack of raw materials or limited seasonal variation. Recently, there has been considerable interest in dietary carotenoids with respect to their antioxidant properties and their ability to reduce the incidence of some chronic diseases where free radicals are involved. Possibly, carotenoids protect cells from oxidative stress by quenching singlet oxygen damage with various mechanisms. Therefore, carotenoids derived from algae could be a leading natural resource in the research for potential functional ingredients. Copyright © 2012 Society of Chemical Industry.

  6. Investigation into the potential chemical mechanism of the pro-oxidant activity of carotenoids with liposomes under UV-irradiation

    Directory of Open Access Journals (Sweden)

    Cvetković Dragan J.

    2017-01-01

    Full Text Available This study focuses on the behavior of β-carotene and lutein inside multilamellar liposomes under continuous UV-irradiation. The liposomes were obtained by the thin film method and carotenoids (Crts were incorporated by mixing at various concentrations (0.005, 0.0075, 0.02, 0.07 and 0.5 mol %. Liposomes formation and the presence of Crts inside them were confirmed by SEM microscopy and FT-IR spectroscopy, respectively. The antioxidant/pro- -oxidant activity of Crts inside liposomes was determined by the thiobarbituric acid–malondialdehyde (TBA–MDA test. The investigated Crts acted more or less unexpected (as pro-oxidants inside the lipid bilayers, interacting with the UV-produced lipid radicals and simultaneously suffering under the UV-irradiation. Their pro-oxidant activity with liposomes and under UV-irradiation could be explained by the formation of unstable adducts in the reaction with peroxyl radicals, or by Crts-cation radicals formation via the electron transfer mechanism. Such tentatively unexpected behavior of carotenoids should be taken into consideration in further carotenoids-based UV-filters projections in cosmetic formulations for skin protection. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. TR-34012

  7. 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. This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in...

  8. Certain aspects of the reactivity of carotenoids. Redox processes and complexation

    International Nuclear Information System (INIS)

    Polyakov, Nikolay E; Leshina, Tatyana V

    2006-01-01

    The published data on the redox reactions of carotenoids, their supramolecular inclusion complexes and the composition, properties and practical application of these complexes are generalised. Special attention is given to the effect of complexation on radical processes involving carotenoids and on the antioxidant activity of carotenoids.

  9. Five Electronic State Beyond Born-Oppenheimer Equations and Their Applications to Nitrate and Benzene Radical Cation.

    Science.gov (United States)

    Mukherjee, Soumya; Mukherjee, Bijit; Adhikari, Satrajit

    2017-08-24

    We present explicit form of Adiabatic to Diabatic Transformation (ADT) equations and expressions of non-adiabatic coupling terms (NACTs) for a coupled five-state electronic manifold in terms of ADT angles between electronic wave functions. ADT matrices eliminate the numerical instability arising from singularity of NACTs and transform the adiabatic Schrödinger equation to its diabatic form. Two real molecular systems NO 3 and C 6 H 6 + (Bz + ) are selectively chosen for the demonstration of workability of those equations. We examine the NACTs among the lowest five electronic states of the NO 3 radical [X̃ 2 A 2 ' (1 2 B 2 ), Ã 2 E″ (1 2 A 2 and 1 2 B 1 ) and B̃ 2 E' (1 2 A 1 and 2 2 B 2 )], in which all types of non-adiabatic interactions, that is, Jahn-Teller (JT) interactions, Pseudo Jahn-Teller (PJT) interactions, and accidental conical intersections (CIs) are present. On the other hand, lowest five electronic states of Bz + [X̃ 2 E 1g (1 2 B 3g and 1 2 B 2g ), B̃ 2 E 2g (1 2 A g and 1 2 B 1g ), and C̃ 2 A 2u (1 2 B 1u )] depict similar kind of complex feature of non-adiabatic effects. For NO 3 radical, the two components of degenerate in-plane asymmetric stretching mode are taken as a plane of nuclear configuration space (CS), whereas in case of Bz + , two pairs are chosen: One is the pair of components of degenerate in-plane asymmetric stretching mode, and the other one is constituted with one of the components each from out-of-plane degenerate bend and in-plane degenerate asymmetric stretching modes. We calculate ab initio adiabatic potential energy surfaces (PESs) and NACTs among the lowest five electronic states at the CASSCF level using MOLPRO quantum chemistry package. Subsequently, the ADT is performed using those newly developed equations to validate the positions of the CIs, evaluate the ADT angles and construct smooth, symmetric, and continuous diabatic PESs for both the molecular systems.

  10. Observation of covalent and electrostatic bonds in nitrogen-containing polycyclic ions formed by gas phase reactions of the benzene radical cation with pyrimidine.

    Science.gov (United States)

    Attah, Isaac Kwame; Soliman, Abdel-Rahman; Platt, Sean P; Meot-Ner Mautner, Michael; Aziz, Saaudallah G; Samy El-Shall, M

    2017-03-01

    Polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocyclics (PANHs) are present in ionizing environments, including interstellar clouds and solar nebulae, where their ions can interact with neutral PAH and PANH molecules leading to the formation of a variety of complex organics including large N-containing ions. Herein, we report on the formation of a covalently-bonded (benzene·pyrimidine) radical cation dimer by the gas phase reaction of pyrimidine with the benzene radical cation at room temperature using the mass-selected ion mobility technique. No ligand exchange reactions with benzene and pyrimidine are observed indicating that the binding energy of the (benzene·pyrimidine)˙ + adduct is significantly higher than both the benzene dimer cation and the proton-bound pyrimidine dimer. The (benzene·pyrimidine)˙ + adduct shows thermal stability up to 541 K. Thermal dissociation of the (C 6 D 6 ·C 4 H 4 N 2 )˙ + adduct at temperatures higher than 500 K produces C 4 H 4 N 2 D + (m/z 82) suggesting the transfer of a D atom from the C 6 D 6 moiety to the C 4 H 4 N 2 moiety before the dissociation of the adduct. Mass-selected ion mobility of the (benzene·pyrimidine)˙ + dimer reveals the presence of two families of isomers formed by electron impact ionization of the neutral (benzene·pyrimidine) dimer. The slower mobility peak corresponds to a non-covalent family of isomers with larger collision cross sections (76.0 ± 1.8 Å 2 ) and the faster peak is consistent with a family of covalent isomers with more compact structures and smaller collision cross sections (67.7 ± 2.2 Å 2 ). The mobility measurements at 509 K show only one peak corresponding to the family of stable covalently bonded isomers characterized by smaller collision cross sections (66.9 ± 1.9 Å 2 at 509 K). DFT calculations at the M06-2X/6-311++G** level show that the most stable (benzene·pyrimidine)˙ + isomer forms a covalent C-N bond with a binding energy of 49

  11. 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...

  12. Carotenoids in Marine Animals

    Science.gov (United States)

    Maoka, Takashi

    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 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. PMID:21566799

  13. Enhanced biological activity of carotenoids stabilized by phenyl groups.

    Science.gov (United States)

    You, Ji Suk; Jeon, Sunhwa; Byun, Youn Jung; Koo, Sangho; Choi, Shin Sik

    2015-06-15

    Carotenoids are lipid soluble food ingredients with multifunction including antioxidant and anticancer activities. However, carotenoids are destructively oxidized upon reaction with radicals resulting in toxic effects on biological systems. Two synthetic carotenoids (BAS and BTS) containing the aromatic phenyl groups with a para-substituent (OMe and Me, respectively) at C-13 and C-13' position were prepared in order to overcome a structural instability of carotenoid. Both BAS and BTS exerted stronger radical scavenging activity than β-carotene in DPPH and ABTS assays. In particular, BTS significantly reduced in vivo ROS (reactive oxygen species) levels and improved body growth and reproduction of Caenorhabditiselegans. BTS has a great potential for the advanced and modified carotenoid material with stability leading to enhanced bioavailability. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Carotenoids in Marine Animals

    OpenAIRE

    Maoka, Takashi

    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...

  15. 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

  16. 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.

  17. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

    Directory of Open Access Journals (Sweden)

    Samuel Hernández Anzaldo

    2016-06-01

    Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  18. Notable effects of metal salts on UV-vis absorption spectra of α-, β-, γ-, and δ-tocopheroxyl radicals in acetonitrile solution. The complex formation between tocopheroxyls and metal cations.

    Science.gov (United States)

    Mukai, Kazuo; Kohno, Yutaro; Ouchi, Aya; Nagaoka, Shin-ichi

    2012-08-02

    The measurements of the UV-vis absorption spectra of α-, β-, γ-, and δ-tocopheroxyl (α-, β-, γ-, and δ-Toc(•)) radicals were performed by reacting aroxyl (ArO(•)) radical with α-, β-, γ-, and δ-tocopherol (α-, β-, γ-, and δ-TocH), respectively, in acetonitrile solution including three kinds of alkali and alkaline earth metal salts (LiClO(4), NaClO(4), and Mg(ClO(4))(2)) (MX or MX(2)), using stopped-flow spectrophotometry. The maximum wavelengths (λ(max)) of the absorption spectra of the α-, β-, γ-, and δ-Toc(•) located at 425-428 nm without metal salts increased with increasing concentrations of metal salts (0-0.500 M) in acetonitrile and approached some constant values, suggesting (Toc(•)···M(+) (or M(2+))) complex formations. Similarly, the values of the apparent molar extinction coefficient (ε(max)) increased drastically with increasing concentrations of metal salts in acetonitrile and approached some constant values. The result suggests that the formations of Toc(•) dimers were suppressed by the metal ion complex formations of Toc(•) radicals. The stability constants (K) were determined for Li(+), Na(+), and Mg(2+) complexes of α-, β-, γ-, and δ-Toc(•). The K values increased in the order of NaClO(4) metal salt. The alkali and alkaline earth metal salts having a smaller ionic radius of the cation and a larger charge of the cation gave a larger shift of the λ(max) value, a larger ε(max) value, and a larger K value. The result of the DFT molecular orbital calculations indicated that the α-, β-, γ-, and δ-Toc(•) radicals were stabilized by the (1:1) complex formation with metal cations (Li(+), Na(+), and Mg(2+)). Stabilization energy (E(S)) due to the complex formation increased in the order of Na(+) complexes, being independent of the kinds of Toc(•) radicals. The calculated result also indicated that the metal cations coordinate to the O atom at the sixth position of α-, β-, γ-, and δ-Toc(•) radicals.

  19. 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.

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

    Science.gov (United States)

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

    2015-09-30

    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.

  1. New Horizons in Cationic Photopolymerization

    Directory of Open Access Journals (Sweden)

    Marco Sangermano

    2018-01-01

    Full Text Available In this review, we report some recent advances and new horizons in UV-induced cationic photopolymerization. In particular, after a brief introduction on the discovery and affirmation of the cationic photopolymerization process, new efforts in the synthesis of cationic photoinitiators are reported. Subsequently, an interesting and absolutely new application is reported, related to the combination of Radical-Induced Cationic Photopolymerization with Frontal Polymerization, achieving the cross-linking of epoxy composites.

  2. Surface functionalized SiO2nanoparticles with cationic polymers via the combination of mussel inspired chemistry and surface initiated atom transfer radical polymerization: Characterization and enhanced removal of organic dye.

    Science.gov (United States)

    Huang, Qiang; Liu, Meiying; Mao, Liucheng; Xu, Dazhuang; Zeng, Guangjian; Huang, Hongye; Jiang, Ruming; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-08-01

    Monodispersed SiO 2 particles functionalized with cationic polymers poly-((3-acrylamidopropyl)trimethylammonium chloride) (PAPTCl) were prepared using mussel inspired surface modification strategy and surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, X-ray photoelectron spectroscopy, and zeta potential were employed to characterize these SiO 2 samples. The adsorption performance of the functionalized SiO 2 (donated as SiO 2 -PDA-PAPTCl) towards anionic organic dye Congo red (CR) was investigated to evaluate their potential environmental applications. We demonstrated that the surface of SiO 2 particles can be successfully functionalized with cationic PAPTCl. The adsorption capability of as-prepared SiO 2 was found to increases from 28.70 and 106.65mg/g after surface grafted with cationic polymers. The significant enhancement in the adsorption capability of SiO 2 -PDA-PAPTCl is mainly attributed to the introduction of cationic polymers. More importantly, this strategy is expected to be promising for fabrication of many other functional polymer nanocomposites for environmental applications due to the universality of mussel inspired chemistry and well designability and good monomer adaptability of SI-ATRP. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. 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

  4. 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...

  5. Carotenoids in Microalgae.

    Science.gov (United States)

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

    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.

  6. 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.

  7. One-electron oxidation of 2-(4-methoxyphenyl)-2-methylpropanoic and 1-(4-methoxyphenyl)cyclopropanecarboxylic acids in aqueous solution. the involvement of radical cations and the influence of structural effects and pH on the side-chain fragmentation reactivity.

    Science.gov (United States)

    Bietti, Massimo; Capone, Alberto

    2008-01-18

    A product and time-resolved kinetic study on the one-electron oxidation of 2-(4-methoxyphenyl)-2-methylpropanoic acid (2), 1-(4-methoxyphenyl)cyclopropanecarboxylic acid (3), and of the corresponding methyl esters (substrates 4 and 5, respectively) has been carried out in aqueous solution. With 2, no direct evidence for the formation of an intermediate radical cation 2*+ but only of the decarboxylated 4-methoxycumyl radical has been obtained, indicating either that 2*+ is not formed or that its decarboxylation is too fast to allow detection under the experimental conditions employed (k > 1 x 10(7) s(-1)). With 3, oxidation leads to the formation of the corresponding radical cation 3*+ or radical zwitterion -3*+ depending on pH. At pH 1.0 and 6.7, 3*+ and -3*+ have been observed to undergo decarboxylation as the exclusive side-chain fragmentation pathway with rate constants k = 4.6 x 10(3) and 2.3 x 10(4) s(-1), respectively. With methyl esters 4 and 5, direct evidence for the formation of the corresponding radical cations 4*+ and 5*+ has been obtained. Both radical cations have been observed to display a very low reactivity and an upper limit for their decay rate constants has been determined as k or=10, with the latter process that becomes the major fragmentation pathway around pH 12.

  8. 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

  9. Dietary factors that affect carotenoid bioavailability

    NARCIS (Netherlands)

    Hof, van het K.H.

    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

  10. Differential expression of carotenoid biosynthetic pathway genes in ...

    Indian Academy of Sciences (India)

    2016-04-08

    Apr 8, 2016 ... 1Division of Biotechnology, 2Division of Plant Physiology and Biochemistry and 3Division of Vegetable Crops, ... animal nutrition. They are efficient free radical scavengers, and modulate the immune system (Rao and Agarwal 1999). Carotenoids are essential nutrients that .... TIP 41 (TIP41-like protein).

  11. Electron paramagnetic resonance detection of carotenoid triplet states

    International Nuclear Information System (INIS)

    Frank, H.A.; Bolt, J.D.; deCosta, S.M.; Sauer, K.

    1980-01-01

    Triplet states of carotenoids have been detected by X-band electron paramagnetic resonance (EPR) and are reported here for the first time. The systems in which carotenoid triplets are observed include cells of photosynthetic bacteria, isolated bacteriochlorophyll-protein complexes, and detergent micelles which contain β-carotene. It is well known that if electron transfer is blocked following the initial acceptor in the bacterial photochemical reaction center, back reaction of the primary radical pair produces a bacteriochlorophyll dimer triplet. Previous optical studies have shown that in reaction centers containing carotenoids the bacteriochlorophyll dimer triplet sensitizes the carotenoid triplet. We have observed this carotenoid triplet state by EPR in reaction centers of Rhodopseudomonas sphaeroides, strain 2.4.1 (wild type), which contain the carotenoid spheroidene. The zero-field splitting parameters of the triplet spectrum are /D/ = 0.0290 +- 0.0005 cm -1 and /E/ = 0.0044 +-0.0006 cm -1 , in contrast with the parameters of the bacteriochlorophyll dimer triplet, which are /D/ = 0.0189 +- 0.0004 cm -1 and /E/ = 0.0032 +- 0.004 cm -1 . Bacteriochlorophyll in a light harvesting protein complex from Rps. sphaeroides, wild type, also sensitizes carotenoid triplet formation. In whole cells the EPR spectra vary with temperature between 100 and 10 K. Carotenoid triplets also have been observed by EPR in whole cells of Rps. sphaeroides and cells of Rhodospirillum rubrum which contain the carotenoid spirilloxanthin. Attempts to observe the triplet state EPR spectrum of β-carotene in numerous organic solvents failed. However, in nonionic detergent micelles and in phospholipid bilayer vesicles β-carotene gives a triplet state spectrum with /D/ = 0.0333 +- 0.0010 cm -1 and /E/ = 0.0037 +- 0.0010 cm -1 . 6 figures, 1 table

  12. Carotenoid Biosynthesis in Fusarium

    Directory of Open Access Journals (Sweden)

    Javier Avalos

    2017-07-01

    Full Text Available Many fungi of the genus Fusarium stand out for the complexity of their secondary metabolism. Individual species may differ in their metabolic capacities, but they usually share the ability to synthesize carotenoids, a family of hydrophobic terpenoid pigments widely distributed in nature. Early studies on carotenoid biosynthesis in Fusarium aquaeductuum have been recently extended in Fusarium fujikuroi and Fusarium oxysporum, well-known biotechnological and phytopathogenic models, respectively. The major Fusarium carotenoid is neurosporaxanthin, a carboxylic xanthophyll synthesized from geranylgeranyl pyrophosphate through the activity of four enzymes, encoded by the genes carRA, carB, carT and carD. These fungi produce also minor amounts of β-carotene, which may be cleaved by the CarX oxygenase to produce retinal, the rhodopsin’s chromophore. The genes needed to produce retinal are organized in a gene cluster with a rhodopsin gene, while other carotenoid genes are not linked. In the investigated Fusarium species, the synthesis of carotenoids is induced by light through the transcriptional induction of the structural genes. In some species, deep-pigmented mutants with up-regulated expression of these genes are affected in the regulatory gene carS. The molecular mechanisms underlying the control by light and by the CarS protein are currently under investigation.

  13. 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.

  14. Actinide cation-cation complexes

    International Nuclear Information System (INIS)

    Stoyer, N.J.; Seaborg, G.T.

    1994-12-01

    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) 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 AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ 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 NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ 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

  15. Site-selective photochemistry and vibrational analysis of matrix-isolated 1,3,5,7-octatetraene radical cations in different conformations

    International Nuclear Information System (INIS)

    Bally, T.; Nitsche, S.; Roth, K.

    1986-01-01

    Upon ionization by x irradiation, all-trans 1,3,5,7-octatetraene (OT) gives an electronic absorption (EA) spectrum which indicates the formation of at least five different (peri)planar conformations (''rotamers'') of OT/sup +/ next to the parent cation. Some of these undergo specific photochemical interconversions which are discussed on the basis of a complete scheme of OT/sup +/ rotamers and their connections via single bond-rotation processes. None of these photoreactions lead to any other than the initially observed six species which seem to form a distinguished set within the 20 possible OT/sup +/ rotamers. By very narrow bandwidth irradiation, interconversions can be induced to take place in a site-selective fashion. The resulting well-resolved difference spectra allow an analysis of the site dependence of the different ion's first two EA bands. Surprisingly, the extent of this site dependence varies greatly between different OT/sup +/ rotamers and between different electronic transitions of a given rotamer. Finally, a detailed vibrational analysis of the first two absorption bands of all-trans OT/sup +/ is given

  16. Antioxidant, Antinociceptive, and Anti-Inflammatory Effects of Carotenoids Extracted from Dried Pepper (Capsicum annuum L.)

    Science.gov (United States)

    Hernández-Ortega, Marcela; Ortiz-Moreno, Alicia; Hernández-Navarro, María Dolores; Chamorro-Cevallos, Germán; Dorantes-Alvarez, Lidia; Necoechea-Mondragón, Hugo

    2012-01-01

    Carotenoids extracted from dried peppers were evaluated for their antioxidant, analgesic, and anti-inflammatory activities. Peppers had a substantial carotenoid content: guajillo 3406 ± 4 μg/g, pasilla 2933 ± 1 μg/g, and ancho 1437 ± 6 μg/g of sample in dry weight basis. A complex mixture of carotenoids was discovered in each pepper extract. The TLC analysis revealed the presence of chlorophylls in the pigment extract from pasilla and ancho peppers. Guajillo pepper carotenoid extracts exhibited good antioxidant activity and had the best scavenging capacity for the DPPH+ cation (24.2%). They also exhibited significant peripheral analgesic activity at 5, 20, and 80 mg/kg and induced central analgesia at 80 mg/kg. The results suggest that the carotenoids in dried guajillo peppers have significant analgesic and anti-inflammatory benefits and could be useful for pain and inflammation relief. PMID:23091348

  17. Antioxidant, Antinociceptive, and Anti-Inflammatory Effects of Carotenoids Extracted from Dried Pepper (Capsicum annuum L.

    Directory of Open Access Journals (Sweden)

    Marcela Hernández-Ortega

    2012-01-01

    Full Text Available Carotenoids extracted from dried peppers were evaluated for their antioxidant, analgesic, and anti-inflammatory activities. Peppers had a substantial carotenoid content: guajillo 3406±4 μg/g, pasilla 2933±1 μg/g, and ancho 1437±6 μg/g of sample in dry weight basis. A complex mixture of carotenoids was discovered in each pepper extract. The TLC analysis revealed the presence of chlorophylls in the pigment extract from pasilla and ancho peppers. Guajillo pepper carotenoid extracts exhibited good antioxidant activity and had the best scavenging capacity for the DPPH+ cation (24.2%. They also exhibited significant peripheral analgesic activity at 5, 20, and 80 mg/kg and induced central analgesia at 80 mg/kg. The results suggest that the carotenoids in dried guajillo peppers have significant analgesic and anti-inflammatory benefits and could be useful for pain and inflammation relief.

  18. Detrimental effects of carotenoid pigments: the dark side of bright coloration

    Science.gov (United States)

    Huggins, Kristal A.; Navara, Kristen J.; Mendonça, Mary T.; Hill, Geoffrey E.

    2010-07-01

    Carotenoid pigments produce yellow, orange, and red integumentary color displays that can serve as reliable signals of health and condition. In many birds and fish, individuals gain competitive or mating advantages by ingesting and utilizing large quantities of carotenoid pigments. Carotenoid pigments serve as antioxidants, performing important functions as free-radical scavengers. The beneficial effects of carotenoid pigments are well documented, but rarely have researchers considered potential detrimental effects of high-level accumulation of carotenoids. We maintained American goldfinches ( Carduelis tristis) on high- or low-carotenoid diets through molt and tested for damage to the liver and skeletal muscle. High intake of carotenoids had no measurable effect on liver enzymes but caused an increase in creatine kinase, an indicator of skeletal muscle breakdown, and a reduction in vertical flight performance, a measure of skeletal muscle integrity. The detrimental effects of high-level carotenoid accumulation were approximately equivalent to the negative effects of removing carotenoids from the diet. The adverse effects observed in this study have important implications for theories of the function and evolution of colorful plumage.

  19. Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria.

    Science.gov (United States)

    Niedzwiedzki, Dariusz M; Hunter, C Neil; Blankenship, Robert E

    2016-11-03

    Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation-bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.

  20. DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species?

    Science.gov (United States)

    Wang, Fang; Sun, Wei; Xia, Chungu; Wang, Yong

    2017-10-01

    Through the introduction of dimethylamino (Me 2 N) substituent at the pyridine ring of 2-((R)-2-[(R)-1-(pyridine-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-ylmethyl)pyridine (PDP) ligand, the non-heme Fe II ( Me2N PDP)/H 2 O 2 /AcOH catalyst system was found to exhibit significant higher catalytic activity and enantioselectivity than the non-substituent one in the asymmetric epoxidation experiments. The mechanistic origin of the remarkable substituent effects in these oxidation reactions has not been well established. To ascertain the potent oxidant and the related reaction mechanism, a detailed DFT calculation was performed. Interestingly, a novel Fe(IV)-oxo Me2N PDP cation radical species, [( Me2N PDP) + · Fe IV (O)(OAc)] 2+ ( Me2N 5), with about one spin spreading over the non-heme Me2N PDP ligand was formed via a carboxylic-acid-assisted O-O bond heterolysis, which is reminiscent of Compound I (an Fe(IV)(O)(porphyrin cation radical) species) in cytochrome P450 chemistry. Me2N 5 is energetically comparable with the cyclic ferric peracetate species Me2N 6, while in the pristine Fe(PDP) catalyst system, H 6 is more stable than H 5. Comparison of the activation energy for the ethylene epoxidation promoted by Me2N 5 and Me2N 6, Me2N 5 is supposed as the true oxidant triggering the epoxidation of olefins. In addition, a systematic research on the substituent effects varied from the electron-donating substituent (dMM, the substituents at sites 3, 4, and 5 of the pyridine ring: methyl, methoxyl, and methyl) to the electron-withdrawing one (CF 3 , 2,6-bis(trifluoromethyl)phenyl) on the electronic structure of the reaction intermediates has also been investigated. An alternative cyclic ferric peracetate complex is obtained, indicating that the substituents at the pyridine ring of PDP ligands have significant impacts on the electronic structure of the oxidants.

  1. Infrared spectra of the 1-pyridinium (C5H5NH+) cation and pyridinyl (C5H5NH and 4-C5H6N) radicals isolated in solid para-hydrogen.

    Science.gov (United States)

    Golec, Barbara; Das, Prasanta; Bahou, Mohammed; Lee, Yuan-Pern

    2013-12-19

    Protonated pyridine and its neutral counterparts (C5H6N) are important intermediates in organic and biological reactions and in the atmosphere. We have recorded the IR absorption spectra of the 1-pyridinium (C5H5NH(+)) cation, 1-pyridinyl (C5H5NH), and 4-pyridinyl (4-C5H6N) produced on electron bombardment during matrix deposition of a mixture of pyridine (C5H5N) and p-H2 at 3.2 K; all spectra were previously unreported. The IR features of C5H5NH(+) diminished in intensity after the matrix was maintained in darkness for 15 h, whereas those of C5H5NH and 4-C5H6N radicals increased. Irradiation of this matrix with light at 365 nm diminished lines of C5H5NH(+) and C5H5NH but enhanced lines of 4-C5H6N slightly, whereas irradiation at 405 nm diminished lines of 4-C5H6N significantly. Observed wavenumbers and relative intensities of these species agree satisfactorily with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3LYP/6-31++G(d,p) method. Assignments of C5H5NH and 4-C5H6N radicals were further supported by the observation of similar spectra when a Cl2/C5H5N/p-H2 matrix was irradiated first at 365 nm and then with IR light to generate H atoms to induce the H + C5H5N reaction.

  2. From Carotenoids to Strigolactones

    KAUST Repository

    Jia, Kunpeng

    2017-12-13

    Strigolactones (SLs) are phytohormones that regulate different plant developmental and adaptation processes. When released into soil, SLs act as chemical signals attracting symbiotic arbuscular fungi and inducing seed germination in root parasitic weeds. SLs are carotenoid-derivatives characterized by the presence of a butenolide ring that is connected by an enol ether bridge to a less conserved, second moiety. Carotenoids are isopenoid pigments that differ in structure, number of conjugated double bonds and stereo-configuration. Genetic analysis and enzymatic studies demonstrate that SLs originate from all-trans-β-carotene in a pathway that involves the all-trans-/9-cis-β-carotene isomerase DWARF27 (D27) and the carotenoid cleavage dioxygenase 7 and 8 (CCD7, 8). The CCD7-mediated, regio- and stereospecific double bond cleavage of 9-cis-β-carotene leads to a 9-cis-configured intermediate that is converted by CCD8 via a combination of reactions into the central metabolite carlactone. By catalyzing repeated oxygenation reactions that can be coupled to ring closure, CYP711 enzymes convert carlactone into tricyclic ring containing, canonical and non-canonical SLs. Mostly unknown, modifying enzymes further increase SLs diversity. In this review, we touch on carotenogenesis, provide an update on SL biosynthesis, with emphasis on the substrate specificity and reactions catalyzed by the different enzymes, and describe the regulation of the pathway.

  3. Wurster's Blue-type cation radicals framed in a 5,10-dihydrobenzo[a]indolo[2,3-c]carbazole (BIC) skeleton: dual electrochromism with drastic changes in UV/Vis/NIR and fluorescence.

    Science.gov (United States)

    Suzuki, Takanori; Sakano, Yuto; Tokimizu, Yusuke; Miura, Youhei; Katoono, Ryo; Fujiwara, Kenshu; Yoshioka, Naoki; Fujii, Nobutaka; Ohno, Hiroaki

    2014-07-01

    Electron-donating dihydrobenzindolocarbazoles (BICs) 1 a-c, which adopt planar disk-shaped geometries, were prepared by gold(I)-catalyzed cyclization as a key step. Due to the presence of a 1,4-phenylenediamine (PD) moiety in the framework, they undergo reversible one-electron oxidation to the corresponding Wurster's Blue (WB)-type species that exhibits NIR absorptions up to λ=1200 nm. In the case of the N,N'-dimethyl derivative, cation radical 1 c(+.) is stable enough to be isolated as a salt and X-ray analysis indicated paraquinoid-type bond alternation in the WB core unit, whereas the bond lengths in the peripheral benzene rings are identical to those in the neutral donor. Upon electrochemical interconversion, the redox pairs of 1 a-c and 1 a-c(+.) exhibited an electrochromic response in the UV/Vis/NIR region, which was accompanied by a drastic change in the fluorescence spectrum because only neutral donors 1 a-c are highly emissive (Φ(F) : 0.7-0.8). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Specific carotenoid pigments in the diet and a bit of oxidative stress in the recipe for producing red carotenoid-based signals

    Science.gov (United States)

    García-de Blas, Esther; Mateo, Rafael

    2016-01-01

    Colorful ornaments have been the focus of sexual selection studies since the work of Darwin. Yellow to red coloration is often produced by carotenoid pigments. Different hypotheses have been formulated to explain the evolution of these traits as signals of individual quality. Many of these hypotheses involve the existence of a signal production cost. The carotenoids necessary for signaling can only be obtained from food. In this line, carotenoid-based signals could reveal an individual’s capacity to find sufficient dietary pigments. However, the ingested carotenoids are often yellow and became transformed by the organism to produce pigments of more intense color (red ketocarotenoids). Biotransformation should involve oxidation reactions, although the exact mechanism is poorly known. We tested the hypothesis that carotenoid biotransformation could be costly because a certain level of oxidative stress is required to correctly perform the conversion. The carotenoid-based signals could thus reveal the efficiency of the owner in successfully managing this challenge. In a bird with ketocarotenoid-based ornaments (the red-legged partridge; Alectoris rufa), the availability of different carotenoids in the diet (i.e. astaxanthin, zeaxanthin and lutein) and oxidative stress were manipulated. The carotenoid composition was analyzed and quantified in the ornaments, blood, liver and fat. A number of oxidative stress biomarkers were also measured in the same tissues. First, we found that color and pigment levels in the ornaments depended on food levels of those carotenoids used as substrates in biotransformation. Second, we found that birds exposed to mild levels of a free radical generator (diquat) developed redder bills and deposited higher amounts of ketocarotenoids (astaxanthin) in ornaments. Moreover, the same diquat-exposed birds also showed a weaker resistance to hemolysis when their erythrocytes were exposed to free radicals, with females also enduring higher oxidative

  5. Specific carotenoid pigments in the diet and a bit of oxidative stress in the recipe for producing red carotenoid-based signals.

    Science.gov (United States)

    García-de Blas, Esther; Mateo, Rafael; Alonso-Alvarez, Carlos

    2016-01-01

    Colorful ornaments have been the focus of sexual selection studies since the work of Darwin. Yellow to red coloration is often produced by carotenoid pigments. Different hypotheses have been formulated to explain the evolution of these traits as signals of individual quality. Many of these hypotheses involve the existence of a signal production cost. The carotenoids necessary for signaling can only be obtained from food. In this line, carotenoid-based signals could reveal an individual's capacity to find sufficient dietary pigments. However, the ingested carotenoids are often yellow and became transformed by the organism to produce pigments of more intense color (red ketocarotenoids). Biotransformation should involve oxidation reactions, although the exact mechanism is poorly known. We tested the hypothesis that carotenoid biotransformation could be costly because a certain level of oxidative stress is required to correctly perform the conversion. The carotenoid-based signals could thus reveal the efficiency of the owner in successfully managing this challenge. In a bird with ketocarotenoid-based ornaments (the red-legged partridge; Alectoris rufa), the availability of different carotenoids in the diet (i.e. astaxanthin, zeaxanthin and lutein) and oxidative stress were manipulated. The carotenoid composition was analyzed and quantified in the ornaments, blood, liver and fat. A number of oxidative stress biomarkers were also measured in the same tissues. First, we found that color and pigment levels in the ornaments depended on food levels of those carotenoids used as substrates in biotransformation. Second, we found that birds exposed to mild levels of a free radical generator (diquat) developed redder bills and deposited higher amounts of ketocarotenoids (astaxanthin) in ornaments. Moreover, the same diquat-exposed birds also showed a weaker resistance to hemolysis when their erythrocytes were exposed to free radicals, with females also enduring higher oxidative

  6. 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.

  7. 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.

  8. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  9. Identification of carotenoids with high antioxidant capacity produced by extremophile microorganisms.

    Science.gov (United States)

    Mandelli, Fernanda; Miranda, Viviane S; Rodrigues, Eliseu; Mercadante, Adriana Z

    2012-04-01

    In this study, the carotenoids produced by the extremophile microorganisms Halococcus morrhuae, Halobacterium salinarium and Thermus filiformis were separated and identified by high-performance liquid chromatography connected to a diode array detector and a tandem mass spectrometer. The in vitro scavenging capacity of the carotenoid extracts against radical and non-radical species was evaluated. In halophilic microorganisms, the following carotenoids were identified: bacterioruberin, bisanhydrobacterioruberin, trisanhydrobacterioruberin and their derivatives. In the thermophilic bacterium, the carotenoids all-trans-zeaxanthin, zeaxanthin monoglucoside, thermozeaxanthins and thermobiszeaxanthins were identified. The antioxidant capacities of the carotenoid extracts of H. morrhuae (trolox equivalent antioxidant capacity = 5.07 and IC(50) = 0.85 μg mL(-1)) and H. salinarium (trolox equivalent antioxidant capacity = 5.28 and IC(50) = 0.84 μg mL(-1)) were similar and higher than those of the bacterium T. filiformis (trolox equivalent antioxidant capacity = 2.87 and IC(50) = 2.41 μg mL(-1)). This difference is related to the presence of acyclic carotenoids with both large numbers of conjugated double bounds and of hydroxyl groups in the major carotenoid of the halophilic microorganisms.

  10. Interactions between Carotenoids from Marine Bacteria and Other Micronutrients: Impact on Stability and Antioxidant Activity.

    Science.gov (United States)

    Sy, Charlotte; Dangles, Olivier; Borel, Patrick; Caris-Veyrat, Catherine

    2015-11-19

    Recently isolated spore-forming pigmented marine bacteria Bacillus indicus HU36 are sources of oxygenated carotenoids with original structures (about fifteen distinct yellow and orange pigments with acylated d-glucosyl groups). In this study, we evaluated the stability (sensitivity to iron-induced autoxidation) and antioxidant activity (inhibition of iron-induced lipid peroxidation) of combinations of bacterial HU36 carotenoids with the bacterial vitamin menaquinone MQ-7 and with phenolic antioxidants (vitamin E, chlorogenic acid, rutin). Unexpectedly, MQ-7 strongly improves the ability of HU36 carotenoids to inhibit Fe(II)-induced lipid peroxidation, although MQ-7 was not consumed in the medium. We propose that their interaction modifies the carotenoid antioxidant mechanism(s), possibly by allowing carotenoids to scavenge the initiating radicals. For comparison, β-carotene and lycopene in combination were shown to exhibit a slightly higher stability toward iron-induced autoxidation, as well as an additive antioxidant activity as compared to the carotenoids, individually. HU36 carotenoids and phenolic antioxidants displayed synergistic activities in the inhibition of linoleic acid peroxidation induced by heme iron, but not by free iron. Synergism could arise from antioxidants interacting via electron transfer through the porphyrin nucleus of heme iron. Overall, combining antioxidants acting via complementary mechanisms could be the key for optimizing the activity of this bacterial carotenoid cocktail.

  11. Biological roles of fungal carotenoids.

    Science.gov (United States)

    Avalos, Javier; Carmen Limón, M

    2015-08-01

    Carotenoids are terpenoid pigments widespread in nature, produced by bacteria, fungi, algae and plants. They are also found in animals, which usually obtain them through the diet. Carotenoids in plants provide striking yellow, orange or red colors to fruits and flowers, and play important metabolic and physiological functions, especially relevant in photosynthesis. Their functions are less clear in non-photosynthetic microorganisms. Different fungi produce diverse carotenoids, but the mutants unable to produce them do not exhibit phenotypic alterations in the laboratory, apart of lack of pigmentation. This review summarizes the current knowledge on the functional basis for carotenoid production in fungi. Different lines of evidence support a protective role of carotenoids against oxidative stress and exposure to visible light or UV irradiation. In addition, the carotenoids are intermediary products in the biosynthesis of physiologically active apocarotenoids or derived compounds. This is the case of retinal, obtained from the symmetrical oxidative cleavage of β-carotene. Retinal is the light-absorbing prosthetic group of the rhodopsins, membrane-bound photoreceptors present also in many fungal species. In Mucorales, β-carotene is an intermediary in the synthesis of trisporoids, apocarotenoid derivatives that include the sexual hormones the trisporic acids, and they are also presumably used in the synthesis of sporopollenin polymers. In conclusion, fungi have adapted their ability to produce carotenoids for different non-essential functions, related with stress tolerance or with the synthesis of physiologically active by-products.

  12. 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.

  13. Carotenoids: biochemistry, pharmacology and treatment.

    Science.gov (United States)

    Milani, Alireza; Basirnejad, Marzieh; Shahbazi, Sepideh; Bolhassani, Azam

    2017-06-01

    Carotenoids and retinoids have several similar biological activities such as antioxidant properties, the inhibition of malignant tumour growth and the induction of apoptosis. Supplementation with carotenoids can affect cell growth and modulate gene expression and immune responses. Epidemiological studies have shown a correlation between a high carotenoid intake in the diet with a reduced risk of breast, cervical, ovarian, colorectal cancers, and cardiovascular and eye diseases. Cancer chemoprevention by dietary carotenoids involves several mechanisms, including effects on gap junctional intercellular communication, growth factor signalling, cell cycle progression, differentiation-related proteins, retinoid-like receptors, antioxidant response element, nuclear receptors, AP-1 transcriptional complex, the Wnt/β-catenin pathway and inflammatory cytokines. Moreover, carotenoids can stimulate the proliferation of B- and T-lymphocytes, the activity of macrophages and cytotoxic T-cells, effector T-cell function and the production of cytokines. Recently, the beneficial effects of carotenoid-rich vegetables and fruits in health and in decreasing the risk of certain diseases has been attributed to the major carotenoids, β-carotene, lycopene, lutein, zeaxanthin, crocin (/crocetin) and curcumin, due to their antioxidant effects. It is thought that carotenoids act in a time- and dose-dependent manner. In this review, we briefly describe the biological and immunological activities of the main carotenoids used for the treatment of various diseases and their possible mechanisms of action. This article is part of a themed section on Principles of Pharmacological Research of Nutraceuticals. To view the other articles in this section visit http://onlinelibrary.wiley.com/doi/10.1111/bph.v174.11/issuetoc. © 2016 The British Pharmacological Society.

  14. 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.

  15. Dietary Intake of Carotenoids and Their Antioxidant and Anti-Inflammatory Effects in Cardiovascular Care

    Directory of Open Access Journals (Sweden)

    Marco Matteo Ciccone

    2013-01-01

    Full Text Available Cardiovascular disease related to atherosclerosis represents nowadays the largest cause of morbidity and mortality in developed countries. Due to inflammatory nature of atherosclerosis, several studies had been conducted in order to search for substances with anti-inflammatory activity on arterial walls, able to exert beneficial roles on health. Researches investigated the role of dietary carotenoids supplementation on cardiovascular disease, due to their free radicals scavenger properties and their skills in improving low-density lipoprotein cholesterol resistance to oxidation. Nevertheless, literature data are conflicting: although some studies found a positive relationship between carotenoids supplementation and cardiovascular risk reduction, others did not find any positive effects or even prooxidant actions. This paper aimed at defining the role of carotenoids supplementation on cardiovascular risk profile by reviewing literature data, paying attention to those carotenoids more present in our diet (β-carotene, α-carotene, β-cryptoxanthin, lycopene, lutein, zeaxanthin, and astaxanthin.

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

    Science.gov (United States)

    Raposo, Maria Filomena de Jesus; de Morais, Alcina Maria Miranda Bernardo; de Morais, Rui Manuel Santos Costa

    2015-08-14

    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.

  17. 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....

  18. Marine Carotenoids: Biological Functions and Commercial Applications

    Directory of Open Access Journals (Sweden)

    José M. Vega

    2011-03-01

    Full Text Available 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 functions of carotenoids relevant for life on earth. Biological properties of carotenoids allow for a wide range of commercial applications. Indeed, recent interest in the carotenoids has been mainly for their nutraceutical properties. A large number of scientific studies have confirmed the benefits of carotenoids to health and their use for this purpose is growing rapidly. In addition, carotenoids have traditionally been used in food and animal feed for their color properties. Carotenoids are also known to improve consumer perception of quality; an example is the addition of carotenoids to fish feed to impart color to farmed salmon.

  19. Marine Carotenoids: Biological Functions and Commercial Applications

    Science.gov (United States)

    Vílchez, Carlos; Forján, Eduardo; Cuaresma, María; Bédmar, Francisco; Garbayo, Inés; Vega, José 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 functions of carotenoids relevant for life on earth. Biological properties of carotenoids allow for a wide range of commercial applications. Indeed, recent interest in the carotenoids has been mainly for their nutraceutical properties. A large number of scientific studies have confirmed the benefits of carotenoids to health and their use for this purpose is growing rapidly. In addition, carotenoids have traditionally been used in food and animal feed for their color properties. Carotenoids are also known to improve consumer perception of quality; an example is the addition of carotenoids to fish feed to impart color to farmed salmon. PMID:21556162

  20. Polarized absorption spectra of aromatic radicals in stretched polymer film. 3. Radical ions of acridine and phenazine

    Energy Technology Data Exchange (ETDEWEB)

    Sekigucki, K.; Hiratsuka, H.; Tanizaki, Y.; Hatano, Y.

    1980-02-21

    Radical anions and cations of acridine and phenazine have been prepared in polymer film by ..gamma..-ray irradiation at 77 K. For the preparation of radical anions the sample was incorporated into polyethylene film by sec-butylamine, while for radical cations poly(vinyl chloride) film and sec-butyl chloride were used. Polarized absorption spectra of these radical ions have been measured in stretched polymer film and analyzed qualitatively in terms of molecular orbital calculations.

  1. 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.

  2. 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.

  3. 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

  4. Carotenoid-dependent signals and the evolution of plasma carotenoid levels in birds.

    Science.gov (United States)

    Simons, Mirre J P; Maia, Rafael; Leenknegt, Bas; Verhulst, Simon

    2014-12-01

    Sexual selection has resulted in a wide array of ornaments used in mate choice, and such indicator traits signal quality honestly when they bear costs, precluding cheating. Carotenoid-dependent coloration has attracted considerable attention in this context, because investing carotenoids in coloration has to be traded off against its physiological functions; carotenoids are antioxidants and increase immunocompetence. This trade-off is hypothesized to underlie the honesty of carotenoid-dependent coloration, signaling the "handicap" of allocating carotenoids away from somatic maintenance toward sexual display. Utilizing recent advances in modeling adaptive evolution, we used a comparative approach to investigate the evolution of plasma carotenoid levels using a species-level phylogeny of 178 bird species. We find that the evolutionary optimum for carotenoid levels is higher in lineages that evolved carotenoid-dependent coloration, with strong attraction toward this optimum. Hence, carotenoids do not appear to be limiting, given that higher carotenoid levels readily evolve in response to the evolution of carotenoid-dependent coloration. These findings challenge the assumption that carotenoids are a scarce resource and thus also challenge the hypothesis that physiological resource value of carotenoids underlies honesty of carotenoid-dependent traits. Therefore, the comparative evidence suggests that other factors, such as the acquisition and incorporation of carotenoids, are involved in maintaining signal honesty.

  5. Saffron and natural carotenoids: Biochemical activities and anti-tumor effects.

    Science.gov (United States)

    Bolhassani, Azam; Khavari, Afshin; Bathaie, S Zahra

    2014-01-01

    Saffron, a spice derived from the flower of Crocus sativus, is rich in carotenoids. Two main natural carotenoids of saffron, crocin and crocetin, are responsible for its color. Preclinical studies have shown that dietary intake of some carotenoids have potent anti-tumor effects both in vitro and in vivo, suggesting their potential preventive and/or therapeutic roles in several tissues. The reports represent that the use of carotenoids without the potential for conversion to vitamin A may provide further protection and avoid toxicity. The mechanisms underlying cancer chemo-preventive activities of carotenoids include modulation of carcinogen metabolism, regulation of cell growth and cell cycle progression, inhibition of cell proliferation, anti-oxidant activity, immune modulation, enhancement of cell differentiation, stimulation of cell-to-cell gap junction communication, apoptosis and retinoid-dependent signaling. Taken together, different hypotheses for the antitumor actions of saffron and its components have been proposed such as a) the inhibitory effect on cellular DNA and RNA synthesis, but not on protein synthesis; b) the inhibitory effect on free radical chain reactions; c) the metabolic conversion of naturally occurring carotenoids to retinoids; d) the interaction of carotenoids with topoisomerase II, an enzyme involved in cellular DNA-protein interaction. Furthermore, the immunomodulatory activity of saffron was studied on driving toward Th1 and Th2 limbs of the immune system. In this mini-review, we briefly describe biochemical and immunological activities and chemo-preventive properties of saffron and natural carotenoids as an anticancer drug. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Effects of carotenoids on lipid bilayers.

    Science.gov (United States)

    Johnson, Quentin R; Mostofian, Barmak; Fuente Gomez, Gabriel; Smith, Jeremy C; Cheng, Xiaolin

    2018-01-31

    Carotenoids have been found to be important in improving the integrity of biomembranes in eukaryotes. However, the molecular details of how carotenoids modulate the physical properties of biomembranes are unknown. To this end, we have conducted a series of molecular dynamics simulations of different biologically-relevant membranes in the presence of carotenoids. The carotenoid effect on the membrane was found to be specific to the identity of the carotenoid and the composition of the membrane itself. Therefore, different classes of carotenoids produce a different effect on the membrane, and different membrane phases are affected differently by carotenoids. It is apparent from our data that carotenoids do trigger the bilayer to become thinner. The mechanism by which this occurs depends on two competing factors, the ability of the lipid tails of opposing monolayers to either (1) compress or (2) interdigitate as the bilayer condenses. Indeed, carotenoids directly influence the physical properties via these two mechanisms, thus compacting the bilayer. However, the degree to which these competing mechanisms are utilized depends on the bilayer phase and the carotenoid identity.

  7. 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.

  8. 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.

  9. Occurrence and biosynthesis of carotenoids in phytoplankton.

    Science.gov (United States)

    Huang, Jim Junhui; Lin, Shaoling; Xu, Wenwen; Cheung, Peter Chi Keung

    2017-09-01

    Naturally occurring carotenoids are important sources of antioxidants, anti-cancer compounds and anti-inflammatory agents and there is thus considerable market demand for their pharmaceutical applications. Carotenoids are widely distributed in marine and freshwater organisms including microalgae, phytoplankton, crustaceans and fish, as well as in terrestrial plants and birds. Recently, phytoplankton-derived carotenoids have received much attention due to their abundance, rapid rate of biosynthesis and unique composition. The carotenoids that accumulate in particular phytoplankton phyla are synthesized by specific enzymes and play unique physiological roles. This review focuses on studies related to the occurrence of carotenoids in different phytoplankton phyla and the molecular aspects of their biosynthesis. Recent biotechnological advances in the isolation and characterization of some representative carotenoid synthases in phytoplankton are also discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Carotenoids content and sunlight susceptibility

    International Nuclear Information System (INIS)

    Oppezzo, Oscar J.; Costa, Cristina; Pizarro, Ramon A.

    2005-01-01

    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 [O 2 ]. 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)

  11. Free radical scavenging activity of papaya juice

    Energy Technology Data Exchange (ETDEWEB)

    Webman, E.J.; Mower, H.F.; Edlin, Gordon

    1989-03-01

    Papaya juice is an efficient scavenger of highly reactive hydroxyl radicals (OH radical) formed during /sup 60/Co 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.

  12. 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.

    2015-01-01

    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 C 000000000000 000000000000 000000000000 111111111111 000000000000 111111111111 000000000000 000000000000 000000000000 C 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

  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

  14. The acid-catalyzed rearrangement CH3Oo --> oCH2OH and its involvement in the dissociation of the methanol dimer radical cation; A Quid pro Quo reaction

    NARCIS (Netherlands)

    Burgers, P.C.; Ruttink, P.J.A.

    2005-01-01

    The barrier for the radical isomerization CH3Oo --> oCH2OH is calculated by CBS-QB3 to be 29.7 kcal mol-1 and lies higher (by 5.7 kcal mol-1) than the dissociation limit CH2O+Ho. Hence, CH3Oo does not isomerize to the more stable oCH2OH on its own. However, this barrier is reduced to 15.8 kcal mol-1

  15. 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...

  16. Carotenoids from Phaffia rhodozyma : Antioxidant activity and ...

    African Journals Online (AJOL)

    The main goal of this work was to establish the stability and antioxidant activity of the extracts obtained through different techniques for recovering carotenoids from Phaffia rhodozyma NRRL-Y 17268. The best conditions for extracting carotenoids through cell rupture with dimethylsulfoxide (DMSO) were found to be a ...

  17. 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...

  18. Carotenoids, sexual signals and immune function in barn swallows from Chernobyl.

    Science.gov (United States)

    Camplani, A; Saino, N; Møller, A P

    1999-06-07

    Carotenoids have been hypothesized to facilitate immune function and act as free-radical scavengers, thereby minimizing the frequency of mutations. Populations of animals exposed to higher levels of free radicals are thus expected to demonstrate reduced sexual coloration if use of carotenoids for free-radical scavenging is traded against use for sexual signals. The intensity of carotenoid-based sexual coloration was compared among three populations of barn swallows Hirundo rustica differing in exposure to radioactive contamination. Lymphocyte and immunoglobulin concentrations were depressed, whereas the heterophil:lymphocyte ratio, an index of stress, was enhanced in Chernobyl swallows compared to controls. Spleen size was reduced in Chernobyl compared to that of two control populations. Sexual coloration varied significantly among populations, with the size of a secondary sexual character (the length of the outermost tail feathers) being positively related to coloration in the two control populations, but not in the Chernobyl population. Thus the positive covariation between coloration and sexual signalling disappeared in the population subject to intense radioactive contamination. These findings suggest that the reliable signalling function of secondary sexual characters breaks down under extreme environmental conditions, no longer providing reliable information about the health status of males.

  19. 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.

  20. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomerization of the linear propargyl cation to the aromatic cyclopropenyl cation, also probing the phenomenon of solvation of this reaction by simple lone pair donors (NH3, H2O, H2S and HF) which bind to the substrate at two sites.

  1. 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.

  2. Carotenoid bioaccessibility in pulp and fresh juice from carotenoid-rich sweet oranges and mandarins.

    Science.gov (United States)

    Rodrigo, María Jesús; Cilla, Antonio; Barberá, Reyes; Zacarías, Lorenzo

    2015-06-01

    Citrus fruits are a good source of carotenoids for the human diet; however, comparative studies of carotenoids in different citrus food matrices are scarce. In this work the concentration and bioaccessibility of carotenoids in sweet oranges and mandarins with marked differences in carotenoid composition were evaluated in pulp and compared to those in fresh juice. The pulp and juice of the red-fleshed Cara Cara sweet orange variety was highly rich in carotenes (mainly lycopene and phytoene) compared to standard Navel orange, while β-cryptoxanthin and phytoene predominated in mandarins. Total carotenoid content in the pulp of the ordinary Navel orange and in the red-fleshed Cara Cara orange, as well as in the Clementine mandarin were higher than in the corresponding juices, although individual carotenoids were differentially affected by juice preparation. Bioaccessibility of the bioactive carotenoids (the ones described to be absorbed by humans) was greater in both pulp and juice of the carotenoid-rich Cara Cara orange compared to the Navel orange while increasing levels of β-cryptoxanthin were detected in the bioaccessible fractions of pulp and juice of mandarins postharvest stored at 12 °C compared to freshly-harvested fruits. Overall, results indicated that higher soluble bioactive carotenoids from citrus fruits and, consequently, potential nutritional and health benefits are obtained by the consumption of pulp with respect to fresh juice.

  3. IMPORTANCE OF CAROTENOIDS FOR HUMAN HEALTH

    Directory of Open Access Journals (Sweden)

    Semih ÖTLEŞ

    1997-01-01

    Full Text Available Carotenoids are brightly yellow to red pigments occuring in plants and are introduced into humans through dietary intake of vegetables and fruits. They do not dissolve in water, they can give maximum absorption in UV region at 400-450 nm., and they are stable in alkali. Some carotenoids have provitamin A activity and they are important because of the synthesis of Vitamin A needed to be taken into the body. In addition to this function, carotenoids play very important roles in preventing diseases caused by Vitamin A deficiency, coronary heart diseases, and cancer. They are effective in preventing or at least slowering cancer as a result of their antioxidative properties. Studies are shown that cancer risk (especially the lung cancer decreases with the intake of carotenoids. As a conclusion vegetables and fruits-rich diet is always important and valuable for healty populations.

  4. 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.

  5. Strong antiferromagnetic coupling of spins in the (MDABCO+)(C60·-) salt with 3D close packing of the C60·- radical anions (MDABCO+: N-methyldiazabicyclooctanium cation).

    Science.gov (United States)

    Konarev, Dmitri V; Khasanov, Salavat S; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

    2014-06-01

    A new salt, (MDABCO(+))(C60(·-)) (1; MDABCO(+) = N-methyldiazabicyclooctanium cation), was obtained as single crystals. The crystal structure of 1 determined at 250 and 100 K showed 3D close packing of fullerenes with eight fullerene neighbors for each C60(·-). These neighbors are located at 10.01-10.11 Å center-to-center distances (250 K) and van der Waals interfullerene C⋅⋅⋅C contacts are formed with four fullerene neighbors arranged in the bc plane. Fullerene ordering observed below 160 K is accompanied by the appearance of one and a half independent C60(·-) and trebling of the unit cell along the b axis. Fullerenes are packed closer to each other at 100 K. As a result, fullerenes are located in the three-dimensional packing at 9.91-10.12 Å center-to-center distances and 18 short interfullerene C⋅⋅⋅C contacts are formed for each C60(·-). Although they are closed packed, fullerenes are not dimerized down to 1.9 K. Magnetic data indicate strong antiferromagnetic coupling of spins in the 70-300 K range with a Weiss temperature of Θ = -118 K. Magnetic susceptibility shows a round maximum at 46 K. Such behavior can be described well by the Heisenberg model for square two-dimensional antiferromagnetic coupling of spins with an exchange interaction of J/kB = -25.3 K. This magnetic coupling is one of the strongest observed for C60(·-) salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Correlations Between Macular, Skin, and Serum Carotenoids

    Science.gov (United States)

    Conrady, Christopher D.; Bell, James P.; Besch, Brian M.; Gorusupudi, Aruna; Farnsworth, Kelliann; Ermakov, Igor; Sharifzadeh, Mohsen; Ermakova, Maia; Gellermann, Werner; Bernstein, Paul S.

    2017-01-01

    Purpose Ocular and systemic measurement and imaging of the macular carotenoids lutein and zeaxanthin have been employed extensively as potential biomarkers of AMD risk. In this study, we systematically compare dual wavelength retinal autofluorescence imaging (AFI) of macular pigment with skin resonance Raman spectroscopy (RRS) and serum carotenoid levels in a clinic-based population. Methods Eighty-eight patients were recruited from retina and general ophthalmology practices from a tertiary referral center and excluded only if they did not have all three modalities tested, had a diagnosis of macular telangiectasia (MacTel) or Stargardt disease, or had poor AFI image quality. Skin, macular, and serum carotenoid levels were measured by RRS, AFI, and HPLC, respectively. Results Skin RRS measurements and serum zeaxanthin concentrations correlated most strongly with AFI macular pigment volume under the curve (MPVUC) measurements up to 9° eccentricity relative to MPVUC or rotationally averaged macular pigment optical density (MPOD) measurements at smaller eccentricities. These measurements were reproducible and not significantly affected by cataracts. We also found that these techniques could readily identify subjects taking oral carotenoid-containing supplements. Conclusions Larger macular pigment volume AFI and skin RRS measurements are noninvasive, objective, and reliable methods to assess ocular and systemic carotenoid levels. They are an attractive alternative to psychophysical and optical methods that measure MPOD at a limited number of eccentricities. Consequently, skin RRS and MPVUC at 9° are both reasonable biomarkers of macular carotenoid status that could be readily adapted to research and clinical settings. PMID:28728169

  7. Associations between circulating carotenoids, genomic instability and the risk of high-grade prostate cancer.

    Science.gov (United States)

    Nordström, Tobias; Van Blarigan, Erin L; Ngo, Vy; Roy, Ritu; Weinberg, Vivian; Song, Xiaoling; Simko, Jeffry; Carroll, Peter R; Chan, June M; Paris, Pamela L

    2016-03-01

    Carotenoids are a class of nutrients with antioxidant properties that have been purported to protect against cancer. However, the reported associations between carotenoids and prostate cancer have been heterogeneous and lacking data on interactions with nucleotide sequence variations and genomic biomarkers. To examine the associations between carotenoid levels and the risk of high-grade prostate cancer, also considering antioxidant-related genes and tumor instability. We measured plasma levels of carotenoids and genotyped 20 single nucleotide polymorphisms (SNP) in SOD1, SOD2, SOD3, XRCC1, and OGG1 among 559 men with non-metastatic prostate cancer undergoing radical prostatectomy. We performed copy number analysis in a subset of these men (n = 67) to study tumor instability assessed as Fraction of the Genome Altered (FGA). We examined associations between carotenoids, genotypes, tumor instability and risk of high-grade prostate cancer (Gleason grade ≥ 4 + 3) using logistic and linear regression. Circulating carotenoid levels were inversely associated with the risk of high-grade prostate cancer; odds ratios (OR) and 95% confidence intervals (CI) comparing highest versus lowest quartiles were: 0.34 (95% CI: 0.18-0.66) for α-carotene, 0.31 (95% CI: 0.15-0.63) for β-carotene, 0.55 (0.28-1.08) for lycopene and 0.37 (0.18-0.75) for total carotenoids. SNPs rs25489 in XRCC1, rs699473 in SOD3 and rs1052133 in OGG1 modified these associations for α-carotene, β-carotene and lycopene, respectively (P ≤ 0.05). The proportion of men with a high degree of FGA increased with Gleason Score (P carotenoids at diagnosis, particularly among men carrying specific somatic variations, were inversely associated with risk of high-grade prostate cancer. In exploratory analyses, higher lycopene level was associated with less genomic instability among men with low-grade disease which is novel and supports the hypothesis that lycopene may inhibit progression of

  8. Amarginal contribution of selected carotenoids to the supression of UV-irradiation-induced lecithin peroxidation in hexane solution

    Directory of Open Access Journals (Sweden)

    DRAGAN CVETKOVIC

    2007-03-01

    Full Text Available The aim of this work was to study the anticipated antioxidant role of four selected carotenoids in mixtures with lecithin lipoidal compounds in hexane solution, under continuous UV-irradiation in three different ranges (UV-A, UV-B and UV-C. Two carotenes (b-carotene and licopene and two xantophylls (lutein and neoxanthin were employed to control the lipid peroxidation process generated by UV-irradiation, by scavenging the involved free radicals. The results show that while carotenoids undergo a substantial, structural dependent destruction (bleaching, which is highly dependent on energy of the UV-photons, their contribution to the expected suppression of lecithin peroxidation is of marginal importance, not exceeding a maximum of 20%. The marginal antioxidant behaviour has been attributed to a highly unordered hexane solution, where the scavenging action of the carotenoids becomes less competitive.

  9. Radical Islam

    Science.gov (United States)

    2002-07-01

    Muslim insurgents have a real following in many countries. In Mao’s parlance, the radical Muslim insurgent is the fish swimming in the ocean of the...indigenous beliefs 5% Tanzania: mainland - Christian 45%, Muslim 35%, indigenous beliefs 20%; Zanzibar - more than 99% Muslim Zambia: Christian 50...leather, frozen fish and seafood Bosnia and Herzegovina NA Brunei: crude oil, natural gas, refined products Chad: cotton, cattle, textiles Cocos Islands

  10. Carotenoid-dependent signals and the evolution of plasma carotenoid levels in birds

    NARCIS (Netherlands)

    Simons, Mirre J. P.; Maia, Rafael; Leenknegt, Bas; Verhulst, Simon

    2014-01-01

    Sexual selection has resulted in a wide array of ornaments used in mate choice, and such indicator traits signal quality honestly when they bear costs, precluding cheating. Carotenoid-dependent coloration has attracted considerable attention in this context, because investing carotenoids in

  11. 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.

  12. 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. © 2015 Society for Experimental Biology, Association of Applied Biologists and John Wiley & Sons Ltd.

  13. Encapsulation of carotenoids extracted from halophilic Archaea in oil-in-water (O/W) micro- and nano-emulsions.

    Science.gov (United States)

    Chaari, Marwa; Theochari, Ioanna; Papadimitriou, Vassiliki; Xenakis, Aristotelis; Ammar, Emna

    2018-01-01

    Carotenoids extracted from halophilc Archaea have potential health benefits. Their poor water-solubility and low bioavailability is a challenge to their incorporation into foods. The aim of this work was the carotenoids encapsulation into two oil-in-water (O/W) dispersions, to increase their use as functional food applications. A nanoemulsion produced by high pressure homogenization and a spontaneously formed microemulsion were conceived. The limonene was the dispersed oil phase, and mixtures of Triton X-100/Tween-80 (3:1) as emulsifiers and of water/glycerol (2:1) as the continuous aqueous phase. The microemulsion monophasic area was determined through the pseudo-ternary phase diagram. Dynamic Light Scattering was used for the structural characterization of the nano- and micro-emulsions in the presence of the carotenoids. Moreover, the radical scavenging activity of the encapsulated carotenoids was examined by Electron Paramagnetic Resonance spectroscopy. The results confirmed the delivery systems design effectiveness to encapsulate and stabilize the carotenoids for food applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Evaluation of the clastogenicity and anticlastogenicity of the carotenoid bixin in human lymphocyte cultures.

    Science.gov (United States)

    Antunes, Lusânia M Greggi; Pascoal, Lívia M; Bianchi, Maria de Lourdes P; Dias, Francisca L

    2005-08-01

    Carotenoids are regarded as effective antioxidants, antimutagenic and anticarcinogenic agents. Annatto, a red-yellow extract obtained from seeds of Bixa orellana L. is a mixture of several carotenoids and one of them bixin (BXN), is known as its major coloring compound. Studies on BXN clastogenicity and anticlastogenicity in cultured human lymphocytes have not been reported so far. Therefore, the present study was undertaken to investigate the ability of BXN to induce chromosomal aberrations in human lymphocytes in vitro and to examine the possible anticlastogenic effect of this carotenoid in chromosomal damage induced by the clastogen cisplatin (cDDP). Human blood samples were obtained from six healthy, non-smoking volunteers; two females and four males aged 18-35 years. The concentrations of BXN (1.0; 2.5; 5.0 or 10 microg/mL) tested in combination with cDDP were established on the basis of mitotic index (MI) measurements. The data showed that BXN was not cytotoxic or clastogenic, when compared to untreated control. A marked decrease in the MI values compared to the untreated control and an increased percentage of aberrant metaphases was seen in all cultures treated with cDDP. The carotenoid efficiency in reducing the inhibitory effect of cDDP on lymphocyte MI is concentration-dependent. Cultures simultaneously treated with BXN and cDDP showed a statistically significant reduction in total chromosomal aberrations and aberrant metaphases. In our experiments, BXN may have acted as an antioxidant by intercepting free radicals generated by cDDP. The data obtained in the present study suggest that dietary carotenoids may act as protective agents against clastogenic effects of antitumor agents. However, extensive studies are necessary to elucidate the mechanism of action of BXN before its therapeutic use.

  15. 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.

  16. [Carotenoids: 2. Diseases and supplementation studies].

    Science.gov (United States)

    Faure, H; Fayol, V; Galabert, C; Grolier, P; Moël, G L; Stephens, J; Nabet, F

    1999-05-01

    Inverse correlations have been found in most studies on the relationship between dietary intake and plasma concentrations of carotenoids on one side and degenerative diseases such as cancer and cardiovascular diseases on the other side. Protective effects of carotenoids have been found for pathologies of the retina and the skin. Concentrations of these molecules in blood are lower in digestive pathologies and HIV. Short- and long-term toxicity of carotenoids was found to be low. In combination with the beneficial effects found for diets rich in carotenoids, this has initiated trials with relatively high doses of carotenoid supplements. In the study in Linxian (China) in a rural population with poor nutritional status, supplementation with beta-carotene, zinc, selenium and vitamin E lowered total mortality and mortality from stomach cancer. Other studies (ATBC, Caret.) on well-fed subjects did not show beneficial effects on mortality from cancer and cardiovascular diseases. On the contrary, higher mortality and lung cancer incidence was found in supplemented subjects that were also exposed to asbestos and cigarette smoke. In these studies, doses of supplemental beta-carotene were high and varied from 20 to 50 mg/day. One still ongoing study, called Suvimax, doses subjects for eight years with a cocktail of vitamins and minerals including 6 mg per day of beta-carotene. This supplementation with physiologically seen more "normal" doses might give clarity on the question if beta-carotene is the protective factor in fruits and vegetables.

  17. Carotenoids: potential allies of cardiovascular health?

    Science.gov (United States)

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

    2015-01-01

    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. PMID:25660385

  18. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1982-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  19. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1981-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in nonpolar solvents (cyclohexane, carbon tetrachloride, n-butyl chloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations (k about 10 11 l mol -1 s -1 ). These cations dimerize in a diffusion-controlled reaction (k approximately 10 10 l mol -1 s -1 ). The next step of chain-growth is slower by 3 to 4 orders of magnitude. Furthermore, in carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of the radical cations with the solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The established reaction mechanism shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  20. Observation of an aromatic radical anion dimer: (C10F8)2 sm-bullet -

    International Nuclear Information System (INIS)

    Werst, D.W.

    1994-01-01

    Radical cation dimers are observed for many alkenes and aromatic hydrocarbons as products of the reaction between monomer radical cation and neutral molecule. In most cases, the dimer radical anions, formed via reaction of the monomer radical anion with a neutral molecule, have not been observed. Here we report the observation of the dimer radical anion of octafluoronaphthalene, formed by reaction of C 10 F 8 ·- with the neutral parent molecules in nonpolar solvents following pulse radiolysis. Both monomer and dimer ions have been characterized by EPR spectra obtained by the time-resolved fluorescence-detected magnetic resonance

  1. An in vitro digestion method adapted for carotenoids and carotenoid esters: moving forward towards standardization.

    Science.gov (United States)

    Rodrigues, Daniele Bobrowski; Mariutti, Lilian Regina Barros; Mercadante, Adriana Zerlotti

    2016-12-07

    In vitro digestion methods are a useful approach to predict the bioaccessibility of food components and overcome some limitations or disadvantages associated with in vivo methodologies. Recently, the INFOGEST network published a static method of in vitro digestion with a proposal for assay standardization. The INFOGEST method is not specific for any food component; therefore, we aimed to adapt this method to assess the in vitro bioaccessibility of carotenoids and carotenoid esters in a model fruit (Byrsonima crassifolia). Two additional steps were coupled to the in vitro digestion procedure, centrifugation at 20 000g for the separation of the aqueous phase containing mixed micelles and exhaustive carotenoid extraction with an organic solvent. The effect of electrolytes, enzymes and bile acids on carotenoid micellarization and stability was also tested. The results were compared with those found with a simpler method that has already been used for carotenoid bioaccessibility analysis. These values were in the expected range for free carotenoids (5-29%), monoesters (9-26%) and diesters (4-28%). In general, the in vitro bioaccessibility of carotenoids assessed by the adapted INFOGEST method was significantly higher (p < 0.05) than those assessed by the simplest protocol, with or without the addition of simulated fluids. Although no trend was observed, differences in bioaccessibility values depended on the carotenoid form (free, monoester or diester), isomerization (Z/E) and the in vitro digestion protocol. To the best of our knowledge, it was the first time that a systematic identification of carotenoid esters by HPLC-DAD-MS/MS after in vitro digestion using the INFOGEST protocol was carried out.

  2. Photodegradation of carotenoids in human subjects

    International Nuclear Information System (INIS)

    Roe, D.A.

    1987-01-01

    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

  3. The intake of carotenoids in Denmark

    DEFF Research Database (Denmark)

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

    2000-01-01

    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 alpha-carotene, beta-carotene, lutein and lycopene, contributed...... significantly to the intake. Women had a 6 g/day higher intake of carrots than men (p zero (5.0 g/day for men and 5.9 g/day for women) indicating that almost everybody consumed at least...

  4. Carotenoids and retinoids: molecular aspects and health issues

    National Research Council Canada - National Science Library

    Packer, Lester

    2005-01-01

    ... are byproducts of metabolism in humans. Indeed, the presence of carotenoids in the diet and their role in human health has become a subject of unprecedented interest. Some carotenoids are called provitamin A compounds because they are precursors of retinol and retinoic acid. The type of carotenoids found in human plasma depends on the...

  5. 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.

    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

  6. Carotenoid levels in human lymphocytes, measured by Raman microspectroscopy

    NARCIS (Netherlands)

    Ramanauskaite, R.; Ramanauskaite, Regina B.; Segers-Nolten, Gezina M.J.; de Grauw, C.J.; de Grauw, Kees J.; Sijtsema, N.M.; van der Maas, Louis; Greve, Jan; Otto, Cornelis; Figdor, Carl

    1997-01-01

    Carotenoid levels in lymphocytes obtained from peripheral blood of healthy people have been investigated by Raman microspectroscopy. We observed that carotenoids are concentrated in so-called “Gall bodies”. The level of carotenoids in living human lymphocytes was found to be age-dependent and to

  7. 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

  8. Carotenoid levels in human lymphocytes, measured by Raman microspectroscopy

    NARCIS (Netherlands)

    Ramanauskaite, R B; SegersNolten, IGMJ; DeGrauw, K J; Sijtsema, N M; VanderMaas, L; Greve, J; Otto, C; Figdor, C G

    1997-01-01

    Carotenoid levels in lymphocytes obtained from peripheral blood of healthy people have been investigated by Raman microspectroscopy. We observed that carotenoids are concentrated in so-called ''Gall bodies''. The level of carotenoids in living human lymphocytes was found to be age-dependent and to

  9. Isomerization of propargyl cation to cyclopropenyl cation ...

    Indian Academy of Sciences (India)

    step) for isomeri- zation of the linear propargyl cation to ..... C3, C4 and C5. The ZPE corrections in each case are derived from the. B3LYP calculations. ..... the converse of which gives the relative capacity of the. LPD's to stabilize TS6 with respect ...

  10. UV Action Spectroscopy of Gas-Phase Peptide Radicals.

    Science.gov (United States)

    Nguyen, Huong T H; Shaffer, Christopher J; Pepin, Robert; Tureček, František

    2015-12-03

    UV photodissociation (UVPD) action spectroscopy is reported to provide a sensitive tool for the detection of radical sites in gas-phase peptide ions. UVPD action spectra of peptide cation radicals of the z-type generated by electron-transfer dissociation point to the presence of multiple structures formed as a result of spontaneous isomerizations by hydrogen atom migration. N-terminal Cα radicals are identified as the dominant components, but the content of isomers differing in the radical defect position in the backbone or side chain depends on the nature of the aromatic residue with phenylalanine being more prone to isomerization than tryptophan. These results illustrate that spontaneous hydrogen atom migrations can occur in peptide cation-radicals upon electron-transfer dissociation.

  11. Carotenoids Database: structures, chemical fingerprints and distribution among organisms.

    Science.gov (United States)

    Yabuzaki, Junko

    2017-01-01

    To promote understanding of how organisms are related via carotenoids, either evolutionarily or symbiotically, or in food chains through natural histories, we built the Carotenoids Database. This provides chemical information on 1117 natural carotenoids with 683 source organisms. For extracting organisms closely related through the biosynthesis of carotenoids, we offer a new similarity search system 'Search similar carotenoids' using our original chemical fingerprint 'Carotenoid DB Chemical Fingerprints'. These Carotenoid DB Chemical Fingerprints describe the chemical substructure and the modification details based upon International Union of Pure and Applied Chemistry (IUPAC) semi-systematic names of the carotenoids. The fingerprints also allow (i) easier prediction of six biological functions of carotenoids: provitamin A, membrane stabilizers, odorous substances, allelochemicals, antiproliferative activity and reverse MDR activity against cancer cells, (ii) easier classification of carotenoid structures, (iii) partial and exact structure searching and (iv) easier extraction of structural isomers and stereoisomers. We believe this to be the first attempt to establish fingerprints using the IUPAC semi-systematic names. For extracting close profiled organisms, we provide a new tool 'Search similar profiled organisms'. Our current statistics show some insights into natural history: carotenoids seem to have been spread largely by bacteria, as they produce C30, C40, C45 and C50 carotenoids, with the widest range of end groups, and they share a small portion of C40 carotenoids with eukaryotes. Archaea share an even smaller portion with eukaryotes. Eukaryotes then have evolved a considerable variety of C40 carotenoids. Considering carotenoids, eukaryotes seem more closely related to bacteria than to archaea aside from 16S rRNA lineage analysis. : http://carotenoiddb.jp. © The Author(s) 2017. Published by Oxford University Press.

  12. Carotenoid pigments in Rosa mosqueta hips, an alternative carotenoid source for foods.

    Science.gov (United States)

    Hornero-Méndez, D; Mínguez-Mosquera, M I

    2000-03-01

    Carotenoid composition has been investigated in Rosa mosqueta hips (Rosa rubiginosa, Rosa eglanteria). Six major carotenoids were identified (beta-carotene, lycopene, rubixanthin, gazaniaxanthin, beta-cryptoxanthin, and zeaxanthin) together with other minor carotenoids (violaxanthin, antheraxanthin, and gamma-carotene). An average composition has been estimated as follows: beta-carotene (497.6 mg/kg of dry wt), lycopene (391.9 mg/kg of dry wt), rubixanthin (703.7 mg/kg of dry wt), gazaniaxanthin (289.2 mg/kg of dry wt), beta-cryptoxanthin (183.5 mg/kg of dry wt), zeaxanthin (266. 6 mg/kg of dry wt), and minor carotenoids (67.1 mg/kg of dry wt). Possible uses in food technology are outlined and discussed including the preparation of highly colored oleoresins as natural colorants of food and beverages and as provitamin A sources.

  13. 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

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

    Science.gov (United States)

    2010-01-01

    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 function based solely on

  15. 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

  16. Patterns of serum carotenoid accumulation and skin colour variation in kestrel nestlings in relation to breeding conditions and different terms of carotenoid supplementation

    NARCIS (Netherlands)

    Casagrande, Stefania; Costantini, David; Fanfani, Alberto; Tagliavini, James; Dell'Omo, Giacomo

    Carotenoids are pigments synthesised by autotrophic organisms. For nestlings of raptorial species, which obtain carotenoids from the consumption of other heterotrophic species, the access to these pigments can be crucial. Carotenoids, indeed, have fundamental health maintenance functions, especially

  17. Carotenoid content, sensory properties and microbiological quality ...

    African Journals Online (AJOL)

    The carotenoid content, sensory properties and microbiological assessment of stored cassava fufu from two cultivars of yellow cassava (TMS 01/1368 and TMS 01/1412) being multiplied for distribution in South-East and South-South Nigeria were investigated using standard techniques. There is scanty information on ...

  18. 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

  19. Molecular Cloning and Characterization of Carotenoid Pathway Genes and Carotenoid Content in Ixeris dentata var. albiflora

    Directory of Open Access Journals (Sweden)

    Chinreddy Subramanyam Reddy

    2017-08-01

    Full Text Available Ixeris dentata var. albiflora is considered as a potential therapeutic agent against mithridatism, calculous, indigestion, pneumonia, hepatitis, and tumors as well as good seasoned vegetable in Far East countries. Phytoene synthase (PSY, phytoene desaturase (PDS ξ-carotene desaturase (ZDS, lycopene β-cyclase (LCYB, lycopene ε-cyclase (LCYE, ε-ring carotene hydroxylase (CHXB, and zeaxanthin epoxidase (ZDS are vital enzymes in the carotenoid biosynthesis pathway. We have examined these seven genes from I. dentata that are participated in carotenoid biosynthesis utilizing an Illumina/Solexa HiSeq 2000 platform. In silico analysis of the seven deduced amino acid sequences were revealed its closest homology with other Asteracea plants. Further, we explored transcript levels and carotenoid accumulation in various organs of I. dentata using quantitative real time PCR and high-performance liquid chromatography, respectively. The highest transcript levels were noticed in the leaf for all the genes while minimal levels were noticed in the root. The maximal carotenoid accumulation was also detected in the leaf. We proposed that these genes expressions are associated with the accumulation of carotenoids. Our findings may suggest the fundamental clues to unravel the molecular insights of carotenoid biosynthesis in various organs of I. dentata.

  20. Resonance Raman Spectroscopic Evaluation of Skin Carotenoids as a Biomarker of Carotenoid Status for Human Studies

    Science.gov (United States)

    Mayne, Susan T.; Cartmel, Brenda; Scarmo, Stephanie; Jahns, Lisa; Ermakov, Igor V.; Gellermann, Werner

    2013-01-01

    Resonance Raman Spectroscopy (RRS) is a non-invasive method that has been developed to assess carotenoid status in human tissues including human skin in vivo. Skin carotenoid status has been suggested as a promising biomarker for human studies. This manuscript describes research done relevant to the development of this biomarker, including its reproducibility, validity, feasibility for use in field settings, and factors that affect the biomarker such as diet, smoking, and adiposity. Recent studies have evaluated the response of the biomarker to controlled carotenoid interventions, both supplement-based and dietary [e.g., provision of a high-carotenoid fruit and vegetable (F/V)-enriched diet], demonstrating consistent response to intervention. The totality of evidence supports the use of skin carotenoid status as an objective biomarker of F/V intake, although in the cross-sectional setting, diet explains only some of the variation in this biomarker. However, this limitation is also a strength in that skin carotenoids may effectively serve as an integrated biomarker of health, with higher status reflecting greater F/V intake, lack of smoking, and lack of adiposity. Thus, this biomarker holds promise as both a health biomarker and an objective indicator of F/V intake, supporting its further development and utilization for medical and public health purposes. PMID:23823930

  1. A Carotenoid Health Index Based on Plasma Carotenoids and Health Outcomes

    Science.gov (United States)

    Donaldson, Michael S.

    2011-01-01

    While there have been many studies on health outcomes that have included measurements of plasma carotenoids, this data has not been reviewed and assembled into a useful form. In this review sixty-two studies of plasma carotenoids and health outcomes, mostly prospective cohort studies or population-based case-control studies, are analyzed together to establish a carotenoid health index. Five cutoff points are established across the percentiles of carotenoid concentrations in populations, from the tenth to ninetieth percentile. The cutoff points (mean ± standard error of the mean) are 1.11 ± 0.08, 1.47 ± 0.08, 1.89 ± 0.08, 2.52 ± 0.13, and 3.07 ± 0.20 µM. For all cause mortality there seems to be a low threshold effect with protection above every cutoff point but the lowest. But for metabolic syndrome and cancer outcomes there tends to be significant positive health outcomes only above the higher cutoff points, perhaps as a triage effect. Based on this data a carotenoid health index is proposed with risk categories as follows: very high risk: 4 µM. Over 95 percent of the USA population falls into the moderate or high risk category of the carotenoid health index. PMID:22292108

  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. 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

    2015-08-25

    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.

  4. Changes in the Polyphenolic Profile, Carotenoids and Antioxidant Potential of Apricot (Prunus armeniaca L. Leaves during Maturation

    Directory of Open Access Journals (Sweden)

    Alam Zeb

    2017-02-01

    Full Text Available Apricot (Prunus armeniaca L. leaves were studied to assess the potential of apricot leaves for future studies and their applications in nutraceutical and bioactive functional ingredients. The changes in the phenolic profile, carotenoids, pigments and antioxidant potential were studied at four maturation stages. Polyphenols and carotenoids were studied using reversed-phase HPLC-DAD. Pigments, total phenolic contents and radical scavenging activity were also measured. Results revealed twelve phenolic compounds in the apricot leaves. The major phenolic compounds were 3-O-caffeoylquinic acid (14.6–49.6 mg/g, 4-O-caffeoylquinic acid (0.56–7.5 mg/g, 5-O-caffeoylquinic acid (5.6–25.7 mg/g and quercetin-3-O-glucosides (8.6–19.9 mg/g, while others include caffeic acid and derivatives of coumaric acid and kaempferol. Significant changes were observed in polyphenolic compounds during maturation. Lutein (56.7–65.7 µg/g, neoxanthin (0.66–4.79 µg/g, 5,6-epoxy-α-carotene (5.89–7.9 µg/g, and β-carotene (12.3–26.9 µg/g were the major carotenoids. There were significant variations in the carotenoids, pigment contents, total phenolic contents and radical scavenging activity during maturation. In conclusion, significant variation occurred in the polyphenolic profile, carotenoids contents and antioxidant potential of apricot leaves under the studied conditions.

  5. A review on factors influencing bioaccessibility and bioefficacy of carotenoids.

    Science.gov (United States)

    Priyadarshani, A M B

    2017-05-24

    Vitamin A deficiency is one of the most prevalent deficiency disorders in the world. As shown by many studies plant food based approaches have a real potential on prevention of vitamin A deficiency in a sustainable way. Carotenoids are important as precursors of vitamin A as well as for prevention of cancers, coronary heart diseases, age-related macular degeneration, cataract etc. Bioaccessibility and bioefficacy of carotenoids are known to be influenced by numerous factors including dietary factors such as fat, fiber, dosage of carotenoid, location of carotenoid in the plant tissue, heat treatment, particle size of food, carotenoid species, interactions among carotenoids, isomeric form and molecular linkage and subject characteristics. Therefore even when carotenoids are found in high quantities in plant foods their utilization may be unsatisfactory because some factors are known to interfere as negative effectors.

  6. 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.

  7. 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...

  8. Electronic Spectra of the Tetraphenylcyclobutadienecyclopentadienylnickel(II) Cation and Radical

    Czech Academy of Sciences Publication Activity Database

    Craig, P. R.; Havlas, Zdeněk; Trujillo, M.; Rempala, P.; Kirby, J. P.; Miller, J. R.; Noll, B. C.; Michl, Josef

    2016-01-01

    Roč. 120, č. 20 (2016), s. 3456-3462 ISSN 1089-5639 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : cyclobutadiene-metal complexes * tetragonal star connectors * square grid polymer * halides Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.847, year: 2016

  9. Cation Exchange Water Softeners

    Science.gov (United States)

    WaterSense released a notice of intent to develop a specification for cation exchange water softeners. The program has made the decision not to move forward with a spec at this time, but is making this information available.

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

    Energy Technology Data Exchange (ETDEWEB)

    Krot, N.N. [Russian Academy of Sciences, Institute of Physical Chemistry (Russian Federation); Saeki, Masakatsu [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2003-03-01

    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)

  11. 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.

  12. Marine carotenoids: Bioactivities and potential benefits to human health.

    Science.gov (United States)

    Chuyen, Hoang Van; Eun, Jong-Bang

    2017-08-13

    Among natural pigments, carotenoids play important roles in physiological functions. The characteristics of carotenoids and their effects on human health have been reported for a long time, but most studies have focused on carotenoids from vegetables, fruits, and other parts of higher plants. Few reports are available on carotenoids from marine sources, such as seaweeds, microalgae, and marine animals, which have attracted attention in recent decades. Hundreds of carotenoids have been identified and isolated from marine organisms and their beneficial physiological functions, such as anticancer, antiobesity, antidiabetic, anti-inflammatory, and cardioprotective activities have been reported. The purpose of this review is to discuss the literature on the beneficial bioactivities of some of the most abundant marine carotenoids, including fucoxanthin, astaxanthin, cantaxanthin, peridinin, fucoxanthinol, and halocynthiaxanthin.

  13. Development of a rapid, simple assay of plasma total carotenoids

    Science.gov (United States)

    2012-01-01

    Background Plasma total carotenoids can be used as an indicator of risk of chronic disease. Laboratory analysis of individual carotenoids by high performance liquid chromatography (HPLC) is time consuming, expensive, and not amenable to use beyond a research laboratory. The aim of this research is to establish a rapid, simple, and inexpensive spectrophotometric assay of plasma total carotenoids that has a very strong correlation with HPLC carotenoid profile analysis. Results Plasma total carotenoids from 29 volunteers ranged in concentration from 1.2 to 7.4 μM, as analyzed by HPLC. A linear correlation was found between the absorbance at 448 nm of an alcohol / heptane extract of the plasma and plasma total carotenoids analyzed by HPLC, with a Pearson correlation coefficient of 0.989. The average coefficient of variation for the spectrophotometric assay was 6.5% for the plasma samples. The limit of detection was about 0.3 μM and was linear up to about 34 μM without dilution. Correlations between the integrals of the absorption spectra in the range of carotenoid absorption and total plasma carotenoid concentration gave similar results to the absorbance correlation. Spectrophotometric assay results also agreed with the calculated expected absorbance based on published extinction coefficients for the individual carotenoids, with a Pearson correlation coefficient of 0.988. Conclusion The spectrophotometric assay of total carotenoids strongly correlated with HPLC analysis of carotenoids of the same plasma samples and expected absorbance values based on extinction coefficients. This rapid, simple, inexpensive assay, when coupled with the carotenoid health index, may be useful for nutrition intervention studies, population cohort studies, and public health interventions. PMID:23006902

  14. ProCarDB: a database of bacterial carotenoids.

    Science.gov (United States)

    Nupur, L N U; Vats, Asheema; Dhanda, Sandeep Kumar; Raghava, Gajendra P S; Pinnaka, Anil Kumar; Kumar, Ashwani

    2016-05-26

    Carotenoids have important functions in bacteria, ranging from harvesting light energy to neutralizing oxidants and acting as virulence factors. However, information pertaining to the carotenoids is scattered throughout the literature. Furthermore, information about the genes/proteins involved in the biosynthesis of carotenoids has tremendously increased in the post-genomic era. A web server providing the information about microbial carotenoids in a structured manner is required and will be a valuable resource for the scientific community working with microbial carotenoids. Here, we have created a manually curated, open access, comprehensive compilation of bacterial carotenoids named as ProCarDB- Prokaryotic Carotenoid Database. ProCarDB includes 304 unique carotenoids arising from 50 biosynthetic pathways distributed among 611 prokaryotes. ProCarDB provides important information on carotenoids, such as 2D and 3D structures, molecular weight, molecular formula, SMILES, InChI, InChIKey, IUPAC name, KEGG Id, PubChem Id, and ChEBI Id. The database also provides NMR data, UV-vis absorption data, IR data, MS data and HPLC data that play key roles in the identification of carotenoids. An important feature of this database is the extension of biosynthetic pathways from the literature and through the presence of the genes/enzymes in different organisms. The information contained in the database was mined from published literature and databases such as KEGG, PubChem, ChEBI, LipidBank, LPSN, and Uniprot. The database integrates user-friendly browsing and searching with carotenoid analysis tools to help the user. We believe that this database will serve as a major information centre for researchers working on bacterial carotenoids.

  15. Comparison of the Proximate Composition, Total Carotenoids and Total Polyphenol Content of Nine Orange-Fleshed Sweet Potato Varieties Grown in Bangladesh

    Directory of Open Access Journals (Sweden)

    Mohammad Khairul Alam

    2016-09-01

    Full Text Available In an attempt to develop the food composition table for Bangladesh, the nutritional composition of nine varieties of orange-fleshed sweet potato was analyzed together with total carotenoids (TCC and total polyphenol content (TPC. Each variety showed significant variation in different nutrient contents. The quantification of the TCC and TPC was done by spectrophotometric measurement, and the proximate composition was done by the AOAC method. The obtained results showed that total polyphenol content varied from 94.63 to 136.05 mg gallic acid equivalent (GAE/100 g fresh weight. Among the selected sweet potatoes, Bangladesh Agricultural Research Institute (BARI Sweet Potato 7 (SP7 contained the highest, whereas BARI SP6 contained the lowest amount of total polyphenol content. The obtained results also revealed that total carotenoids content ranged from 0.38 to 7.24 mg/100 g fresh weight. BARI SP8 showed the highest total carotenoids content, whereas BARI SP6 showed the lowest. Total carotenoids content was found to be higher in dark orange-colored flesh varieties than their light-colored counterparts. The results of the study indicated that selected sweet potato varieties are rich in protein and carbohydrate, low in fat, high in polyphenol and carotenoids and, thus, could be a good source of dietary antioxidants to prevent free radical damage, which leads to chronic diseases, and also to prevent vitamin A malnutrition.

  16. Comparison of the Proximate Composition, Total Carotenoids and Total Polyphenol Content of Nine Orange-Fleshed Sweet Potato Varieties Grown in Bangladesh.

    Science.gov (United States)

    Alam, Mohammad Khairul; Rana, Ziaul Hasan; Islam, Sheikh Nazrul

    2016-09-14

    In an attempt to develop the food composition table for Bangladesh, the nutritional composition of nine varieties of orange-fleshed sweet potato was analyzed together with total carotenoids (TCC) and total polyphenol content (TPC). Each variety showed significant variation in different nutrient contents. The quantification of the TCC and TPC was done by spectrophotometric measurement, and the proximate composition was done by the AOAC method. The obtained results showed that total polyphenol content varied from 94.63 to 136.05 mg gallic acid equivalent (GAE)/100 g fresh weight. Among the selected sweet potatoes, Bangladesh Agricultural Research Institute (BARI) Sweet Potato 7 (SP7) contained the highest, whereas BARI SP6 contained the lowest amount of total polyphenol content. The obtained results also revealed that total carotenoids content ranged from 0.38 to 7.24 mg/100 g fresh weight. BARI SP8 showed the highest total carotenoids content, whereas BARI SP6 showed the lowest. Total carotenoids content was found to be higher in dark orange-colored flesh varieties than their light-colored counterparts. The results of the study indicated that selected sweet potato varieties are rich in protein and carbohydrate, low in fat, high in polyphenol and carotenoids and, thus, could be a good source of dietary antioxidants to prevent free radical damage, which leads to chronic diseases, and also to prevent vitamin A malnutrition.

  17. Carotenoids and Carotenoid Esters of Red and Yellow Physalis (Physalis alkekengi L. and P. pubescens L.) Fruits and Calyces.

    Science.gov (United States)

    Wen, Xin; Hempel, Judith; Schweiggert, Ralf M; Ni, Yuanying; Carle, Reinhold

    2017-08-02

    Carotenoid profiles of fruits and calyces of red (Physalis alkekengi L.) and yellow (P. pubescens L.) Physalis were characterized by HPLC-DAD-APCI-MS n . Altogether 69 carotenoids were detected in red Physalis, thereof, 45 were identified. In yellow Physalis, 40 carotenoids were detected and 33 were identified. Zeaxanthin esters with various fatty acids were found to be the most abundant carotenoids in red Physalis, accounting for 51-63% of total carotenoids, followed by β-cryptoxanthin esters (16-24%). In yellow Physalis, mainly free carotenoids such as lutein and β-carotene were found. Total carotenoid contents ranged between 19.8 and 21.6 mg/100 g fresh red Physalis fruits and 1.28-1.38 mg/100 g fresh yellow Physalis fruits, demonstrating that Physalis fruits are rich sources of dietary carotenoids. Yellow Physalis calyces contained only 153-306 μg carotenoids/g dry weight, while those of red Physalis contained substantially higher amounts (14.6-17.6 mg/g dry weight), thus possibly exhibiting great potential as a natural source for commercial zeaxanthin extraction.

  18. A radical approach to radical innovation

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

  19. Identifi cation of Sectarianism

    Directory of Open Access Journals (Sweden)

    Martinovich Vladimir

    2016-03-01

    Full Text Available «New religious movements and society» is traditionally one of the most sophisticated topics in the area of new religions studies. Its problem field is so huge that up to now by far not all important research themes where even touched by scientists from all over the world. The problem of the process of the identification of sectarianism by diff erent societal institutions is one of such untouched themes that is taken as the main subject of this article. This process by itself is an inseparable part of the every societal deliberate reaction to the very existence of unconventional religiosity, its unstructured and mainly structured types. The focal point of the article is step-by-step analysis of the general structure elements of the process of the identification of sectarianism without any reference to the specific time and place of its flow. Special attention is paid to the analysis of the subjects of the identification of sectarianism, to the criteria for religious groups to be qualified as new religious movements, and to the specific features of the process of documents filtration. The causes of selective perception of sectarianism are disclosed. Some main consequences and unpredictable outcomes of the process of the identification of sectarianism are described.

  20. Health Effects of Carotenoids during Pregnancy and Lactation

    Directory of Open Access Journals (Sweden)

    Monika A. Zielińska

    2017-08-01

    Full Text Available Adequate nutrition is particularly important during pregnancy since it is needed not only for maintaining the health of the mother, but also determines the course of pregnancy and its outcome, fetus development as well as the child’s health after birth and during the later period of life. Data coming from epidemiological and interventions studies support the observation that carotenoids intake provide positive health effects in adults and the elderly population. These health effects are the result of their antioxidant and anti-inflammatory properties. Recent studies have also demonstrated the significant role of carotenoids during pregnancy and infancy. Some studies indicate a correlation between carotenoid status and lower risk of pregnancy pathologies induced by intensified oxidative stress, but results of these investigations are equivocal. Carotenoids have been well studied in relation to their beneficial role in the prevention of preeclampsia. It is currently hypothesized that carotenoids can play an important role in the prevention of preterm birth and intrauterine growth restriction. Carotenoid status in the newborn depends on the nutritional status of the mother, but little is known about the transfer of carotenoids from the mother to the fetus. Carotenoids are among the few nutrients found in breast milk, in which the levels are determined by the mother’s diet. Nutritional status of the newborn directly depends on its diet. Both mix feeding and artificial feeding may cause depletion of carotenoids since infant formulas contain only trace amounts of these compounds. Carotenoids, particularly lutein and zeaxanthin play a significant role in the development of vision and nervous system (among others, they are important for the development of retina as well as energy metabolism and brain electrical activity. Furthermore, more scientific evidence is emerging on the role of carotenoids in the prevention of disorders affecting preterm

  1. [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% (pisolate has an antioxidant

  2. Expression of carotenoid biosynthetic pathway genes and changes in carotenoids during ripening in tomato (Lycopersicon esculentum).

    Science.gov (United States)

    Namitha, Kanakapura Krishnamurthy; Archana, Surya Narayana; Negi, Pradeep Singh

    2011-04-01

    To study the expression pattern of carotenoid biosynthetic pathway genes, changes in their expression at different stages of maturity in tomato fruit (cv. Arka Ahuti) were investigated. The genes regulating carotenoid production were quantified by a dot blot method using a DIG (dioxigenin) labelling and detection kit. The results revealed that there was an increase in the levels of upstream genes of the carotenoid biosynthetic pathway such as 1-deoxy-d-xylulose-5-phosphate reductoisomerase (DXR), 4-hydroxy-3-methyl-but-2-enyl diphosphate reductase (Lyt B), phytoene synthase (PSY), phytoene desaturase (PDS) and ζ-carotene desaturase (ZDS) by 2-4 fold at the breaker stage as compared to leaf. The lycopene and β-carotene content was analyzed by HPLC at different stages of maturity. The lycopene (15.33 ± 0.24 mg per 100 g) and β-carotene (10.37 ± 0.46 mg per 100 g) content were found to be highest at 5 days post-breaker and 10 days post-breaker stage, respectively. The lycopene accumulation pattern also coincided with the color values at different stages of maturity. These studies may provide insight into devising gene-based strategies for enhancing carotenoid accumulation in tomato fruits.

  3. Ultrafast spectroscopy tracks carotenoid configurations in the orange and red carotenoid proteins from cyanobacteria

    Czech Academy of Sciences Publication Activity Database

    Šlouf, V.; Kuznetsova, V.; Fuciman, M.; de Carbon, C.B.; Wilson, A.; Kirilowsky, D.; Polívka, Tomáš

    2017-01-01

    Roč. 131, č. 1 (2017), s. 105-117 ISSN 0166-8595 R&D Projects: GA ČR GBP501/12/G055 Institutional support: RVO:60077344 Keywords : Intramolecular charge-transfer state * Non-photochemical quenching * Orange carotenoid protein Subject RIV: BO - Biophysics OBOR OECD: Biophysics Impact factor: 3.864, year: 2016

  4. 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

  5. Contemporary Radical Economics.

    Science.gov (United States)

    Sherman, Howard J.

    1984-01-01

    The origins of contemporary radical economics are examined. Applications of radical economics to price and value theory, labor segmentation theory, business cycles, industrial organization, government and business, imperialism and development, and comparative systems are reviewed. (Author/RM)

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

    International Nuclear Information System (INIS)

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

    2000-01-01

    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

  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 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

  9. 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.

  10. 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)

    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 ω 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

  11. 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.

  12. Carotenoids biosynthesis and cleavage related genes from bacteria to plants.

    Science.gov (United States)

    Liang, Ming-Hua; Zhu, Jianhua; Jiang, Jian-Guo

    2017-06-13

    Carotenoids are essential for photosynthesis and photoprotection in photosynthetic organisms and beneficial for human health. Apocarotenoids derived from carotenoid degradation can serve critical functions including hormones, volatiles, and signals. They have been used commercially as food colorants, animal feed supplements, and nutraceuticals for cosmetic and pharmaceutical purposes. This review focuses on the molecular evolution of carotenogenic enzymes and carotenoid cleavage oxygenases (CCOs) from bacteria, fungi, cyanobacteria, algae, and plants. The diversity of carotenoids and apocarotenoids as well as their complicated biosynthetic pathway in different species can shed light on the history of early molecular evolution. Some carotenogenic genes (such as phytoene synthases) have high protein sequence similarity from bacteria to land plants, but some (such as phytoene desaturases, lycopene cyclases, carotenoid hydroxylases, and CCOs) have low similarity. The broad diversity of apocarotenoid volatile compounds can be attributed to large numbers of carotenoid precursors and the various cleavage sites catalyzed by CCOs enzymes. A variety of carotenogenic enzymes and CCOs indicate the functional diversification of carotenoids and apocrotenoids in different species. New carotenoids, new apocarotenoids, new carotenogenic enzymes, new CCOs, and new pathways still need to be explored.

  13. Differential expression of carotenoid biosynthetic pathway genes in ...

    Indian Academy of Sciences (India)

    2016-08-26

    Aug 26, 2016 ... Tomato (Solanum lycopersicum L.) is one of the model plants to study the carotenoid biosynthesis. In the present study, the fruit carotenoid content were quantified at different developmental stages for two contrasting genotypes viz. IIHR-249-1and IIHR-2866 by UPLC. Lycopene content was high in ...

  14. 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.

  15. Differential expression of carotenoid biosynthetic pathway genes in ...

    Indian Academy of Sciences (India)

    2016-04-08

    Apr 8, 2016 ... Carotenoids are a group of pigments that are red, yellow and orange in colour, present in flowers, fruits and vegetables. Carotenoids are not only present in plants, but also in algae. (cyanobacteria) and non-photosynthetic organisms like fun- gi. ..... for the production of β-carotene and xanthophylls in plants.

  16. (gnld) and carrot extracted carotenoids on immune param

    African Journals Online (AJOL)

    Summary: The immunomodulatory effect of Carotenoid complex from Golden Neo-Life Dynamite. (GNLD) and carrot extracted Carotenoid was assessed using 24 albino Wistar rats. The rats were assigned to 4 groups of 6 rats each consisting of group 1(control group treated with distilled water), group 2 (treated with olive ...

  17. Comparative effect of carotenoid complex from golden neo-life ...

    African Journals Online (AJOL)

    Summary: The immunomodulatory effect of Carotenoid complex from Golden Neo-Life Dynamite (GNLD) and carrot extracted Carotenoid was assessed using 24 albino Wistar rats. The rats were assigned to 4 groups of 6 rats each consisting of group 1(control group treated with distilled water), group 2 (treated with olive oil) ...

  18. 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.

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

    NARCIS (Netherlands)

    Beekwilder, M.J.; Meer, van der I.M.; Simic, A.; Uitdewilligen, J.; Arkel, van J.; Vos, de C.H.; Jonker, H.H.; Verstappen, F.W.A.; Bouwmeester, H.J.; Sibbesen, O.; Qvist, I.; Mikkelsen, J.D.; Hall, R.D.

    2008-01-01

    Carotenoids are important lipophilic antioxidants in fruits. Apocarotenoids such as ¿-ionone and ß-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

  20. 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.

  1. Carotenoids from microalgae: A review of recent developments.

    Science.gov (United States)

    Gong, Mengyue; Bassi, Amarjeet

    2016-12-01

    Carotenoids have been receiving increasing attention due to their potential health benefits. Microalgae are recognized as a natural source of carotenoids and other beneficial byproducts. However, the production of micro-algal carotenoids is not yet sufficiently cost-effective to compete with traditional chemical synthetic methods and other technologies such as extraction from plant based sources. This review presents the recent biotechnological developments in microalgal carotenoid production. The current technologies involved in their bioprocessing including cultivation, harvesting, extraction, and purification are discussed with a specific focus on downstream processing. The recent advances in chemical and biochemical synthesis of carotenoids are also reviewed for a better understanding of suitable and economically feasible biotechnological strategies. Some possible future directions are also proposed. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. 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...

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

    International Nuclear Information System (INIS)

    Prokhorova, L.I.; Revina, A.A.

    2001-01-01

    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)x10 17 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 [ru

  4. Impact of postharvest handling on carotenoid concentration and composition in high-carotenoid maize (Zea mays L.) kernels.

    Science.gov (United States)

    Burt, Andrew J; Grainger, Christopher M; Young, J Christopher; Shelp, Barry J; Lee, Elizabeth A

    2010-07-28

    High carotenoid maize is an ideal source of high value dietary carotenoids, especially lutein and zeaxanthin, in human and animal feed and has been proposed as a feedstock for high carotenoid egg production. A modified analytical method was demonstrated to have reliability, reproducibility, and improved run-time and separation of xanthophylls. This method was used to confirm the localization of carotenoids in endosperm and to determine the effects of drying and storage on carotenoid levels in maize grain. A preliminary trial using room temperature drying indicated that while carotenoid profiles remain stable during storage, carotenoid levels decrease significantly from initial levels between 3 and 6 months of storage, but then remain stable for another year. A more rigorous trial using three drying and storage regimes (freeze-drying and storage at -80 degrees C; room temperature drying and storage; 90 degrees C drying and room temperature storage) indicated that extreme caution is needed to maintain carotenoid levels in maize during handling and storage, but in situations where freeze-drying is not possible, high heat drying is no more detrimental than low heat drying.

  5. Evaluation of carotenoids and reactive oxygen species in human skin after UV irradiation: a critical comparison between in vivo and ex vivo investigations.

    Science.gov (United States)

    Meinke, Martina C; Müller, Robert; Bechtel, Anne; Haag, Stefan F; Darvin, Maxim E; Lohan, Silke B; Ismaeel, Fakher; Lademann, Jürgen

    2015-03-01

    UV irradiation is one of the most harmful exogenous factors for the human skin. In addition to the development of erythema, free radicals, that is reactive oxygen species (ROS), are induced under its influence and promote the development of oxidative stress in the skin. Several techniques are available for determining the effect of UV irradiation. Resonance Raman spectroscopy (RRS) measures the reduction of the carotenoid concentration, while electron paramagnetic resonance (EPR) spectroscopy enables the analysis of the production of free radicals. Depending on the method, the skin parameters are analysed in vivo or ex vivo. This study provides a critical comparison between in vivo and ex vivo investigations on the ROS formation and carotenoid depletion caused by UV irradiation in human skin. The oxygen content of tissue was also determined. It was shown that the antioxidant status measured in the skin samples in vivo and ex vivo was different. The depletion in the carotenoid concentration in vivo exceeded the value determined ex vivo by a factor of about 1.5, and the radical formation after UV irradiation was significantly greater in vivo by a factor of 3.5 than that measured in excised human skin, which can be explained by the lack of oxygen ex vivo. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  6. Introducing Stable Radicals into Molecular Machines.

    Science.gov (United States)

    Wang, Yuping; Frasconi, Marco; Stoddart, J Fraser

    2017-09-27

    Ever since their discovery, stable organic radicals have received considerable attention from chemists because of their unique optical, electronic, and magnetic properties. Currently, one of the most appealing challenges for the chemical community is to develop sophisticated artificial molecular machines that can do work by consuming external energy, after the manner of motor proteins. In this context, radical-pairing interactions are important in addressing the challenge: they not only provide supramolecular assistance in the synthesis of molecular machines but also open the door to developing multifunctional systems relying on the various properties of the radical species. In this Outlook, by taking the radical cationic state of 1,1'-dialkyl-4,4'-bipyridinium (BIPY •+ ) as an example, we highlight our research on the art and science of introducing radical-pairing interactions into functional systems, from prototypical molecular switches to complex molecular machines, followed by a discussion of the (i) limitations of the current systems and (ii) future research directions for designing BIPY •+ -based molecular machines with useful functions.

  7. 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

  8. [Lavoisier and radicals].

    Science.gov (United States)

    Lafont, Olivier

    2007-01-01

    Lavoisier and his co-workers (Guyton de Morveau, Bertholet, Fourcroy) considered that acids were constituted of oxygen and of something else that they called radicals. These radicals were known in some cases, i.e. nitrogen for nitrous acid, carbon for carbonic acid, phosphorus for phosphoric acid. In the case of sulfur, the sulfuric radical could be associated with different quantities of oxigen leading to sulfuric or sulfurous acids. In other cases radicals remained unknown at the time i.e. muriatic radical for muriatic acid, or benzoyl radical for benzoic acid. It is interesting to notice that Lavoisier evoked the case of compound radicals constituted of different substances such as carbon and hydrogen.

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

    Science.gov (United States)

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

    2015-07-03

    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. We identified 67 carotenoid biosynthetic genes in B. rapa, which were orthologs of the 47 carotenoid genes in A. thaliana. A high level of synteny was observed for carotenoid biosynthetic genes between A. thaliana and B. rapa. Out of 47 carotenoid biosynthetic genes in A. thaliana, 46 were successfully mapped to the 10 B. rapa chromosomes, and most of the genes retained more than one copy in B. rapa. The gene expansion was caused by the whole-genome triplication (WGT) event experienced by Brassica species. An expression analysis of the carotenoid biosynthetic genes suggested that their expression levels differed in root, stem, leaf, flower, callus, and silique tissues. Additionally, the paralogs of each carotenoid biosynthetic gene, which were generated from the WGT in B. rapa, showed significantly different expression levels among tissues, suggesting differentiated functions for these multi-copy genes in the carotenoid pathway. This first systematic study of carotenoid biosynthetic genes in B. rapa provides insights into the carotenoid metabolic mechanisms of Brassica crops. In addition, a better understanding of carotenoid biosynthetic genes in B. rapa will contribute to the development of conventional and transgenic B. rapa cultivars with enriched carotenoid levels in the future.

  10. Contemporary Radical Prostatectomy

    Directory of Open Access Journals (Sweden)

    Qiang Fu

    2011-01-01

    Full Text Available Purpose. Patients diagnosed with clinically localized prostate cancer have more surgical treatment options than in the past. This paper focuses on the procedures' oncological or functional outcomes and perioperative morbidities of radical retropubic prostatectomy, radical perineal prostatectomy, and robotic-assisted laparoscopic radical prostatectomy. Materials and Methods. A MEDLINE/PubMed search of the literature on radical prostatectomy and other new management options was performed. Results. Compared to the open procedures, robotic-assisted radical prostatectomy has no confirmed significant difference in most literatures besides less blood loss and blood transfusion. Nerve sparing is a safe means of preserving potency on well-selected patients undergoing radical prostatectomy. Positive surgical margin rates of radical prostatectomy affect the recurrence and survival of prostate cancer. The urinary and sexual function outcomes have been vastly improved. Neoadjuvant treatment only affects the rate of positive surgical margin. Adjuvant therapy can delay and reduce the risk of recurrence and improve the survival of the high risk prostate cancer. Conclusions. For the majority of patients with organ-confined prostate cancer, radical prostatectomy remains a most effective approach. Radical perineal prostatectomy remains a viable approach for patients with morbid obesity, prior pelvic surgery, or prior pelvic radiation. Robot-assisted laparoscopic prostatectomy (RALP has become popular among surgeons but has not yet become the firmly established standard of care. Long-term data have confirmed the efficacy of radical retropubic prostatectomy with disease control rates and cancer-specific survival rates.

  11. Carotenoids from Marine Organisms: Biological Functions and Industrial Applications

    Directory of Open Access Journals (Sweden)

    Christian Galasso

    2017-11-01

    Full Text Available As is the case for terrestrial organisms, carotenoids represent the most common group of pigments in marine environments. They are generally biosynthesized by all autotrophic marine organisms, such as bacteria and archaea, algae and fungi. Some heterotrophic organisms also contain carotenoids probably accumulated from food or partly modified through metabolic reactions. These natural pigments are divided into two chemical classes: carotenes (such as lycopene and α- and β-carotene that are composed of hydrogen and carbon; xanthophylls (such as astaxanthin, fucoxanthin and lutein, which are constituted by hydrogen, carbon and oxygen. Carotenoids, as antioxidant compounds, assume a key role in the protection of cells. In fact, quenching of singlet oxygen, light capture and photosynthesis protection are the most relevant biological functions of carotenoids. The present review aims at describing (i the biological functions of carotenoids and their benefits for human health, (ii the most common carotenoids from marine organisms and (iii carotenoids having large success in pharmaceutical, nutraceutical and cosmeceutical industries, highlighting the scientific progress in marine species cultivation for natural pigments production.

  12. Limiting immunopathology: Interaction between carotenoids and enzymatic antioxidant defences.

    Science.gov (United States)

    Babin, A; Saciat, C; Teixeira, M; Troussard, J-P; Motreuil, S; Moreau, J; Moret, Y

    2015-04-01

    The release of reactive oxygen and nitrogen species (ROS and RNS) during the inflammatory response generates damages to host tissues, referred to as immunopathology, and is an important factor in ecological immunology. The integrated antioxidant system, comprising endogenous antioxidant enzymes (e.g. superoxide dismutase SOD, and catalase CAT) and dietary antioxidants (e.g. carotenoids), helps to cope with immune-mediated oxidative stress. Crustaceans store large amounts of dietary carotenoids for yet unclear reasons. While being immunostimulants and antioxidants, the interaction of these pigments with antioxidant enzymes remains unclear. Here, we tested the interaction between dietary supplementation with carotenoids and immune challenge on immune defences and the activity of the antioxidant enzymes SOD and CAT, in the amphipod crustacean Gammarus pulex. Dietary supplementation increased the concentrations of circulating carotenoids and haemocytes in the haemolymph, while the immune response induced the consumption of circulating carotenoids and a drop of haemocyte density. Interestingly, supplemented gammarids exhibited down-regulated SOD activity but high CAT activity compared to control ones. Our study reveals specific interactions of dietary carotenoids with endogenous antioxidant enzymes, and further underlines the potential importance of carotenoids in the evolution of immunity and/or of antioxidant mechanisms in crustaceans. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Biotechnological production of carotenoids by yeasts: an overview

    Science.gov (United States)

    2014-01-01

    Nowadays, carotenoids are valuable molecules in different industries such as chemical, pharmaceutical, poultry, food and cosmetics. These pigments not only can act as vitamin A precursors, but also they have coloring and antioxidant properties, which have attracted the attention of the industries and researchers. The carotenoid production through chemical synthesis or extraction from plants is limited by low yields that results in high production costs. This leads to research of microbial production of carotenoids, as an alternative that has shown better yields than other aforementioned. In addition, the microbial production of carotenoids could be a better option about costs, looking for alternatives like the use of low-cost substrates as agro-industrials wastes. Yeasts have demonstrated to be carotenoid producer showing an important growing capacity in several agro-industrial wastes producing high levels of carotenoids. Agro-industrial wastes provide carbon and nitrogen source necessary, and others elements to carry out the microbial metabolism diminishing the production costs and avoiding pollution from these agro-industrial wastes to the environmental. Herein, we discuss the general and applied concepts regarding yeasts carotenoid production and the factors influencing carotenogenesis using agro-industrial wastes as low-cost substrates. PMID:24443802

  14. Carotenoid accumulation in the tissues of zebra finches: predictors of integumentary pigmentation and implications for carotenoid allocation strategies.

    Science.gov (United States)

    McGraw, Kevin J; Toomey, Matthew B

    2010-01-01

    Carotenoid pigments produce the bright yellow to red ornamental colors of many animals, especially birds, and must ultimately be derived from the diet. However, they are also valuable for many physiological functions (e.g., antioxidants, immunostimulants, photoprotection, visual tuning, yolk nourishment to embryos), and as a result they are present in numerous internal body tissues (e.g., liver, adipose tissue, retina) whose carotenoid types and amounts are rarely studied in the context of color acquisition. Because male and female animals typically place different priorities on fitness-enhancing activities (e.g., gametic investment in females, sexual attraction in males), carotenoid allocation may track such investment patterns in the two sexes, and we can test for such sex-specific priorities of carotenoids by assessing body-tissue distributions of these pigments. We used high-performance liquid chromatography to identify and quantify carotenoid pigments from the plasma, liver, adipose tissue, and retina as well as the beak and legs of male and female zebra finches (Taeniopygia guttata), a species in which males display sexually attractive, red, carotenoid-based beak coloration and females also display some (albeit a less rich orange) beak color. To our knowledge, this is the first study of the predictors of carotenoid-based leg coloration-another potentially important visual signal-in this species. The same suite of dietary (e.g., lutein, zeaxanthin, beta-cryptoxanthin) and metabolically derived (e.g., dehydrolutein, anhydrolutein) yellow and orange carotenoids was present in plasma, liver, and adipose tissue of both sexes. Retina contained two different metabolites (astaxanthin and galloxanthin) that serve specific functions in association with unique photoreceptor types in the eye. Beaks were enriched with four red ketocarotenoid derivatives in both sexes (alpha-doradexanthin, adonirubin, astaxanthin, and canthaxanthin), while the carotenoid profile of legs

  15. Antioxidants, free radicals, storage proteins, puroindolines, and proteolytic activities in bread wheat (Triticum aestivum) seeds during accelerated aging.

    Science.gov (United States)

    Calucci, Lucia; Capocchi, Antonella; Galleschi, Luciano; Ghiringhelli, Silvia; Pinzino, Calogero; Saviozzi, Franco; Zandomeneghi, Maurizio

    2004-06-30

    Seeds of bread wheat were incubated at 40 degrees C and 100% relative humidity for 0, 3, 4, 6, and 10 days. The effects of accelerated aging on seed germinability and some biochemical properties of flour (carotenoid, free radical, and protein contents and proteolytic activity) and gluten (free radical content and flexibility) were investigated. Seed germinability decreased during aging, resulting in seed death after 10 days. A progressive decrease of carotenoid content, in particular, lutein, was observed, prolonging the incubation, whereas the free radical content increased in both flour and gluten. A degradation of soluble and storage proteins was found, associated with a marked increase of proteolytic activity and a loss of viscoelastic properties of gluten. On the contrary, puroindolines were quite resistant to the treatment. The results are discussed in comparison with those previously obtained during accelerated aging of durum wheat seeds.

  16. 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

  17. Effects of high temperature frying of Spinach leaves in sunflower oil on carotenoids, chlorophylls and tocopherol composition

    Science.gov (United States)

    Zeb, Alam; Nisar, Parveen

    2017-03-01

    Spinach is one of the highly consumed vegetable, with significant nutritional and beneficial properties. This study revealed for the first time, the effects of high temperature frying on the carotenoids, chlorophylls and tocopherol contents of spinach leaves. Spinach leaves were thermally processed in the sunflower oil for 15, 30, 45 and 60 min at 250 °C. HPLC-DAD results revealed a total of eight carotenoids, four chlorophylls and α-tocopherol in the spinach leaves. Lutein, neoxanthin, violaxanthin and β-carotene-5,6-epoxide were the major carotenoids, while chlorophyll a and b' were present in higher amounts. Frying of spinach leaves increased significantly the amount of α-tocopherol, β-carotene-5,6-epoxide, luteoxanthin, lutein and its Z-isomers and chlorophyll b' isomer. There was a dose dependent decrease in the amounts of neoxanthin, violaxanthin, chlorophyll b, b' and chlorophyll a with increase of frying time. The increase of frying time increased the total phenolic contents in spinach leaves and fried sunflower oil samples. Chemical characteristics such as peroxide values, free fatty acids, conjugated dienes, conjugated trienes and radical scavenging activity were significantly affected by frying, while spinach leaves increased the stability of the frying oil. This study can be used to improve the quality of fried vegetable leaves or their products at high temperature frying in food industries for increasing consumer acceptability.

  18. Identification and quantification, by HPLC-DAD-MS/MS, of carotenoids and phenolic compounds from the Amazonian fruit Caryocar villosum.

    Science.gov (United States)

    Chisté, Renan Campos; Mercadante, Adriana Zerlotti

    2012-06-13

    The Amazonian region from Brazil has a wide variety of native and wild noncommercially cultivated fruits. This article reports for the first time the composition of carotenoids and phenolic compounds from Caryocar villosum fruit pulp, and, in addition, its proximate composition and antioxidant capacity (ORAC assay) were determined. According to the nutritional composition, water (52%) and lipids (25%) were the major components found in the pulp, and the total energetic value was 291 kcal/100 g. The major phenolic compounds identified by HPLC-DAD-ESI-MS/MS were gallic acid (182.4 μg/g pulp), followed by ellagic acid rhamnoside (107 μg/g pulp) and ellagic acid (104 μg/g pulp). The main carotenoids identified by HPLC-DAD-APCI-MS/MS were all-trans-antheraxanthin (3.4 μg/g pulp), all-trans-zeaxanthin (2.9 μg/g pulp), and a lutein-like carotenoid (2.8 μg/g pulp). The antioxidant capacity of the pulp (3.7 mMol Trolox/100 g pulp) indicates that it can be considered a good peroxyl radical scavenger.

  19. 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...... 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...

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

    Science.gov (United States)

    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 decaprenoxanthin from Cellulomonas dehydrogenans. PMID:6245065

  1. THE ISOLATION, ANALISIS AND TESTING OF SEA BUCKTHORN CAROTENOIDS ON MURINE MACROPHAGE CULTURES

    Directory of Open Access Journals (Sweden)

    ILEANA MICLEA

    2007-05-01

    Full Text Available Our aim was to characterize a sea buckthorn (Hippophae rhamnoides fruitcarotenoidic extract and evaluate its influence on macrophage phagocytic responsegiven that carotenoids function as antioxidants. Carotenoids were isolated,saponified and analysed using HPLC before and after saponification. Murineperitoneal macrophages were cultured in medium containing carotenoidic extract.Carotenoid influence on phagocytosis was assessed by calculating the phagocyticindex (PI % and mean phagocytosis (MP. The positive significant differences(p<0,05 picture carotenoid ability to enhance cell phagocytic activity.

  2. THE ISOLATION, ANALISIS AND TESTING OF SEA BUCKTHORN CAROTENOIDS ON MURINE MACROPHAGE CULTURES

    Directory of Open Access Journals (Sweden)

    MICLEA ILEANA

    2007-01-01

    Full Text Available Our aim was to characterize a sea buckthorn (Hippophae rhamnoides fruitcarotenoidic extract and evaluate its influence on macrophage phagocytic responsegiven that carotenoids function as antioxidants. Carotenoids were isolated,saponified and analysed using HPLC before and after saponification. Murineperitoneal macrophages were cultured in medium containing carotenoidic extract.Carotenoid influence on phagocytosis was assessed by calculating the phagocyticindex (PI % and mean phagocytosis (MP. The positive significant differences(p<0,05 picture carotenoid ability to enhance cell phagocytic activity.

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

    International Nuclear Information System (INIS)

    Craft, N.E.; Wise, S.A.

    1993-01-01

    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

  4. Propargyl radical chemistry: renaissance instigated by metal coordination.

    Science.gov (United States)

    Melikyan, Gagik G

    2015-04-21

    Over the last two decades, radical chemistry of propargyl systems was developed into a potent synthetic field providing access to classes of organic compounds that are otherwise hardly accessible. The levels of diastereoselection thus achieved (up to 100%) are unprecedented for free propargyl radicals, as well as for organic radicals π-bonded to transition metals. These advances were enabled by the coordination of the triple bond to a Co2(CO)6 core that precluded an acetylene-allene rearrangement, stabilized requisite propargyl cations, created conformational constraints at the carbon-carbon bond formation site, configurationally altered the acetylenic moiety allowing for 1,3-steric induction upon the newly formed stereocenters, increased bulkiness of propargyl triads thus controlling the spatial orientation of converging radicals, and allowed for α-to-γ projection of the reaction site and alteration of the transiency of radical intermediates. In the course of these studies, a number of popular "beliefs" were proven to be untrue. First, cobalt-complexed propargyl cations, which have long been considered to be thermally labile species, were engaged in synthetically meaningful transformation at temperatures as high as 147 °C. Second, in radical dimerization reactions, higher reaction temperatures did not adversely impact the yields and levels of d,l-diastereoselectivity. Third, π-bonded organometallic radicals, deemed unruly, were effectively controlled with complementary mechanistic tools, thus achieving the highest levels of stereoselectivity (up to 100%) in inter- and intramolecular reactions. Fourth, meso stereoisomers, being thermally labile and kinetically disfavored, were discovered to be major products in intramolecular cyclizations induced by cobaltocene. Fifth, propargyl cations were synthesized in the absence of strong acids, thus increasing the functional tolerance and achieving a long sought after compatibility with acid-sensitive functionalities. A

  5. Carotenoids Functionality, Sources, and Processing by Supercritical Technology: A Review

    Directory of Open Access Journals (Sweden)

    Natália Mezzomo

    2016-01-01

    Full Text Available Carotenoid is a group of pigments naturally present in vegetal raw materials that have biological properties. These pigments have been used mainly in food, pharmaceutical, and cosmetic industries. Currently, the industrial production is executed through chemical synthesis, but natural alternatives of carotenoid production/attainment are in development. The carotenoid extraction occurs generally with vegetal oil and organic solvents, but supercritical technology is an alternative technique to the recovery of these compounds, presenting many advantages when compared to conventional process. Brazil has an ample diversity of vegetal sources inadequately investigated and, then, a major development of optimization and validation of carotenoid production/attainment methods is necessary, so that the benefits of these pigments can be delivered to the consumer.

  6. Carotenoid-based breast plumage colour, body condition and clutch ...

    African Journals Online (AJOL)

    dependent ornamental trait. In some species of birds, red, orange and yellow feather colouration reflects male quality and advertises the carotenoid concentration of feathers. Such colouration is an important aspect of mate selection by females.

  7. 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.

  8. Total carotenoids and antioxidant activity of fillets and shells (in natura or cooked of “Vila Franca” shrimp (Litopenaeus Schmitti in different intervals of storage under freezing

    Directory of Open Access Journals (Sweden)

    Giselda Macena Lira

    Full Text Available ABSTRACT Shrimps are sources of carotenoids, astaxanthin is the predominant, responsible for their special and desirable properties, as well as for their instability under heat treatment during the domestic preparation, industrial processing or storage under freezing. These can cause discoloration and reduce the beneficial health properties. This study aimed to evaluate the effect of heat treatment and storage under freezing (0, 45 and 90 days on the levels of total carotenoids and stability of the antioxidant activity of ethanolic extracts of fillets and shells, raw and cooked, of the white shrimp (“Vila Franca” Litopenaeus schmitti (Burkenroad, 1938. The antioxidant ability of the extracts was evaluated using the radicals DPPH• (2,2-diphenyl-1-picryl-hydrazyl and ABTS+• (2,2’-azino-bis (3-ethylbenzothiazoline-6 sulfonic acid, as well as by the iron reducing power (FRAP test. The extracts of cooked or in natura shrimps (fillets and shells represent dietary sources of carotenoids, displaying antioxidant activity through all the tested methods, after heat treatment and storage under freezing. The antioxidant activity of the extracts was superior to the one of ascorbic acid, mainly in the cooked fillet and shells. The samples of shrimp shells seemed a valuable source of carotenoids, whose antioxidant activity was verified even 90 days after freezing, and can be used in food products as functional natural supplement, adding value to this waste.

  9. A comprehensive overview on the micro- and nano-technological encapsulation advances for enhancing the chemical stability and bioavailability of carotenoids.

    Science.gov (United States)

    Soukoulis, Christos; Bohn, Torsten

    2018-01-02

    Carotenoids are lipophilic secondary plant compounds, and their consumption within fruits and vegetables has been positively correlated with a decreased risk of developing several chronic diseases. However, their bioavailability is often compromised due to incomplete release from the food matrix, poor solubility and potential degradation during digestion. In addition, carotenoids in food products are prone to oxidative degradation, not only lowering the nutritional value of the product but also triggering other quality deteriorative changes, such as formation of lipid pro-oxidants (free radicals), development of discolorations or off-flavor defects. Encapsulation refers to a physicochemical process, aiming to entrap an active substance in structurally engineered micro- or nano-systems, in order to develop an effective thermodynamical and physical barrier against deteriorative environmental conditions, such as water vapor, oxygen, light, enzymes or pH. In this context, encapsulation of carotenoids has shown to be a very effective strategy to improve their chemical stability under common processing conditions including storage. In addition, encapsulation may also enhance bioavailability (via influencing bioaccessibility and absorption) of lipophilic bioactives, via modulating their release kinetics from the carrier system, solubility and interfacial properties. In the present paper, it is aimed to present the state of the art of carotenoid microencapsulation in order to enhance storability and bioavailability alike.

  10. Cationic Antimicrobial Polymers and Their Assemblies

    Science.gov (United States)

    Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

    2013-01-01

    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. PMID:23665898

  11. 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.

  12. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  13. Raman spectroscopy for intracellular monitoring of carotenoid in Blakeslea trispora.

    Science.gov (United States)

    Papaioannou, Emmanouil H; Liakopoulou-Kyriakides, Maria; Christofilos, Dimitrios; Arvanitidis, Ioannis; Kourouklis, Gerasimos

    2009-11-01

    In the present study, we explore the feasibility of Raman spectroscopy for intracellular monitoring of carotenoid in filamentous fungi Blakeslea trispora. Although carotenoid production from this fungus has been extensively studied through various chromatographic methods and ultraviolet-visible spectroscopy, no intracellular monitoring has been demonstrated until now. The intensity of the Raman spectrum, and more conveniently that of the strongest nu(1) carotenoid band at approximately 1,519 cm(-1), exhibits a good linear correlation with the carotenoid content of the sample as determined by high-performance liquid chromatography (HPLC) and ultraviolet-visible (UV-Vis) spectroscopy. Our results suggest that Raman spectroscopy can serve as an alternative method for the study and quantification of carotenoid in batch-mated submerged cultivations of B. trispora and similar organisms. Although not as accurate as HPLC, it allows a rapid sampling and analysis, avoiding the prolonged and tedious classical isolation procedures required for carotenoid determination by HPLC and UV-Vis spectroscopy.

  14. 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.

  15. 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

    2014-06-09

    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.

  16. Sorption by cation exchange

    International Nuclear Information System (INIS)

    Bradbury, M.H.; Baeyens, B.

    1994-04-01

    A procedure for introducing exchange into geochemical/surface complexation codes is described. Beginning with selectivity coefficients, K c , defined in terms of equivalent fractional ion occupancies, a general expression for the molar based exchange code input parameters, K ex , is derived. In natural systems the uptake of nuclides onto complex sorbents often occurs by more than one mechanism. The incorporation of cation exchange and surface complexation into a geochemical code therefore enables sorption by both mechanisms to be calculated simultaneously. The code and model concepts are tested against sets of experimental data from widely different sorption studies. A proposal is made to set up a data base of selectivity coefficients. Such a data base would form part of a more general one consisting of sorption mechanism specific parameters to be used in conjunction with geochemical/sorption codes to model and predict sorption. (author) 6 figs., 6 tabs., 26 refs

  17. 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.

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

    Directory of Open Access Journals (Sweden)

    Hamed Safafar

    2015-12-01

    Full Text Available This study aimed at investigating the potential of microalgae species grown on industrial waste water as a new source of natural antioxidants. Six microalgae from different classes, including Phaeodactylum sp. (Bacillariophyceae, Nannochloropsis sp. (Eustigmatophyceae, Chlorella sp., Dunaniella sp., and Desmodesmus sp. (Chlorophyta, were screened for their antioxidant properties using different in vitro assays. Natural antioxidants, including pigments, phenolics, and tocopherols, were measured in methanolic extracts of microalgae biomass. Highest and lowest concentrations of pigments, phenolic compounds, and tocopherols were found in Desmodesmus sp. and Phaeodactylum tricornuotom microalgae species, respectively. The results of each assay were correlated to the content of natural antioxidants in microalgae biomass. Phenolic compounds were found as major contributors to the antioxidant 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.

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

    Science.gov (United States)

    Safafar, Hamed; van Wagenen, Jonathan; Møller, Per; Jacobsen, Charlotte

    2015-01-01

    This study aimed at investigating the potential of microalgae species grown on industrial waste water as a new source of natural antioxidants. Six microalgae from different classes, including Phaeodactylum sp. (Bacillariophyceae), Nannochloropsis sp. (Eustigmatophyceae), Chlorella sp., Dunaniella sp., and Desmodesmus sp. (Chlorophyta), were screened for their antioxidant properties using different in vitro assays. Natural antioxidants, including pigments, phenolics, and tocopherols, were measured in methanolic extracts of microalgae biomass. Highest and lowest concentrations of pigments, phenolic compounds, and tocopherols were found in Desmodesmus sp. and Phaeodactylum tricornuotom microalgae species, respectively. The results of each assay were correlated to the content of natural antioxidants in microalgae biomass. Phenolic compounds were found as major contributors to the antioxidant 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. PMID:26690454

  20. No evidence that carotenoid pigments boost either immune or antioxidant defenses in a songbird.

    Science.gov (United States)

    Koch, Rebecca E; Kavazis, Andreas N; Hasselquist, Dennis; Hood, Wendy R; Zhang, Yufeng; Toomey, Matthew B; Hill, Geoffrey E

    2018-02-05

    Dietary carotenoids have been proposed to boost immune system and antioxidant functions in vertebrate animals, but studies aimed at testing these physiological functions of carotenoids have often failed to find support. Here we subject yellow canaries (Serinus canaria), which possess high levels of carotenoids in their tissue, and white recessive canaries, which possess a knockdown mutation that results in very low levels of tissue carotenoids, to oxidative and pathogen challenges. Across diverse measures of physiological performance, we detect no differences between carotenoid-rich yellow and carotenoid-deficient white canaries. These results add further challenge to the assumption that carotenoids are directly involved in supporting physiological function in vertebrate animals. While some dietary carotenoids provide indirect benefits as retinoid precursors, our observations suggest that carotenoids themselves may play little to no direct role in key physiological processes in birds.

  1. Carotenoids, carotenoid esters, and anthocyanins of yellow-, orange-, and red-peeled cashew apples (Anacardium occidentale L.).

    Science.gov (United States)

    Schweiggert, Ralf M; Vargas, Ester; Conrad, Jürgen; Hempel, Judith; Gras, Claudia C; Ziegler, Jochen U; Mayer, Angelika; Jiménez, Víctor; Esquivel, Patricia; Carle, Reinhold

    2016-06-01

    Pigment profiles of yellow-, orange-, and red-peeled cashew (Anacardium occidentale L.) apples were investigated. Among 15 identified carotenoids and carotenoid esters, β-carotene, and β-cryptoxanthin palmitate were the most abundant in peels and pulp of all samples. Total carotenoid concentrations in the pulp of yellow- and red-peeled cashew apples were low (0.69-0.73 mg/100g FW) compared to that of orange-peeled samples (2.2mg/100g FW). The color difference between the equally carotenoid-rich yellow and red colored samples indicated the presence of a further non-carotenoid pigment type in red peels. Among four detected anthocyanins, the major anthocyanin was unambiguously identified as 7-O-methylcyanidin 3-O-β-D-galactopyranoside by NMR spectroscopy. Red and yellow peel color was chiefly determined by the presence and absence of anthocyanins, respectively, while the orange appearance of the peel was mainly caused by increased carotenoid concentrations. Thus, orange-peeled fruits represent a rich source of provitamin A (ca. 124 μg retinol-activity-equivalents/100g pulp, FW). Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Understanding titanium-catalysed radical-radical reactions: a DFT study unravels the complex kinetics of ketone-nitrile couplings.

    Science.gov (United States)

    Streuff, Jan; Himmel, Daniel; Younas, Sara L

    2018-04-03

    The computational investigation of a titanium-catalysed reductive radical-radical coupling is reported. The results match the conclusions from an earlier experimental study and enable a further interpretation of the previously observed complex reaction kinetics. Furthermore, the interplay between neutral and cationic reaction pathways in titanium(iii)-catalysed reactions is investigated for the first time. The results show that hydrochloride additives and reaction byproducts play an important role in the respective equilibria. A full reaction profile is assembled and the computed activation barrier is found to be in reasonable agreement with the experiment. The conclusions are of fundamental importance to the field of low-valent titanium catalysis and the understanding of related catalytic radical-radical coupling reactions.

  3. [Recent knowledge about intestinal absorption and cleavage of carotenoids].

    Science.gov (United States)

    Borel, P; Drai, J; Faure, H; Fayol, V; Galabert, C; Laromiguière, M; Le Moël, G

    2005-01-01

    Our knowledge about intestinal absorption and cleavage of carotenoids has rapidly grown during the last years. New facts about carotenoid absorption have emerged while some controversies about cleavage are close to end. The knowledge of the absorption and conversion processes is indispensable to understand and interpret the perturbations that can occur in the metabolism of carotenoids and vitamin A. Recently, it has been shown that the absorption of certain carotenoids is not passive - as believed for a long time - but is a facilitated process that requires, at least for lutein, the class B-type 1 scavenger receptor (SR-B1). Various epidemiological and clinical studies have shown wide variations in carotenoid absorption from one subject to another, such differences are now explained by the structure of the concerned carotenoid, by the nature of the food that is absorbed with the carotenoid, by diverse exogenous factors like the intake of medicines or interfering components, by diet factors, by genetic factors, and by the nutritional status of the subject. Recently, the precise mechanism of beta-carotene cleavage by betabeta-carotene 15,15' monooxygenase (EC 1.14.99.36) - formerly called beta-carotene 15,15' dioxygenase (ex EC 1.13.11.21) - has been discovered, and a second enzyme which cleaves asymmetrically the beta-carotene molecule has been found. beta-carotene 15,15' monooxygenase only acts on the 15,15' bond, thus forming two molecules of retinal from one molecule of beta-carotene by central cleavage. Even though the betabeta-carotene 15,15' monooxygenase is much more active on the beta-carotene molecule, a study has shown that it can act on all carotenoids. Searchers now agree that other enzymes that can catalyse an eccentric cleavage of carotenoids probably exist, but under physiological conditions the betabeta-carotene 15,15' monooxygenase is by far the most active, and it is mainly effective in the small bowel mucosa and in the liver. However the

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

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    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

  5. 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.

  6. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  7. Gas phase hydration of halogenated benzene cations. Is it hydrogen or halogen bonding?

    Science.gov (United States)

    Mason, Kyle A; Pearcy, Adam C; Attah, Isaac K; Platt, Sean P; Aziz, Saadullah G; El-Shall, M Samy

    2017-07-19

    Halogen bonding (XB) non-covalent interactions can be observed in compounds containing chlorine, bromine, or iodine which can form directed close contacts of the type R1-XY-R2, where the halogen X acts as a Lewis acid and Y can be any electron donor moiety including electron lone pairs on hetero atoms such as O and N, or π electrons in olefin double bonds and aromatic conjugated systems. In this work, we present the first evidence for the formation of ionic halogen bonds (IXBs) in the hydration of bromobenzene and iodobenzene radical cations in the gas phase. We present a combined thermochemical investigation using the mass-selected ion mobility (MSIM) technique and density functional theory (DFT) calculations of the stepwise hydration of the fluoro, chloro, bromo, and iodobenzene radical cations. The binding energy associated with the formation of an IXB in the hydration of the iodobenzene cation (11.2 kcal mol -1 ) is about 20% higher than the typical unconventional ionic hydrogen bond (IHB) of the CH δ+ OH 2 interaction. The formation of an IXB in the hydration of the iodobenzene cation involves a significant entropy loss (29 cal mol -1 K -1 ) resulting from the formation of a more ordered structure and a highly directional interaction between the oxygen lone pair of electrons of water and the electropositive region around the iodine atom of the iodobenzene cation. In comparison, the hydration of the fluorobenzene and chlorobenzene cations where IHBs are formed, -ΔS° = 18-21 cal mol -1 K -1 consistent with the formation of less ordered structures and loose interactions. The electrostatic potentials on the lowest energy structures of the hydrated halogenated benzene radical cations show clearly that the formation of an IXB is driven by a positively charged σ-hole on the external side of the halogen atom X along the C-X bond axis. The size of the σ-hole increases significantly in bromobenzene and iodobenzene radical cations which results in strong

  8. Synthetic biology and metabolic engineering for marine carotenoids: new opportunities and future prospects.

    Science.gov (United States)

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

    2014-09-17

    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 are also reviewed, in hopes that this review will promote the exploration of marine carotenoid for their utilizations.

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

    Directory of Open Access Journals (Sweden)

    Chonglong Wang

    2014-09-01

    Full Text Available 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 are also reviewed, in hopes that this review will promote the exploration of marine carotenoid for their utilizations.

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

    Science.gov (United States)

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

    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 are also reviewed, in hopes that this review will promote the exploration of marine carotenoid for their utilizations. PMID:25233369

  11. 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....

  12. Radical's view of sciences

    International Nuclear Information System (INIS)

    Mittal, J.P.

    2004-01-01

    Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

  13. [Carotenoid intake in the German National Food Consumption Survey].

    Science.gov (United States)

    Pelz, R; Schmidt-Faber, B; Heseker, H

    1998-12-01

    In nutritional epidemiological studies high consumption of fruits and vegetables was shown to be an important preventive measure to reduce the risk of cancer, coronary heart disease, and cataracts. These effects cannot be explained completely and in a sufficient way by the intake of beta-carotene and vitamin C. Other carotenoids differing in their antioxidative and biological properties are also provided with fruits and vegetables in significant amounts. Because data for other carotenoids than beta-carotene are not considered in computerized German food database and food composition tables, representative carotenoid intake calculations for the German population are missing. Therefore a carotenoid database, containing alpha- and beta-carotene, lycopene, lutein/zeaxanthin, and cryptoxanthin values for different fruits, vegetables, and other carotenoid-containing foods, was developed. With this database the carotenoid intake of the German population--stratified by sex and age--was evaluated on the basis of the German National Food Consumption Survey (NVS). The mean total carotenoid intake amounts to 5.33 mg/day. The average intake lutein was 1.91 mg/day, beta-carotene intake amounts to 1.81 mg/day, lycopene intake was 1.28 mg/day, alpha-carotene intake was 0.29 mg/day, and cryptoxanthin intake was 0.05 mg/day. Tomatoes and tomato products provide most of the lycopene. Green salads and vegetables are the most important contributors of lutein in Germany. Zeaxanthin is mainly consumed with maize but also with spinach and other vegetables like cabbage; alpha- and beta-carotene are mainly consumed with carrots. Peppers, oranges, and orange-juice are the most important cryptoxanthin sources.

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

    Directory of Open Access Journals (Sweden)

    Elisa eLuengo

    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.

  15. Carotenoids of Microalgae Used in Food Industry and Medicine.

    Science.gov (United States)

    Gateau, Hélène; Solymosi, Katalin; Marchand, Justine; Schoefs, Benoît

    2017-01-01

    Since the industrial revolution, the consumption of processed food increased dramatically. During processing, food material loses many of its natural properties. The simple restoration of the original properties of the processed food as well as fortification require food supplementation with compounds prepared chemically or of natural origin. The observations that natural food additives are safer and better accepted by consumers than synthetic ones have strongly increased the demand for natural compounds. Because some of them have only a low abundance or are even rare, their market price can be very high. This is the case for most carotenoids of natural origin to which this review is dedicated. The increasing demand for food additives of natural origin contributes to an accelerated depletion of traditional natural resources already threatened by intensive agriculture and pollution. To overcome these difficulties and satisfy the demand, alternative sources for natural carotenoids have to be found. In this context, photosynthetic microalgae present a very high potential because they contain carotenoids and are able to produce particular carotenoids under stress. Their potential also resides in the fact that only ten thousands of microalgal strains have been described while hundred thousands of species are predicted to exist. Carotenoids have been known for ages for their antioxidant and coloring properties, and a large body of evidence has been accumulated about their health potential. This review summarizes both the medicinal and food industry applications of microalgae with emphasis on the former. In addition, traditional and alternative microalgal sources used for industrial carotenoid extraction, the chemical and physical properties, the biosynthesis and the localization of carotenoids in algae are also briefly discussed. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  16. Incorporation of [1-C14] Isopentenyl Pyrophosphate into Carotenoids and Homo carotenoids using a Cell-free Preparation of Micrococcus Luteus

    International Nuclear Information System (INIS)

    Al-Wandawi, H.

    1998-01-01

    The early steps up to the formation of acyclic unsaturated carotenes (e.g.,phytoene to lycopene) are presumed to be common to the biosynthesis of all carotenoids with 40 or more carbon atoms, nevertheless, no direct evidence so far available to confirm this for homo carotenoids (c 45 and c 50 carotenoids). In the present study, an active cell-free preparation was obtained from diphenylamine-inhibited cells of Micrococcus Iuteus and found to be capable to incorporate radioactivity from Isopentenyl pyrophosphate (labelled with C-14)into carotenoids and homo carotenoids, providing for the first time a direct evidence which suggests that both carotenoids and homo carotenoids are sharing the same biological origin. Furthermore, the technique developed in this study may be considered as a valuable method for preparation of biological-active labelled compounds which may have some advantages over conventional chemical syntheses methods

  17. 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

  18. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    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 explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... and their families. Existing literature and ways of defining the social psychological process of radicalization will be discussed, and a theoretical framework based on a focus on (non-)belonging, Otherness and sense of community will be proposed. The framework will be utilized in an analysis of narratives from...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  19. Radical prostatectomy - discharge

    Science.gov (United States)

    ... to 6 months. You will learn exercises (called Kegel exercises) that strengthen the muscles in your pelvis. ... Radical prostatectomy Retrograde ejaculation Urinary incontinence Patient Instructions Kegel exercises - self-care Suprapubic catheter care Urinary catheters - ...

  20. Moderate and Radical Islam

    National Research Council Canada - National Science Library

    Rabasa, Angel

    2005-01-01

    This report presents the statement of Angel Rabasa, PhD, Senior Policy Analyst, The RAND Corporation, to the Committee on Armed Services, Defense Review Terrorism and Radical Islam Gap Panel, United...

  1. The fate of primary cations in radiolysis of alkanes as studied by ESR

    International Nuclear Information System (INIS)

    Iwasaki, M.; Toriyama, K.; Nunome, K.

    1983-01-01

    The structures and reactions of alkane cations (RH + ) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2 H 6 , C 3 H 8 , iso-C 4 H 10 and neo-C 5 H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6 , CFCl 2 CF 2 Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2 CF 2 Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers. (author)

  2. Plasma carotenoids and tocopherols in relation to prostate-specific antigen (PSA) levels among men with biochemical recurrence of prostate cancer.

    Science.gov (United States)

    Antwi, Samuel O; Steck, Susan E; Zhang, Hongmei; Stumm, Lareissa; Zhang, Jiajia; Hurley, Thomas G; Hebert, James R

    2015-10-01

    Although men presenting with clinically localized prostate cancer (PrCA) often are treated with radical prostatectomy or radiation therapy with curative intent, about 25-40% develop biochemically recurrent PrCA within 5 years of treatment, which has no known cure. Studies suggest that carotenoid and tocopherol intake may be associated with PrCA risk and progression. We examined plasma carotenoid and tocopherol levels in relation to prostate-specific antigen (PSA) levels among men with PSA-defined biochemical recurrence of PrCA. Data analyzed were from a 6-month diet, physical activity and stress-reduction intervention trial conducted in South Carolina among biochemically recurrent PrCA patients (n=39). Plasma carotenoids and tocopherol levels were measured using high-performance liquid chromatography (HPLC). Linear regression was used to estimate least-square means comparing PSA levels of men with high versus low carotenoid/tocopherol levels, adjusting for covariates. After adjusting for baseline PSA level, plasma cis-lutein/zeaxanthin level at 3 months was related inversely to PSA level at 3 months (P=0.0008), while α-tocopherol (P=0.01), β-cryptoxanthin (P=0.01), and all-trans-lycopene (P=0.004) levels at 3 months were related inversely to PSA levels at 6-months. Percent increase in α-tocopherol and trans-β-carotene levels from baseline to month 3 were associated with lower PSA levels at 3 and 6 months. Percent increase in β-cryptoxanthin, cis-lutein/zeaxanthin and all-trans-lycopene were associated with lower PSA levels at 6 months only. Certain plasma carotenoids and tocopherols were related inversely to PSA levels at various timepoints, suggesting that greater intake of foods containing these micronutrients might be beneficial to men with PSA-defined PrCA recurrence. Copyright © 2015. Published by Elsevier Ltd.

  3. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu

    2017-04-27

    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  4. Carotenoid content impacts flavor acceptability in tomato (Solanum lycopersicum).

    Science.gov (United States)

    Vogel, Jonathan T; Tieman, Denise M; Sims, Charles A; Odabasi, Asli Z; Clark, David G; Klee, Harry J

    2010-10-01

    Tomatoes contain high levels of several carotenoids including lycopene and β-carotene. Beyond their functions as colorants and nutrients, carotenoids are precursors for important volatile flavor compounds. In order to assess the importance of apocarotenoid volatiles in flavor perception and acceptability, we conducted sensory evaluations of near-isogenic carotenoid biosynthetic mutants and their parent, Ailsa Craig. The carotenoid contents of these tomatoes were extremely low in the r mutant, increased in lycopene in old gold, and higher in tetra-cis-lycopene and ζ-carotene in tangerine. The volatiles derived from these carotenoids (β-ionone, geranylacetone and 6-methyl-5-hepten-2-one) were proportionally altered relative to their precursors. Fruits were also analyzed for soluble solids, sugars, acids and flavor volatiles. Consumer panels rated the r mutant lowest for all sensory attributes, while Ailsa Craig was generally rated highest. Old gold and tangerine were rated intermediate in two of the three harvests. Several chemicals were negatively correlated with at least one of the hedonic scores while several others were positively correlated with tomato flavor acceptability. The results permitted identification of positive and negative interactions of volatiles with tomato flavor. Copyright © 2010 Society of Chemical Industry.

  5. A comprehensive review on the colorless carotenoids phytoene and phytofluene.

    Science.gov (United States)

    Meléndez-Martínez, Antonio J; Mapelli-Brahm, Paula; Benítez-González, Ana; Stinco, Carla M

    2015-04-15

    Carotenoids and their derivatives are versatile isoprenoids involved in many varied actions, hence their importance in the agri-food industry, nutrition, health and other fields. All carotenoids are derived from the colorless carotenes phytoene and phytofluene, which are oddities among carotenoids due to their distinct chemical structure. They occur together with lycopene in tomato and other lycopene-containing foods. Furthermore, they are also present in frequently consumed products like oranges and carrots, among others. The intake of phytoene plus phytofluene has been shown to be higher than that of lycopene and other carotenoids in Luxembourg. This is likely to be common in other countries. However, they are not included in food carotenoid databases, hence they have not been linked to health benefits in epidemiological studies. Interestingly, there are evidences in vitro, animal models and humans indicating that they may provide health benefits. In this sense, the study of these colorless carotenes in the context of food science, nutrition and health should be further encouraged. In this work, we review much of the existing knowledge concerning their chemical characteristics, physico-chemical properties, analysis, distribution in foods, bioavailability and likely biological activities. Copyright © 2015 Elsevier Inc. All rights reserved.

  6. Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources.

    Science.gov (United States)

    Lalevée, Jacques; Mokbel, Haifaa; Fouassier, Jean-Pierre

    2015-04-20

    Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

  7. Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources

    OpenAIRE

    Jacques Lalevée; Haifaa Mokbel; Jean-Pierre Fouassier

    2015-01-01

    Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under vario...

  8. Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources

    Directory of Open Access Journals (Sweden)

    Jacques Lalevée

    2015-04-01

    Full Text Available Photoinitiators (PI or photoinitiating systems (PIS usable in light induced cationic polymerization (CP and free radical promoted cationic polymerization (FRPCP reactions (more specifically for cationic ring opening polymerization (ROP together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

  9. Stability of carotenoids recovered from shrimp waste and their use as colorant in fish sausage.

    Science.gov (United States)

    Sachindra, N M; Mahendrakar, N S

    2010-01-01

    The stability of carotenoids recovered from shrimp waste using organic solvents and vegetable oils as affected by antioxidants and pigment carriers was evaluated during storage under different conditions. Solvent extracted carotenoid incorporated into alginate and starch as carriers was stored in metallised polyester and polypropylene pouches. Oil extracted carotenoids were stored in transparent and amber bottles. Also the use of recovered pigments as colorants in fish sausage was evaluated. Antioxidants, packaging material and storage period had a significant effect (p≤0.001) on the reduction of carotenoid content, while type of carrier had marginal effect (p≥0.05) on solvent extracted carotenoids during storage. Carotenoid content in pigmented oil was significantly affected by antioxidants (p≤0.001), packaging material (p≤0.05) and storage period (p≤0.001). Addition of carotenoid to the sausage enhanced the sensory colour, flavour and overall quality score of sausage and the added carotenoid was stable during processing.

  10. 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)

  11. Host-related factors explaining interindividual variability of carotenoid bioavailability and tissue concentrations in humans

    DEFF Research Database (Denmark)

    Bohn, Torsten; Desmarchelier, Charles; Dragsted, Lars Ove

    2017-01-01

    .g. smoking), gender and age, as well as genetic variations including single nucleotide polymorphisms that govern carotenoid metabolism. These are expected to explain interindividual differences that contribute to carotenoid uptake, distribution, metabolism and excretion, and therefore possibly also...

  12. 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....

  13. 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…

  14. Effect of Carotenoid Supplemented Formula on Carotenoid Bioaccumulation in Tissues of Infant Rhesus Macaques: A Pilot Study Focused on Lutein.

    Science.gov (United States)

    Jeon, Sookyoung; Neuringer, Martha; Johnson, Emily E; Kuchan, Matthew J; Pereira, Suzette L; Johnson, Elizabeth J; Erdman, John W

    2017-01-10

    Lutein is the predominant carotenoid in the developing primate brain and retina, and may have important functional roles. However, its bioaccumulation pattern during early development is not understood. In this pilot study, we investigated whether carotenoid supplementation of infant formula enhanced lutein tissue deposition in infant rhesus macaques. Monkeys were initially breastfed; from 1 to 3 months of age they were fed either a formula supplemented with lutein, zeaxanthin, β-carotene and lycopene, or a control formula with low levels of these carotenoids, for 4 months ( n = 2/group). All samples were analyzed by high pressure liquid chromatography (HPLC). Final serum lutein in the supplemented group was 5 times higher than in the unsupplemented group. All brain regions examined showed a selective increase in lutein deposition in the supplemented infants. Lutein differentially accumulated across brain regions, with highest amounts in occipital cortex in both groups. β-carotene accumulated, but zeaxanthin and lycopene were undetectable in any brain region. Supplemented infants had higher lutein concentrations in peripheral retina but not in macular retina. Among adipose sites, abdominal subcutaneous adipose tissue exhibited the highest lutein level and was 3-fold higher in the supplemented infants. The supplemented formula enhanced carotenoid deposition in several other tissues. In rhesus infants, increased intake of carotenoids from formula enhanced their deposition in serum and numerous tissues and selectively increased lutein in multiple brain regions.

  15. New Insight into the Cleavage Reaction of Nostoc sp. Strain PCC 7120 Carotenoid Cleavage Dioxygenase in Natural and Nonnatural Carotenoids

    Science.gov (United States)

    Heo, Jinsol; Kim, Se Hyeuk

    2013-01-01

    Carotenoid cleavage dioxygenases (CCDs) are enzymes that catalyze the oxidative cleavage of carotenoids at a specific double bond to generate apocarotenoids. In this study, we investigated the activity and substrate preferences of NSC3, a CCD of Nostoc sp. strain PCC 7120, in vivo and in vitro using natural and nonnatural carotenoid structures. NSC3 cleaved β-apo-8′-carotenal at 3 positions, C-13C-14, C-15C-15′, and C-13′C-14′, revealing a unique cleavage pattern. NSC3 cleaves the natural structure of carotenoids 4,4′-diaponeurosporene, 4,4′-diaponeurosporen-4′-al, 4,4′-diaponeurosporen-4′-oic acid, 4,4′-diapotorulene, and 4,4′-diapotorulen-4′-al to generate novel cleavage products (apo-14′-diaponeurosporenal, apo-13′-diaponeurosporenal, apo-10′-diaponeurosporenal, apo-14′-diapotorulenal, and apo-10′-diapotorulenal, respectively). The study of carotenoids with natural or nonnatural structures produced by using synthetic modules could provide information valuable for understanding the cleavage reactions or substrate preferences of other CCDs in vivo and in vitro. PMID:23524669

  16. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...

  17. Carotenoid and color changes in traditionally flaked and extruded products.

    Science.gov (United States)

    Cueto, Mario; Farroni, Abel; Schoenlechner, Regine; Schleining, Gerhard; Buera, Pilar

    2017-08-15

    The objective of this study was to evaluate the impact of process and formulation on individual carotenoid loss in traditionally prepared cornflakes and those prepared by extrusion. The first step in the traditional process (maize grits cooking) promoted a 60% lutein content reduction and 40% in zeaxanthin loss, showing lutein more susceptibility to isomerization and decomposition. After toasting, the last step, the total loss averaged 80% for both compounds. The extruded maize in a plain formulation showed a 35% lutein and zeaxanthin reduction. However, in samples containing quinoa the decrease reached 60%, and the major loss (80%) was found in chia-containing formulations. Correlations between the color coordinate b ∗ , total and individual carotenoid content, were obtained. It is of a major importance that the efforts to increase carotenoid content in raw materials are complemented with attempts to reduce the losses during processing. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Photoprotection by dietary carotenoids: concept, mechanisms, evidence and future development.

    Science.gov (United States)

    Stahl, Wilhelm; Sies, Helmut

    2012-02-01

    Carotenoids are micronutrients present mainly in fruits and vegetables, and they are ingested from these sources with the diet. They exhibit specific antioxidant activity but also influence signaling and gene expression at the cellular level. β-Carotene and lycopene, the colorants of carrots and tomatoes, respectively, are among the most prominent members of this group of lipids, and they are usually the dominating carotenoids in human blood and tissues. Both compounds modulate skin properties when ingested as supplements or as dietary products. There is evidence that they protect the skin against sunburn (solar erythema) by increasing the basal defense against UV light-mediated damage. Their photoprotective efficacy, however, is not comparable to the use of a sunscreen. In vitro data show that also other carotenoids are efficient photoprotectors. Among them are lutein and structurally unusual phenolic polyenes like 3,3'-dihydroxyisorenieratene. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. High-dynamic-range cationic two-photon photopolymerization

    Science.gov (United States)

    Boiko, Yuri B.; Costa, Joannes M.; Wang, Mark M.; Esener, Sadik C.

    2001-06-01

    Cationic-induced two-photon photopolymerization is demonstrated at 710 nm, using an isopropylthioxanthone/diarylidonium salt initiating system for the cationic polymerization of an epoxide. The polymerization threshold J2th is found to be approximately 1 GW/cm2, with a dynamic range of > 100, i.e. the material can be fully polymerized at intensities > 100 times the threshold level without damage. The polymerization rate R is found to be proportional to the m equals 1.7 power of the intensity, or R equals [C (J-J2th)]m equals [C (J-J2th)]1.7, which implies a significantly stronger localization of the photochemical response than that of free radical photoinitiators. R and J2th significantly improve when the concentration z of the initiator (onium salt) increases.

  1. Stability of bacterial carotenoids in the presence of iron in a model of the gastric compartment - comparison with dietary reference carotenoids.

    Science.gov (United States)

    Sy, Charlotte; Dangles, Olivier; Borel, Patrick; Caris-Veyrat, Catherine

    2015-04-15

    Recently isolated spore-forming pigmented marine bacteria, Bacillus indicus HU36 and Bacillus firmus GB1 are sources of carotenoids (∼fifteen distinct yellow and orange pigments and ∼thirteen distinct pink pigments, respectively). They are glycosides of oxygenated lycopene derivatives (apo-lycopenoids) and are assumed to be more heat- and gastric-stable than common carotenoids. In this study, the oxidation by O2 of the bacterial carotenoids was initiated by free iron (Fe(II) and Fe(III)) or by heme iron (metmyoglobin) in a mildly acidic aqueous solution mimicking the gastro-intestinal compartment and compared to the oxidation of the common dietary carotenoids β-carotene, lycopene and astaxanthin. Under these conditions, all bacterial carotenoids appear more stable in the presence of heme iron vs. free iron. Carotenoid autoxidation initiated by Fe(II) is relatively fast and likely involves reactive oxygen-iron species derived from Fe(II) and O2. By contrast, the corresponding reaction with Fe(III) is kinetically blocked by the slow preliminary reduction of Fe(III) into Fe(II) by the carotenoids. The stability of carotenoids toward autoxidation increases as follows: β-carotenecarotenoids react more quickly than reference carotenoids with Fe(III), but much more slowly than the reference carotenoids with Fe(II). This reaction is correlated with the structure of the carotenoids, which can have opposite effects in a micellar system: bacterial carotenoids with electro-attracting terminal groups have a lower reducing capacity than β-carotene and lycopene. However, their polar head favours their location close to the interface of micelles, in closer contact with oxidative species. Kinetic analyses of the iron-induced autoxidation of astaxanthin and HU36 carotenoids has been performed and gives insights in the underlying mechanisms. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Detection of carotenoids in psychrotrophic bacteria by spectroscopic approach

    Directory of Open Access Journals (Sweden)

    Kirti Kushwaha

    2014-12-01

    Full Text Available The combination of Raman and Infrared spectroscopic signatures were used to find the different vibrational modes of individual carotenoid as their spectral fingerprint. Both have been previously demonstrated to be highly useful methodology for the identification and/or typing of microorganisms. In this study, we set out to evaluate whether these technologies could be applied to detect the presence of carotenoids in psychrotrophic bacterial isolates. FTIR and Raman spectra of four psychrotrophic bacteria viz. Kocuria rosea, K. turfanensis, Sanguibacter suarezii and Planococcus maritimus were examined during the investigation. FTIR spectra bands at 1653-1661cm-1 in different samples were assigned as part of chlorophyll, 1424-1426 cm-1 as -C-H- (CH2 bending vibration from methylene of carotenoids or lycopene, 1366-1367 cm-1 band as the -ionone ring of β-carotene due to the C-H, (–CH3 symmetrical bending. Interestingly, Raman spectra revealed intense Raman bands in the range of 1511-1530, 1153-1159 and 1003-1010 cm-1 representing bacterial carotenoids. We hypothesize the biosynthesis of carotenoid as adaptive strategy to cope up inhospitable cold environments of Leh and Ladakh. The strong, scattering bands by different isolates attributable to ν(C=C phase stretching, ν(C-C and δ(C-CH3 methyl components systems, which could be probably membrane-associated C50 carotenoids. Their high intensities are due to resonance enhancement. It can be concluded that Raman spectroscopy is a sensitive and convenient detection tool for typing of the bacterial biomarkers with less time consumption.

  3. Carotenoids in a food chain along a pollution gradient.

    Science.gov (United States)

    Sillanpää, Saila; Salminen, Juha-Pekka; Lehikoinen, Esa; Toivonen, Eija; Eeva, Tapio

    2008-11-15

    Carotenoids are synthesized by plants, therefore insects and birds must obtain them from their diet. They function in pigmentation and as antioxidants. We studied the carotenoid profiles in a model food chain (plant-insect-bird) in an air pollution gradient to find out whether heavy metal pollution affects the transfer of carotenoids across the trophic levels. Birch leaves showed higher beta-carotene and, one of the birch species (Betula pendula), higher total carotenoids levels in the polluted area. There was no difference in the lutein concentration of caterpillars' food source, birch leaves, between the study areas. Autumnal moth larvae accumulated lutein more efficiently than beta-carotene while sawfly larvae accumulated beta-carotene over lutein. Because of different antioxidant profiles in different leaf chewing insects their sensitivity to pollution stress may differ. The lutein concentration of plasma and feathers of Great tit nestlings did not differ along the pollution gradient. The lack of difference in lutein concentration of autumnal moth larvae along pollution gradient may partly explain the lutein concentrations of Great tit nestlings, since the abundance of autumnal moth larvae peak during the nestling phase of Great tit. The lutein concentration of autumnal moth larvae was positively associated to circulating plasma lutein level of Great tit indicating the importance of carotenoid rich diet during the nestling phase. In addition, the higher the plasma lutein concentration the more lutein was deposited to feathers, irrespective of the other possible functions of lutein in nestlings. We found that carotenoid levels differed between the polluted and the unpolluted area especially at lower levels of food chain: in birches and in caterpillars.

  4. Metabolic regulation of carotenoid-enriched Golden rice line

    Directory of Open Access Journals (Sweden)

    Dipak Gayen

    2016-10-01

    Full Text Available Vitamin A deficiency (VAD is the leading cause of blindness among children and is associated with high risk of maternal mortality. In order to enhance the bioavailability of vitamin A, high carotenoid transgenic golden rice has been developed by manipulating enzymes, such as phytoene synthase (psy and phytoene desaturase (crtI. In this study, proteome and metabolite analyses were carried out to comprehend metabolic regulation and adaptation of transgenic golden rice after the manipulation of endosperm specific carotenoid pathways. The main alteration was observed in carbohydrate metabolism pathways of the transgenic seeds. The 2D based proteomic studies demonstrated that carbohydrate metabolism-related enzymes, such as pullulanase, UDP-glucose pyrophosphorylase and glucose-1-phosphate adenylyl transferase, were primarily up-regulated in transgenic rice seeds. In addition, the enzyme PPDK was also elevated in transgenic seeds thus enhancing pyruvate biosynthesis, which is the precursor in the carotenoids biosynthetic pathway. GC-MS based metabolite profiling demonstrated an increase in the levels of glyceric acid, fructo-furanose, and galactose, while decrease in galactonic acid and gentiobiose in the transgenic rice compared to WT. It is noteworthy to mention that the carotenoid content, especially β-carotene level in transgenic rice (4.3 µg/g was significantly enhanced. The present study highlights the metabolic adaptation process of a transgenic golden rice line (homozygous T4 progeny of SKBR-244 after enhancing carotenoid biosynthesis. The presented information would be helpful in the development of crops enriched in carotenoids by expressing metabolic flux of pyruvate biosynthesis.

  5. Metabolic Regulation of Carotenoid-Enriched Golden Rice Line.

    Science.gov (United States)

    Gayen, Dipak; Ghosh, Subhrajyoti; Paul, Soumitra; Sarkar, Sailendra N; Datta, Swapan K; Datta, Karabi

    2016-01-01

    Vitamin A deficiency (VAD) is the leading cause of blindness among children and is associated with high risk of maternal mortality. In order to enhance the bioavailability of vitamin A, high carotenoid transgenic golden rice has been developed by manipulating enzymes, such as phytoene synthase ( psy) and phytoene desaturase ( crtI ). In this study, proteome and metabolite analyses were carried out to comprehend metabolic regulation and adaptation of transgenic golden rice after the manipulation of endosperm specific carotenoid pathways. The main alteration was observed in carbohydrate metabolism pathways of the transgenic seeds. The 2D based proteomic studies demonstrated that carbohydrate metabolism-related enzymes, such as pullulanase, UDP-glucose pyrophosphorylase, and glucose-1-phosphate adenylyltransferase, were primarily up-regulated in transgenic rice seeds. In addition, the enzyme PPDK was also elevated in transgenic seeds thus enhancing pyruvate biosynthesis, which is the precursor in the carotenoids biosynthetic pathway. GC-MS based metabolite profiling demonstrated an increase in the levels of glyceric acid, fructo-furanose, and galactose, while decrease in galactonic acid and gentiobiose in the transgenic rice compared to WT. It is noteworthy to mention that the carotenoid content, especially β-carotene level in transgenic rice (4.3 μg/g) was significantly enhanced. The present study highlights the metabolic adaptation process of a transgenic golden rice line (homozygous T4 progeny of SKBR-244) after enhancing carotenoid biosynthesis. The presented information would be helpful in the development of crops enriched in carotenoids by expressing metabolic flux of pyruvate biosynthesis.

  6. 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.

  7. Differential effects of testosterone, dihydrotestosterone and estradiol on carotenoid deposition in an avian sexually selected signal

    NARCIS (Netherlands)

    Casagrande, Stefania; Dijkstra, Cor; Tagliavini, James; Goerlich, Vivian C.; Groothuis, Ton G. G.

    Recent studies have demonstrated that carotenoid-based traits are under the control of testosterone (T) by up-regulation of carotenoid carriers (lipoproteins) and/or tissue-specific uptake of carotenoids. T can be converted to dihydrotestosterone (DHT) and estradiol (E2), and variation in conversion

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

    Directory of Open Access Journals (Sweden)

    Stancuta Scrob

    2013-11-01

    Full Text Available 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.

  9. Effects of carotenoids, immune activation and immune suppression on the intensity of chronic coccidiosis in greenfinches.

    Science.gov (United States)

    Sepp, Tuul; Karu, Ulvi; Sild, Elin; Männiste, Marju; Hõrak, Peeter

    2011-03-01

    Allocation trade-offs of carotenoids between their use in the immune system and production of integumentary colouration have been suggested as a proximate mechanism maintaining honesty of signal traits. We tested how dietary carotenoid supplementation, immune activation and immune suppression affect intensity of coccidian infection in captive greenfinches Carduelis chloris, a passerine with carotenoid-based plumage. Immune activation with phytohaemagglutinin (PHA) decreased body mass among birds not supplemented with lutein, while among the carotenoid-fed birds, PHA had no effect on mass dynamics. Immune suppression with dexamethasone (DEX) induced loss of body mass and reduced the swelling response to PHA. DEX and PHA increased the concentration of circulating heterophils. Lutein supplementation increased plasma carotenoid levels but had no effect on the swelling response induced by PHA. PHA and DEX treatments did not affect plasma carotenoids. Immune stimulation by PHA suppressed the infection, but only among carotenoid-supplemented birds. Priming of the immune system can thus aid in suppressing chronic infection but only when sufficient amount of carotenoids is available. Our experiment shows the importance of carotenoids in immune response, but also the complicated nature of this impact, which could be the reason for inconsistent results in studies investigating the immunomodulatory effects of carotenoids. The findings about involvement of carotenoids in modulation of an immune response against coccidiosis suggest that carotenoid-based ornaments may honestly signal individuals' ability to manage chronic infections. Copyright © 2010 Elsevier Inc. All rights reserved.

  10. Absorption of beta-carotene and other carotenoids in humans and animal models : a review

    NARCIS (Netherlands)

    Vliet, T. van

    1996-01-01

    Objective: To review available information on absorption and further metabolism of different carotenoids in man and to discuss animal models and approaches in the study of carotenoid absorption and metabolism in man. Conclusions: Humans appear to absorb various carotenoids in a relatively

  11. Novel expression patterns of carotenoid pathway-related gene in citrus leaves and maturing fruits

    Science.gov (United States)

    Carotenoids are abundant in citrus fruits and vary among cultivars and species. In the present study, HPLC and real-time PCR were used to investigate the expression patterns of 23 carotenoid biosynthesis gene family members and their possible relation with carotenoid accumulation in flavedo, juice s...

  12. Laparoscopic radical trachelectomy.

    Science.gov (United States)

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

    2012-01-01

    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. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  13. Electron paramagnetic resonance evidence for the occurrence of hydrogen and/or proton transfer between C7, C8 and C11 n-alkanes and their cations in irradiated CCl3F matrices at 77 K

    International Nuclear Information System (INIS)

    Luyckx, G.; Ceulemans, J.

    1991-01-01

    After γ-irradiation of heptane and octane at low concentration in CCI 3 F at 77 K, only the EPR spectrum of the corresponding radical cations is observed. At higher concentrations, the spectrum of alkyl radicals also appears. Clear alkyl radical features are also observed after irradiation of 1 mol% undecane in CCI 3 F. In contrast, alkane radical cations but no alkyl radicals are observed after irradiation of heptane, octane and undecane in CCI 3 CF 3 and other saturated chlorofluorocarbon matrices at concentrations where alkyl radicals are already very prominent in CCI 3 F. Different mechanisms for the formation of these alkyl radicals are considered, viz. direct radiolysis of the alkane solutes, formation as a result of electronic excitation energy transfer and formation via the corresponding alkane radical cations that are formed by hole transfer from matrix cations. In the latter case, unimolecular deprotonation, charge neutralization by electron tunnelling and hydrogen/proton transfer with alkane molecules are taken into consideration. It is concluded that the hydrogen/proton transfer reaction (RH dot+ + RH→R dot + RH + 2 ) mainly accounts for the observed alkyl radicals. The results further indicate that in CCI 3 F at 77 K alkanes are present as small aggregates, to which hole transfer from matrix cations still occurs efficiently. (author)

  14. Los carotenoides dietéticos en el organismo animal

    OpenAIRE

    Brenes-Soto, Andrea

    2014-01-01

    Los compuestos carotenoides se encuentran en plantas, algas y bacterias, principalmente, y son ingeridos por los animales en sus dietas. Estos compuestos lipofílicos se dividen en carotenos y xantofilas, dependiendo de su estructura y composición molecular.  Además de su función como precursores de la vitamina A y como antioxidantes, los carotenoides también se pueden depositar en varios tejidos y órganos como el ojo, hígado, músculo, piel, picos y plumas de aves, en los cuales también cumple...

  15. Liquid-solid extraction of cationic metals by cationic amphiphiles

    International Nuclear Information System (INIS)

    Muller, W.

    2010-01-01

    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 - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) 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) [fr

  16. 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.

  17. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

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

    2017-01-01

    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...

  18. Radical dematerialization and degrowth

    Science.gov (United States)

    Kallis, Giorgos

    2017-05-01

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable `degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money. This article is part of the themed issue 'Material demand reduction'.

  19. 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 will be proposed....... The framework will be utilized in an analysis of narratives from youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious...

  20. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  1. Antioxidants, free radicals, storage proteins, and proteolytic activities in wheat (Triticum durum) seeds during accelerated aging.

    Science.gov (United States)

    Galleschi, Luciano; Capocchi, Antonella; Ghiringhelli, Silvia; Saviozzi, Franco; Calucci, Lucia; Pinzino, Calogero; Zandomeneghi, Maurizio

    2002-09-11

    Accelerated aging was performed by incubation of wheat seeds at 40 degrees C and 100% relative humidity for 3, 4, 6, 10, and 14 days. The effects of the treatment on seed germinability and on several biochemical characteristics of flour (carotenoids, free radical and protein contents, and proteolytic activity) and gluten (free radical content and flexibility) were evaluated. A decrease of germinability was found during aging, the germination being completely inhibited after 14 days. The lutein content decreased gradually, without going to zero, while that of free radicals increased. A reduction of soluble proteins and a degradation of glutenins and gliadins were observed, associated with a substantial increase of protease activity and a decrease in gluten flexibility. The results were discussed in reference to those previously obtained by natural aging of wheat seeds of the same species and cultivar.

  2. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    and foiled plots inspired by militant Islamism have grabbed European and American headlines. This article identifies and discusses empirical studies of radicalization and points to the strengths as well as the weaknesses characterizing these studies. The aim is to take stock of the current state of research...

  3. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and place demand an explanation; my attempt to do so also takes into account the important differences between the gnostic and the radical feminist postures, notably the latter belief in progress and the former nostalgia for an ungendered era. Both the similarities and the differences, however, may offer...

  4. Counter radicalization development assistance

    OpenAIRE

    van Hippel, Karin

    2006-01-01

    The paper reviews current research and practice and recommends strategies for development agencies working in the Arab and Muslim world. It builds on the basic assumption that the realization of the Millennium Development Goals will be vital to reduce support for terrorism in the long term. Within this overall framework, emphasis is placed on particular programs that could be specifically applied to counter radicalization.

  5. Electromeric rhodium radical complexes

    NARCIS (Netherlands)

    Puschmann, F.F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin, B.; Grützmacher, H.

    2010-01-01

    Radical changes: One single P-Rh-P angle determines whether the odd electron in the paramagnetic complex [Rh(trop2PPh)(PPh3)] is delocalized over the whole molecule (see picture, blue) or is localized on the P—Rh unit (red). The two energetically almost degenerate electromers exist in a fast

  6. Radical Behaviorist Epistemology.

    Science.gov (United States)

    Zuriff, G. E.

    1980-01-01

    Various epistemological positions attributed to radical behaviorism are reviewed, and their problems are discussed. It is suggested that these problems may be resolved by interpreting the criterion of truth generated by a science of behavior as logically analagous to the set of ethical values generated by that science. (Author/DB)

  7. Free Radical Scavenging Properties of Annona squamosa

    Science.gov (United States)

    Vikas, Biba; S, Akhil B; P, Remani; Sujathan, K

    2017-01-01

    Annona squamosa has extensively been used in the traditional and folkloric medicine and found to possess many biological activities. Different solvents, petroleum ether, chloroform, ethyl acetate and methanol extracts of Annona squamosa seeds (ASPE, ASCH, ASEA, ASME) have been used to prepare plant extracts. The present investigations dealt with the free radical scavenging activity of four extracts using various techniques such as total reducing power estimation, total phenolic count, 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging effect, evaluation of ABTS cation decolorisation capacity, FRAP assay, hdroxyl radical scavenging assay, super oxide assay and Nitric oxide radical scavenging assay of the extracts. The results showed that the four extracts of Annona squamosa showed significant reducing power in four extracts. The total phenolic contents in petroleum ether, chloroform, ethyl acetate, methanol extracts and positive control were 0.64±0.17, 0.54±0.27, 0.49±0.24, 0.57±0.22 and 0.66±0.33. The antioxidant capacity by ABTS assay of ASPE, ASCH, ASEA, ASME and positive control, trolox showed 77.75±0.5,73.25±1.7,78.5± 1.2, 80 ± 0.8 μg/ml and 94.2 ± 0.9 respectively. The (50 % scavenging activity) SA50 of ASPE and ASCH, ASEA and ASME was found to be 34.4 µg/ml, 43.8 µg/ml 34.7 µg/m and 28.8 µg/ml respectively by DPPH assay. The percentage of hydroxyl radical scavenging increased with the increasing concentration of the extracts. ASPE, ASCH, ASEA and ASME showed superoxide radical scavenging activity, as indicated by their values 66 ± 0.5, 68 ± 1, 63 ± 1 and 70 ± 0.5 μg/ml respectively compared to gallic acid which was 97 ± 0.5 μg/ml. The values for scavenging of nitric oxide for ASPE, ASCH, ASEA and ASME were 91.0 ± 1.0, 66.75 ± 0.5, 71.75 ± 1.1 and 75.75 ± 1.15 μg/ml while value for standard ascorbic acid was 91.0 ± 1.0 μg/ml. The results revealed strong antioxidants in four extracts may lead to the development of potent

  8. Free Radical Scavenging Properties of Annona squamosa

    Science.gov (United States)

    Vikas, Biba; Akhil B, S; P, Remani; Sujathan, K

    2017-10-26

    Annona squamosa has extensively been used in the traditional and folkloric medicine and found to possess many biological activities. Different solvents, petroleum ether, chloroform, ethyl acetate and methanol extracts of Annona squamosa seeds (ASPE, ASCH, ASEA, ASME) have been used to prepare plant extracts. The present investigations dealt with the free radical scavenging activity of four extracts using various techniques such as total reducing power estimation, total phenolic count, 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging effect, evaluation of ABTS cation decolorisation capacity, FRAP assay, hdroxyl radical scavenging assay, super oxide assay and Nitric oxide radical scavenging assay of the extracts. The results showed that the four extracts of Annona squamosa showed significant reducing power in four extracts. The total phenolic contents in petroleum ether, chloroform, ethyl acetate, methanol extracts and positive control were 0.64±0.17, 0.54±0.27, 0.49±0.24, 0.57±0.22 and 0.66±0.33. The antioxidant capacity by ABTS assay of ASPE, ASCH, ASEA, ASME and positive control, trolox showed 77.75±0.5,73.25±1.7,78.5± 1.2 , 80 ± 0.8 μg/ml and 94.2 ± 0.9 respectively. The (50 % scavenging activity) SA50 of ASPE and ASCH, ASEA and ASME was found to be 34.4 μg/ml, 43.8 μg/ml 34.7 μg/m and 28.8 μg/ml respectively by DPPH assay. The percentage of hydroxyl radical scavenging increased with the increasing concentration of the extracts. ASPE, ASCH, ASEA and ASME showed superoxide radical scavenging activity, as indicated by their values 66 ± 0.5, 68 ± 1 ,63 ± 1 and 70 ± 0.5 μg/ml respectively compared to gallic acid which was 97 ± 0.5 μg/ml. The values for scavenging of nitric oxide for ASPE, ASCH, ASEA and ASME were 91.0 ± 1.0, 66.75 ± 0.5, 71.75 ± 1.1 and 75.75 ± 1.15 μg/ml while value for standard ascorbic acid was 91.0 ± 1.0 μg/ml. The results revealed strong antioxidants in four extracts may lead to the development of potent

  9. Expression profile of genes coding for carotenoid biosynthetic ...

    Indian Academy of Sciences (India)

    vated tomato and also provide dietary nutrition to humans. (Bramley 2002). Therefore, tomato is preferred as an important model plant for studying carotenoid biosynthesis pathway during fruit ripening (Wiebke and Ralph 2009). The pathway is highly active in tomato fruits during ripen- ing, leading to the accumulation of ...

  10. Retention of phenolics, carotenoids, and antioxidant activity in the ...

    African Journals Online (AJOL)

    The effects of three drying methods on phenolic and carotenoid content and antioxidant activity (AOA) of Tainong 66 cultivar sweet potato (Ipomoea batatas Lam.) were investigated. Roots of 12 batches of freshly harvested tuberous root were washed in tap water, allowed to dry, peeled and cut into small pieces of 0.5 to 1 ...

  11. Expression profile of genes coding for carotenoid biosynthetic

    Indian Academy of Sciences (India)

    Fruit ripening process is associated with change in carotenoid profile and accumulation of lycopene in tomato (Solanum lycopersicum L.). In this study, we quantified the -carotene and lycopene content at green, breaker and red-ripe stages of fruit ripening in eight tomato genotypes by using high-performance liquid ...

  12. Expression profile of genes coding for carotenoid biosynthetic ...

    Indian Academy of Sciences (India)

    Expression profile of genes coding for carotenoid biosynthetic pathway during ripening and their association with accumulation of lycopene in tomato fruits. Shuchi Smita, Ravi Rajwanshi, Sangram Keshari Lenka, Amit Katiyar, Viswanathan Chinnusamy and. Kailash Chander Bansal. J. Genet. 92, 363–368. Table 1.

  13. Phenols, essential oils and carotenoids of Rosa canina from Tunisia ...

    African Journals Online (AJOL)

    The antioxidant activity of leaf extracts of Rosa canina from diverse localities of Tunisia were evaluated by ABTS and DPPH methods, whereas in those of essential oils and carotenoids extracts such activity was determined only by the ABTS method. Total phenols determined by the Folin method revealed that at Aindraham, ...

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

    International Nuclear Information System (INIS)

    Van Tassle, Aaron Justin

    2006-01-01

    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

  15. Changes in membrane lipids and carotenoids during light ...

    Indian Academy of Sciences (India)

    2012-07-24

    Jul 24, 2012 ... increased their content, the changes of PG(18:3/16:0) and MGDG(18:3/16:0) being primarily significant. Major lipid changes were also ... reported to increase with exposure to high light in Cyano- bacteria (Masamoto and .... Absorption spectrum of the other carotenoid (unkn1) has absorption maxima at 448/.

  16. Liver retinol and carotenoid concentration of rats experimentally ...

    African Journals Online (AJOL)

    This study investigated the liver retinol and carotenoid concentration of rats experimentally infected with Trypanosoma brucei. Results of the liver retinol determination showed that T. brucei infection led to a progressively significant (P < 0.01) depletion of liver retinol concentration (body vitamin A status) of infected rats from ...

  17. Innovative Alternative Technologies to Extract Carotenoids from Microalgae and Seaweeds

    Science.gov (United States)

    Poojary, Mahesha M.; Barba, Francisco J.; Aliakbarian, Bahar; Donsì, Francesco; Pataro, Gianpiero; Dias, Daniel A.; Juliano, Pablo

    2016-01-01

    Marine microalgae and seaweeds (microalgae) represent a sustainable source of various bioactive natural carotenoids, including β-carotene, lutein, astaxanthin, zeaxanthin, violaxanthin and fucoxanthin. Recently, the large-scale production of carotenoids from algal sources has gained significant interest with respect to commercial and industrial applications for health, nutrition, and cosmetic applications. Although conventional processing technologies, based on solvent extraction, offer a simple approach to isolating carotenoids, they suffer several, inherent limitations, including low efficiency (extraction yield), selectivity (purity), high solvent consumption, and long treatment times, which have led to advancements in the search for innovative extraction technologies. This comprehensive review summarizes the recent trends in the extraction of carotenoids from microalgae and seaweeds through the assistance of different innovative techniques, such as pulsed electric fields, liquid pressurization, supercritical fluids, subcritical fluids, microwaves, ultrasounds, and high-pressure homogenization. In particular, the review critically analyzes technologies, characteristics, advantages, and shortcomings of the different innovative processes, highlighting the differences in terms of yield, selectivity, and economic and environmental sustainability. PMID:27879659

  18. Innovative Alternative Technologies to Extract Carotenoids from Microalgae and Seaweeds

    Directory of Open Access Journals (Sweden)

    Mahesha M. Poojary

    2016-11-01

    Full Text Available Marine microalgae and seaweeds (microalgae represent a sustainable source of various bioactive natural carotenoids, including β-carotene, lutein, astaxanthin, zeaxanthin, violaxanthin and fucoxanthin. Recently, the large-scale production of carotenoids from algal sources has gained significant interest with respect to commercial and industrial applications for health, nutrition, and cosmetic applications. Although conventional processing technologies, based on solvent extraction, offer a simple approach to isolating carotenoids, they suffer several, inherent limitations, including low efficiency (extraction yield, selectivity (purity, high solvent consumption, and long treatment times, which have led to advancements in the search for innovative extraction technologies. This comprehensive review summarizes the recent trends in the extraction of carotenoids from microalgae and seaweeds through the assistance of different innovative techniques, such as pulsed electric fields, liquid pressurization, supercritical fluids, subcritical fluids, microwaves, ultrasounds, and high-pressure homogenization. In particular, the review critically analyzes technologies, characteristics, advantages, and shortcomings of the different innovative processes, highlighting the differences in terms of yield, selectivity, and economic and environmental sustainability.

  19. 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

  20. Vitamins, carotenoids, dietary fiber, and the risk of gastric carcinoma

    NARCIS (Netherlands)

    Botterweck, A.A.M.; Brandt, P.A. van den; Goldbohm, R.A.

    2000-01-01

    BACKGROUND. Numerous components of fruit and vegetables are considered to decrease the risk of gastric carcinoma. In the current prospective study, the authors examined the association between the intake of vitamins, carotenoids, and dietary fiber and vitamin supplement use and the incidence rate of

  1. Strigolactones, a Novel Carotenoid-Derived Plant Hormone

    NARCIS (Netherlands)

    Al-Babili, S.; Bouwmeester, H.J.

    2015-01-01

    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

  2. Vibronic coupling in the excited-states of carotenoids

    Energy Technology Data Exchange (ETDEWEB)

    Miki, Takeshi [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany; Buckup, Tiago [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany; Krause, Marie S. [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany; Southall, June [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow, UK; Cogdell, Richard J. [College of Medical; Veterinary, and Life Science; University of Glasgow; G12 8QQ Glasgow, UK; Motzkus, Marcus [Physikalisch-Chemisches Institut; Ruprecht-Karls-Universität Heidelberg; D-69120 Heidelberg, Germany

    2016-01-01

    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 S2to the optically dark state S1.

  3. 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

  4. 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

  5. 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: CE - Biochemistry Impact factor: 4.864, year: 2015

  6. Innovative Alternative Technologies to Extract Carotenoids from Microalgae and Seaweeds.

    Science.gov (United States)

    Poojary, Mahesha M; Barba, Francisco J; Aliakbarian, Bahar; Donsì, Francesco; Pataro, Gianpiero; Dias, Daniel A; Juliano, Pablo

    2016-11-22

    Marine microalgae and seaweeds (microalgae) represent a sustainable source of various bioactive natural carotenoids, including β-carotene, lutein, astaxanthin, zeaxanthin, violaxanthin and fucoxanthin. Recently, the large-scale production of carotenoids from algal sources has gained significant interest with respect to commercial and industrial applications for health, nutrition, and cosmetic applications. Although conventional processing technologies, based on solvent extraction, offer a simple approach to isolating carotenoids, they suffer several, inherent limitations, including low efficiency (extraction yield), selectivity (purity), high solvent consumption, and long treatment times, which have led to advancements in the search for innovative extraction technologies. This comprehensive review summarizes the recent trends in the extraction of carotenoids from microalgae and seaweeds through the assistance of different innovative techniques, such as pulsed electric fields, liquid pressurization, supercritical fluids, subcritical fluids, microwaves, ultrasounds, and high-pressure homogenization. In particular, the review critically analyzes technologies, characteristics, advantages, and shortcomings of the different innovative processes, highlighting the differences in terms of yield, selectivity, and economic and environmental sustainability.

  7. 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

  8. Expression profile of genes coding for carotenoid biosynthetic ...

    Indian Academy of Sciences (India)

    Fruit ripening process is associated with change in carotenoid profile and accumulation of lycopene in tomato (Solanum lycopersicum L.). In this study, we quantified the -carotene and lycopene content at green, breaker and red-ripe stages of fruit ripening in eight tomato genotypes by using high-performance liquid ...

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

    Science.gov (United States)

    Dilbeck, Preston L; Tang, Qun; Mothersole, David J; Martin, Elizabeth C; Hunter, C Neil; Bocian, David F; Holten, Dewey; Niedzwiedzki, Dariusz M

    2016-06-23

    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.

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

    Science.gov (United States)

    Maoka, Takashi; Kuwahara, Takashi; Narita, Masanao

    2014-01-01

    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. PMID:24633249

  11. 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.

  12. Circulating carotenoid concentrations are positively correlated with later clutch initiation in Florida Scrub-Jays (Aphelocoma coerulescens).

    Science.gov (United States)

    Heiss, Rebecca S; Cohen, Alan A; Bowman, Reed; Boughton, Raoul K; Bridge, Eli; McGraw, Kevin J; Schoech, Stephan J

    2011-02-01

    Antioxidants play key roles in preventing free radical damage to various molecules, cells, and tissues, but it is not well understood how variation in antioxidant levels may relate to the reproductive success or health of wild animals. We explored the relationship between circulating antioxidant concentrations and both body condition and timing of reproduction in male and female Florida Scrub-Jays (Aphelocoma coerulescens), a cooperatively breeding passerine bird. We examined whether levels of uric acid, vitamin E, and carotenoids (all potentially important antioxidants) were linked to body condition and timing of reproduction, two measures that are directly related to reproductive success. Antioxidant concentrations were not correlated with body condition, but they were related to timing of first clutch initiation, though not always in the predicted direction. Elevated circulating levels of carotenoids were associated with delayed clutch initiation in female breeders. Relatively higher vitamin E levels in control birds were associated with earlier clutch initiation, whereas male breeders that received long-term food supplementation had elevated levels of vitamin E and delayed reproduction. Several potential explanations for the link between elevated levels of antioxidants and delayed clutch initiation are discussed. Separate explanations for each sex include, but are not limited to, oxidative stress as a result of territory defense efforts in males, different dietary regimes due to supplementation, and mobilized plasma antioxidants in females that were coping with a stressor. © 2010 Wiley-Liss, Inc.

  13. 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)

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

    International Nuclear Information System (INIS)

    Silva, Jaqueline M. da; Coelho, Maysa J.; Lima, Keila S.C.; Lima, Antonio L.S.; Ferreira, Rubemar S.

    2007-01-01

    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 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)

  15. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    This article offers a conceptual framework to understand radical change. It opens with a typology that defines change in terms of its pace and scope, and defines radical change as the swift transformation of an entire system...

  16. GMP and AMP as methyl radical traps in the reaction with pentaamminemethylcobalt(III)

    DEFF Research Database (Denmark)

    Kofod, Pauli

    2004-01-01

    C8 methylation of the title purine nucleotides was achieved in near neutral aqueous solution by reaction with 13C enriched [Co(NH 3) 5(CH 3)] 2+. This cation decomposes upon dissolution in water by release of a methyl radical. The latter was identified by electron spin resonance (ESR) spectroscopy...

  17. Free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  18. 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.

  19. Carotenoids, immune response and the expression of sexual ornaments in male greenfinches ( Carduelis chloris)

    Science.gov (United States)

    Aguilera, Eduardo; Amat, Juan A.

    2007-11-01

    Allocation trade-offs of carotenoids between their use in the immune system and production of sexual ornaments have been suggested as a proximate mechanism maintaining honesty of sexual signals. To test this idea, we experimentally examined whether carotenoid availability in the diet was related to variation in antibody response to novel antigens in male greenfinches ( Carduelis chloris aurantiiventris), a species with extensive carotenoid-dependent plumage colouration. We also measured the cost of mounting a humoral response in terms of circulating carotenoids. Finally, we examined the relationship between plumage colour, immune response and circulating carotenoids. We found that males with carotenoid-supplemented diets showed stronger antibody response than non-supplemented birds. We also found that activation of the immune system significantly reduced circulating carotenoids (24.9% lower in immune-challenged birds than in control birds). Finally, intensity (chroma) of ventral plumage colouration of males, a character directly related to concentration of total carotenoids in feathers, was negatively correlated with the immune response and circulating carotenoids in winter. These results support the idea that carotenoids are a limiting resource and that males trade ornamental colouration against immune response.

  20. 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

    2016-03-22

    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.

  1. 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.

  2. The mechanochemical production of phenyl cations through heterolytic bond scission.

    Science.gov (United States)

    Shiraki, Tomohiro; Diesendruck, Charles E; Moore, Jeffrey S

    2014-01-01

    High mechanical forces applied to polymeric materials typically induce unselective chain scission. For the last decade, mechanoresponsive molecules, mechanophores, have been designed to harness the mechanical energy applied to polymers and provide a productive chemical response. The selective homolysis of chemical bonds was achieved by incorporating peroxide and azo mechanophores into polymer backbones. However, selective heterolysis in polymer mechanochemistry is still mostly unachieved. We hypothesized that highly polarized bonds in ionic species are likely to undergo heterolytic bond scission. To test this, we examined a triarylsulfonium salt (TAS) as a mechanophore. Poly(methyl acrylate) possessing TAS at the center of the chain (PMA-TAS) is synthesized by a single electron transfer living radical polymerization (SET-LRP) method. Computational and experimental studies in solution reveal the mechanochemical production of phenyl cations from PMA-TAS. Interestingly, the generated phenyl cation reacts with its counter-anion (trifluoromethanesulfonate) to produce a terminal trifluoromethyl benzene structure that, to the best of our knowledge, is not observed in the photolysis of TAS. Moreover, the phenyl cation can be trapped by the addition of a nucleophile. These findings emphasize the interesting reaction pathways that become available by mechanical activation.

  3. 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.

  4. 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...

  5. A noninvasive assessment of skin carotenoid status through reflection spectroscopy is a feasible and reliable measure of dietary carotenoid consumption in a diverse community sample

    Science.gov (United States)

    Background: Skin carotenoid status, as assessed by reflection spectroscopy (RS), is a promising means of approximating fruit and vegetable consumption. This study’s purpose was to assess the feasibility, reliability, and validity of RS to assess skin carotenoids in a racially diverse community sampl...

  6. Radical distinction : Support for radical left and radical right parties in Europe

    NARCIS (Netherlands)

    Rooduijn, Matthijs; Burgoon, Brian; van Elsas, Erika J.; van de Werfhorst, Herman G.

    2017-01-01

    Support for radical parties on both the left and right is on the rise, fueling intuition that both radicalisms have similar underpinnings. Indeed, existing studies show that radical left and right voters have overlapping positions and preferences. In this article, however, we focus on the

  7. 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...

  8. Synchrotron-based valence shell photoionization of CH radical

    Energy Technology Data Exchange (ETDEWEB)

    Gans, B., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr; Falvo, C. [Institut des Sciences Moléculaires d’Orsay (ISMO), CNRS, Univ. Paris-Sud, Université Paris-Saclay, F-91405 Orsay (France); Holzmeier, F.; Röder, A. [Institut of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg (Germany); Krüger, J.; Garcia, G. A. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette Cedex (France); Lopes, A.; Alcaraz, C., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr [Laboratoire de Chimie Physique, UMR 8000 CNRS—Univ. Paris-Sud, Univ. Paris-Saclay, Bât. 350, Centre Universitaire Paris-Sud, F-91405 Orsay Cedex (France); Fittschen, C. [Université Lille, CNRS, UMR 8522–PC2A–Physicochimie des Processus de Combustion et de l’Atmosphère, F-59000 Lille (France); Loison, J.-C. [Institut des Sciences Moléculaires, UMR 5255 CNRS—Université de Bordeaux, Bât. A12, 351 cours de la Libération, F-33405 Talence Cedex (France)

    2016-05-28

    We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

  9. Assessment of leaf carotenoids content with a new carotenoid index: Development and validation on experimental and model data

    Science.gov (United States)

    Zhou, Xianfeng; Huang, Wenjiang; Kong, Weiping; Ye, Huichun; Dong, Yingying; Casa, Raffaele

    2017-05-01

    Leaf carotenoids content (LCar) is an important indicator of plant physiological status. Accurate estimation of LCar provides valuable insight into early detection of stress in vegetation. With spectroscopy techniques, a semi-empirical approach based on spectral indices was extensively used for carotenoids content estimation. However, established spectral indices for carotenoids that generally rely on limited measured data, might lack predictive accuracy for carotenoids estimation in various species and at different growth stages. In this study, we propose a new carotenoid index (CARI) for LCar assessment based on a large synthetic dataset simulated from the leaf radiative transfer model PROSPECT-5, and evaluate its capability with both simulated data from PROSPECT-5 and 4SAIL and extensive experimental datasets: the ANGERS dataset and experimental data acquired in field experiments in China in 2004. Results show that CARI was the index most linearly correlated with carotenoids content at the leaf level using a synthetic dataset (R2 = 0.943, RMSE = 1.196 μg/cm2), compared with published spectral indices. Cross-validation results with CARI using ANGERS data achieved quite an accurate estimation (R2 = 0.545, RMSE = 3.413 μg/cm2), though the RBRI performed as the best index (R2 = 0.727, RMSE = 2.640 μg/cm2). CARI also showed good accuracy (R2 = 0.639, RMSE = 1.520 μg/cm2) for LCar assessment with leaf level field survey data, though PRI performed better (R2 = 0.710, RMSE = 1.369 μg/cm2). Whereas RBRI, PRI and other assessed spectral indices showed a good performance for a given dataset, overall their estimation accuracy was not consistent across all datasets used in this study. Conversely CARI was more robust showing good results in all datasets. Further assessment of LCar with simulated and measured canopy reflectance data indicated that CARI might not be very sensitive to LCar changes at low leaf area index (LAI) value, and in these conditions soil moisture

  10. Micronutrient Fortification of Foods

    African Journals Online (AJOL)

    Micronutrient Fortification of Foods: Developing A Program. Mahshid Lotti, M.G. Venkatesh Manar, Richard J. H. M. .... Develop the fortification technology. 11. Perform studies on interactions, potency, stability, ... Fortification with vitamin A is a long-term strategy capable of maintaining adequate vitamin A status over time.

  11. 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.

  12. Carotenoid-cleavage activities of crude enzymes from Pandanous amryllifolius.

    Science.gov (United States)

    Ningrum, Andriati; Schreiner, Matthias

    2014-11-01

    Carotenoid degradation products, known as norisoprenoids, are aroma-impact compounds in several plants. Pandan wangi is a common name of the shrub Pandanus amaryllifolius. The genus name 'Pandanus' is derived from the Indonesian name of the tree, pandan. In Indonesia, the leaves from the plant are used for several purposes, e.g., as natural colorants and flavor, and as traditional treatments. The aim of this study was to determine the cleavage of β-carotene and β-apo-8'-carotenal by carotenoid-cleavage enzymes isolated from pandan leaves, to investigate dependencies of the enzymatic activities on temperature and pH, to determine the enzymatic reaction products by using Headspace Solid Phase Microextraction Gas Chromatography/Mass Spectrophotometry (HS-SPME GC/MS), and to investigate the influence of heat treatment and addition of crude enzyme on formation of norisoprenoids. Crude enzymes from pandan leaves showed higher activity against β-carotene than β-apo-8'-carotenal. The optimum temperature of crude enzymes was 70°, while the optimum pH value was 6. We identified β-ionone as the major volatile reaction product from the incubations of two different carotenoid substrates, β-carotene and β-apo-8'-carotenal. Several treatments, e.g., heat treatment and addition of crude enzymes in pandan leaves contributed to the norisoprenoid content. Our findings revealed that the crude enzymes from pandan leaves with carotenoid-cleavage activity might provide a potential application, especially for biocatalysis, in natural-flavor industry. Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich.

  13. 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...

  14. Carotenoid status among preschool children with vitamin A deficiency in the Republic of the Marshall Islands.

    Science.gov (United States)

    Gamble, Mary V; Palafox, Neal A; Dancheck, Barbara; Ricks, Michelle O; Briand, Kennar; Semba, Richard D

    2004-01-01

    Although carotenoids are known to be important dietary sources of vitamin A, there have been few epidemiological studies that have characterized the serum concentrations of major dietary carotenoids among preschool children with vitamin A deficiency. We conducted a population-based, cross-sectional study of serum pro-vitamin A carotenoids (alpha -carotene, beta-carotene, beta-cryptoxanthin), non-provitamin A carotenoids (lutein/zeaxanthin, and lycopene), and retinol among 278 children, aged 1-5 y, in the Republic of the Marshall Islands. Vitamin A deficiency was defined as serum retinol Marshall Islands have extremely low serum concentrations of provitamin A carotenoids and interventions are needed to improve the dietary intake of provitamin A carotenoids among Marshallese children.

  15. Concurrent production of carotenoids and lipid by a filamentous microalga Trentepohlia arborum.

    Science.gov (United States)

    Chen, Lin; Zhang, Lanlan; Liu, Tianzhong

    2016-08-01

    During the study of Trentepohlia arborum it became clear that its cells are rich in lipids and carotenoids. Thus, lipid content, composition and fatty acids profiles in individual lipid classes, as well as pigment profiles, responding to different culture conditions, were further investigated. The results showed that the predominant carotenoids and lipid fraction in total lipid in this study was β-carotene and TAG, respectively. The lipid content increased significantly under high light while nitrogen-replete conditions induced the highest carotenoids content. However, only with a double stress of high light and nitrogen-deficiency it was possible to maximize the productivities of both carotenoids and lipids. Carotenoids (mainly β-carotene) accounted for ca. 5% of the microalgal lipid under the double stress. Data herein show the potential of T. arborum for the production of both lipids and carotenoids, and hence provide an appropriate way to produce different products from T. arborum. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. In vivo Raman spectroscopy detects increased epidermal antioxidative potential with topically applied carotenoids

    International Nuclear Information System (INIS)

    Lademann, J; Richter, H; Patzelt, A; Darvin, M; Sterry, W; Fluhr, J W; Caspers, P J; Van der Pol, A; Zastrow, L

    2009-01-01

    In the present study, the distribution of the carotenoids as a marker for the complete antioxidative potential in human skin was investigated before and after the topical application of carotenoids by in vivo Raman spectroscopy with an excitation wavelength of 785 nm. The carotenoid profile was assessed after a short term topical application in 4 healthy volunteers. In the untreated skin, the highest concentration of natural carotenoids was detected in different layers of the stratum corneum (SC) close to the skin surface. After topical application of carotenoids, an increase in the antioxidative potential in the skin could be observed. Topically applied carotenoids penetrate deep into the epidermis down to approximately 24 μm. This study supports the hypothesis that antioxidative substances are secreted via eccrine sweat glands and/or sebaceous glands to the skin surface. Subsequently they penetrate into the different layers of the SC

  17. 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

    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.

  18. Identification of Carotenoids in Halimeda macroloba Reef Associated Bacteria

    Directory of Open Access Journals (Sweden)

    Wiwik Astuti

    2016-12-01

    Full Text Available Several carotenoid pigments which are produced by sea microorganisms are shown to function as antimicrobe compounds and potential antioxidants. Coral reefs with high levels of diverse biota facilitate Halimeda as a primary component and producer to have associated bacteria that produce relatively unknown metabolic compounds. This research attempts to isolate bacteria that are associated with Halimeda macroloba, identify it, as well as analyze the pigment content produced. A yellow-orange bacteria colony is successfully isolated and given the temporary name MK_HM. This bacteria is in the shape of circular (oval rods and are gram-variable bacteria. Based on the sequencing analytical results, Blast homology, as well as a phylogenetic analysis, it shows that the bacteria have a relationship with Exiguobacterium aestuarii TF-16 at 94%, so that it can be strongly predicted that the MK_HM strain is a new species. This pigment analysis, which is conducted on the Exiguobacterium sp. MK_HM bacteria extract, reveals that this strain produces carotenoid pigments of diadinochrome, semi-α-carotenone, dinoxanthin, and P457.   Keywords: Exiguobacterium, carotenoid, diadinochrome, semi-α-carotenone, dinoxanthin, and P457.

  19. 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.

  20. Carotenoid production and phenotypic variation in Azospirillum brasilense.

    Science.gov (United States)

    Brenholtz, Gal Reem; Tamir-Ariel, Dafna; Okon, Yaacov; Burdman, Saul

    2017-06-01

    We assessed the occurrence of phenotypic variation in Azospirillum brasilense strains Sp7, Cd, Sp245, Az39 and phv2 during growth in rich media, screening for variants altered in colony pigmentation or extracellular polysaccharide (EPS) production. Previous studies showed that EPS-overproducing variants of Sp7 appear frequently following starvation or growth in minimal medium. In contrast, no such variants were detected during growth in rich media in the tested strains except for few variants of phv2. Regarding alteration in colony pigmentation (from pink to white in strain Cd and from white to pink in the others), strain Sp7 showed a relatively high frequency of variation (0.009-0.026%). Strain Cd showed a lower frequency of alteration in pigmentation (0-0.008%), and this type of variation was not detected in the other strains. In A. brasilense, carotenoid synthesis is controlled by two RpoE sigma factors and their cognate ChrR anti-sigma factors, the latter acting as negative regulators of carotenoid synthesis. Here, all tested (n = 28) pink variants of Sp7 carried mutations in one of the anti-sigma factor genes, chrR1. Our findings indicate that, in A. brasilense, phenotypic variation is strain- and environment-dependent and support the central role of ChrR1 in regulation of carotenoid production. Copyright © 2017 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  1. Impact of canning and storage on apricot carotenoids and polyphenols.

    Science.gov (United States)

    Le Bourvellec, Carine; Gouble, Barbara; Bureau, Sylvie; Reling, Patrice; Bott, Romain; Ribas-Agusti, Albert; Audergon, Jean-Marc; Renard, Catherine M G C

    2018-02-01

    Apricot polyphenols and carotenoids were monitored after industrial and domestic cooking, and after 2months of storage for industrial processing. The main apricot polyphenols were flavan-3-ols, flavan-3-ol monomers and oligomers, with an average degree of polymerization between 4.7 and 10.7 and caffeoylquinic acids. Flavonols and anthocyanins were minor phenolic compounds. Upon processing procyanidins were retained in apricot tissue. Hydroxycinnamic acids, flavan-3-ol monomers, flavonols and anthocyanins leached in the syrup. Flavonol concentrations on per-can basis were significantly increased after processing. Industrial processing effects were higher than domestic cooking probably due to higher temperature and longer duration. After 2months of storage, among polyphenols only hydroxycinnamic acids, flavan-3-ol monomers and anthocyanins were reduced. Whichever the processing method, no significant reductions of total carotenoids were observed after processing. The cis-β-carotene isomer was significantly increased after processing but with a lower extent in domestic cooking. Significant decreased in total carotenoid compounds occurred during storage. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Blue light dosage affects carotenoids and tocopherols in microgreens.

    Science.gov (United States)

    Samuolienė, Giedrė; Viršilė, Akvilė; Brazaitytė, Aušra; Jankauskienė, Julė; Sakalauskienė, Sandra; Vaštakaitė, Viktorija; Novičkovas, Algirdas; Viškelienė, Alina; Sasnauskas, Audrius; Duchovskis, Pavelas

    2017-08-01

    Mustard, beet and parsley were grown to harvest time under selected LEDs: 638+660+731+0% 445nm; 638+660+731+8% 445nm; 638+660+731+16% 445nm; 638+660+731+25% 445nm; 638+660+731+33% 445nm. From 1.2 to 4.3 times higher concentrations of chlorophylls a and b, carotenoids, α- and β-carotenes, lutein, violaxanthin and zeaxanthin was found under blue 33% treatment in comparison to lower blue light dosages. Meanwhile, the accumulation of metabolites, which were not directly connected with light reactions, such as tocopherols, was more influenced by lower (16%) blue light dosage, increasing about 1.3 times. Thus, microgreen enrichment of carotenoid and xanthophyll pigments may be achieved using higher (16-33%) blue light intensities. Changes in metabolite quantities were not the result of changes of other carotenoid concentration, but were more influenced by light treatment and depended on the species. Significant quantitative changes in response to blue light percentage were obtained for both directly and not directly light-dependent metabolite groups. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Biotechnological conversion of spent coffee grounds into polyhydroxyalkanoates and carotenoids.

    Science.gov (United States)

    Obruca, Stanislav; Benesova, Pavla; Kucera, Dan; Petrik, Sinisa; Marova, Ivana

    2015-12-25

    Coffee is one of the world's most popular beverages and has been growing steadily in commercial importance. Nowadays, coffee is the second largest traded commodity in the world, after petroleum. Hence, coffee industry is responsible for the generation of large amounts of waste, especially spent coffee grounds (SCG). Various attempts to valorize this waste stream of coffee industry were made. This article summarizes our research and publications aiming at the conversion of SCG into valuable products - polyhydroxyalkanoates (PHAs) and carotenoids. At first, oil extracted from SCG (approx. 15 wt% oil in SCG) can be efficiently (YP/S=0.82 g/g) converted into PHA employing Cupriavidus necator H16. Further, the solid residues after oil extraction can be hydrolyzed (by the combination of chemical and enzymatic hydrolysis) yielding fermentable sugars, which can be further used as a substrate for the production of PHAs employing Bacillus megaterium (YP/S=0.04 g/g) or Burkholderia cepacia (YP/S=0.24 g/g). Alternatively, SCG hydrolysate can be used as a substrate for biotechnological production of carotenoids by carotenogenic yeast Sporobolomyces roseus. Solid residues after either oil extraction or hydrolysis can be used as fuel in industrial boilers to generate heat and energy. Therefore, entire biomass of SCG can be used for sustainable production of PHAs and/or carotenoids employing bio-refinery approach. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Catalysis of Radical Reactions: A Radical Chemistry Perspective.

    Science.gov (United States)

    Studer, Armido; Curran, Dennis P

    2016-01-04

    The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in "catalytic amounts" is a catalyst, an initiator, or something else? Herein we critically address both catalyst-free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non-chain processes afford diverse opportunities for catalysis, as illustrated with selected examples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Comparative genomics reveals candidate carotenoid pathway regulators of ripening watermelon fruit

    Science.gov (United States)

    2013-01-01

    Background Many fruits, including watermelon, are proficient in carotenoid accumulation during ripening. While most genes encoding steps in the carotenoid biosynthetic pathway have been cloned, few transcriptional regulators of these genes have been defined to date. Here we describe the identification of a set of putative carotenoid-related transcription factors resulting from fresh watermelon carotenoid and transcriptome analysis during fruit development and ripening. Our goal is to both clarify the expression profiles of carotenoid pathway genes and to identify candidate regulators and molecular targets for crop improvement. Results Total carotenoids progressively increased during fruit ripening up to ~55 μg g-1 fw in red-ripe fruits. Trans-lycopene was the carotenoid that contributed most to this increase. Many of the genes related to carotenoid metabolism displayed changing expression levels during fruit ripening generating a metabolic flux toward carotenoid synthesis. Constitutive low expression of lycopene cyclase genes resulted in lycopene accumulation. RNA-seq expression profiling of watermelon fruit development yielded a set of transcription factors whose expression was correlated with ripening and carotenoid accumulation. Nineteen putative transcription factor genes from watermelon and homologous to tomato carotenoid-associated genes were identified. Among these, six were differentially expressed in the flesh of both species during fruit development and ripening. Conclusions Taken together the data suggest that, while the regulation of a common set of metabolic genes likely influences carotenoid synthesis and accumulation in watermelon and tomato fruits during development and ripening, specific and limiting regulators may differ between climacteric and non-climacteric fruits, possibly related to their differential susceptibility to and use of ethylene during ripening. PMID:24219562

  6. The production and analysis of carotenoid preparations from some strains of xylotrophic Basidiomycetes

    Directory of Open Access Journals (Sweden)

    A. K. Velygodska

    2016-07-01

    Full Text Available The aim of the study was selection of optimal conditions for obtaining carotenoid drugs of mycelium origin from the basidiomycete strains Laetiporus sulphureus Ls-08, Fomes fomentarius Ff-1201 and Fistulina hepatica Fh-18 and the study of antibacterial and total antioxidant activity of these compounds. The strains were surface grown on a glucose-peptone medium modified for each producer. The homogenized pigments of the mycelium strains were extracted with ethanol and the solvent was separated under vacuum at 60 ºC. The absorption spectra of the carotenoid drugs were recorded for alcoholic solutions at 350–500 nm. The antibacterial activity of the carotenoids was determined by the agar diffusion method, and the total antioxidant activity was determined by the DPPH-method. It was found that the optimum temperature for carotenoid extraction is 60 °C. The absorption spectra of carotenoid drugs showed three peaks in 420, 450 and 470 nm. These results respond to the β-carotene absorption spectra. The highest antioxidant activity was noted for carotenoid drugs from F. hepatica Fh-18 and L. sulphureus Ls-08 strains obtained at an extraction temperature of 40 and 60 °C respectively. The antibacterial activity of carotenoid drugs against the test cultures was not species dependent. Carotenoid drugs with a 20% concentrate obtained from the L. sulphureus Ls-08 strain had the highest antibacterial activity against the test cultures Staphylococcus aureus and Escherichia coli. Carotenoids from the mycelium of F. hepatica Fh-18 had the highest antibacterial activity against the test culture Candida albicans. Extraction temperature of 60 °C is optimal for mycelial yield of carotenoids from the studied strains. All preparations of carotenoids exhibited antibacterial activity against the test microorganism cultures. The carotenoid drugs obtained at 40 and 60 °C from the strains F. hepatica Fh-18 and L. sulphureus Ls-08 respectively showed the highest

  7. 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.

  8. Use of Several waste substrates for carotenoid-rich yeast biomass production

    International Nuclear Information System (INIS)

    Marova, I.; Carnecka, M.; Halienova, A.; Dvorakova, T.; Haronikova, A.

    2009-01-01

    Carotenoids are industrially significant pigments produced in many bacteria, fungi, and plants. Carotenoid biosynthesis in yeasts is involved in stress response mechanisms. Thus, control ed physiological and nutrition stress can be used for enhanced pigment production. Huge commercial demand for natural carotenoids has focused attention on developing of suitable biotechnological techniques including use of liquid waste substrates as carbon and/or nitrogen source. (Author)

  9. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  10. 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

    2014-01-01

    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.

  11. Ecological, morphological and phylogenetic correlates of interspecific variation in plasma carotenoid concentration in birds.

    Science.gov (United States)

    Tella, J L; Figuerola, J; Negro, J J; Blanco, G; Rodríguez-Estrella, R; Forero, M G; Blázquez, M C; Green, A J; Hiraldo, F

    2004-01-01

    Carotenoids are important as pigments for bright coloration of animals, and as physiologically active compounds with a wide array of health-related benefits. However, the causes of variation in carotenoid acquisition and physiology among species are poorly known. We measured the concentration of carotenoids in the blood of 80 wild bird species differing in diet, body size and the extent of carotenoid-based traits. Preliminary analyses showed that diet significantly explains interspecific variability in plasma carotenoids. However, dietary influences were apparently overridden by phylogenetic relationships among species, which explained most (65%) of this variability. This phylogenetic effect could be due partly to its covariation with diet, but may also be caused by interspecific differences in carotenoid absorption from food to the blood stream, mediated, for example by endothelial carriers or gut parasites. Carotenoid concentrations also decreased with body size (which may be explained by the allometric relationship between ingestion rate and body mass), and correlated positively with the extent of carotenoid-dependent coloration of plumage and bare parts. Therefore, the acquisition of carotenoids from the diet and their use for both health and display functions seem to be constrained by ecological and physiological aspects linked to the phylogeny and size of the species.

  12. Testosterone increases bioavailability of carotenoids: insights into the honesty of sexual signaling.

    Science.gov (United States)

    Blas, J; Pérez-Rodríguez, L; Bortolotti, G R; Viñuela, J; Marchant, T A

    2006-12-05

    Androgens and carotenoids play a fundamental role in the expression of secondary sex traits in animals that communicate information on individual quality. In birds, androgens regulate song, aggression, and a variety of sexual ornaments and displays, whereas carotenoids are responsible for the red, yellow, and orange colors of the integument. Parallel, but independent, research lines suggest that the evolutionary stability of each signaling system stems from tradeoffs with immune function: androgens can be immunosuppressive, and carotenoids diverted to coloration prevent their use as immunostimulants. Despite strong similarities in the patterns of sex, age and seasonal variation, social function, and proximate control, there has been little success at integrating potential links between the two signaling systems. These parallel patterns led us to hypothesize that testosterone increases the bioavailability of circulating carotenoids. To test this hypothesis, we manipulated testosterone levels of red-legged partridges Alectoris rufa while monitoring carotenoids, color, and immune function. Testosterone treatment increased the concentration of carotenoids in plasma and liver by >20%. Plasma carotenoids were in turn responsible for individual differences in coloration and immune response. Our results provide experimental evidence for a link between testosterone levels and immunoenhancing carotenoids that (i) reconciles conflicting evidence for the immunosuppressive nature of androgens, (ii) provides physiological grounds for a connection between two of the main signaling systems in animals, (iii) explains how these signaling systems can be evolutionary stable and honest, and (iv) may explain the high prevalence of sexual dimorphism in carotenoid-based coloration in animals.

  13. Carotenoid responses to environmental stimuli: integrating redox and carbon controls into a fruit model.

    Science.gov (United States)

    Fanciullino, A L; Bidel, L P R; Urban, L

    2014-02-01

    Carotenoids play an important role in plant adaptation to fluctuating environments as well as in the human diet by contributing to the prevention of chronic diseases. Insights have been gained recently into the way individual factors, genetic, environmental or developmental, control the carotenoid biosynthetic pathway at the molecular level. The identification of the rate-limiting steps of carotenogenesis has paved the way for programmes of breeding, and metabolic engineering, aimed at increasing the concentration of carotenoids in different crop species. However, the complexity that arises from the interactions between the different factors as well as from the coordination between organs remains poorly understood. This review focuses on recent advances in carotenoid responses to environmental stimuli and discusses how the interactions between the modulation factors and between organs affect carotenoid build-up. We develop the idea that reactive oxygen species/redox status and sugars/carbon status can be considered as integrated factors that account for most effects of the major environmental factors influencing carotenoid biosynthesis. The discussion highlights the concept of carotenoids or carotenoid-derivatives as stress signals that may be involved in feedback controls. We propose a conceptual model of the effects of environmental and developmental factors on carotenoid build-up in fruits. © 2013 John Wiley & Sons Ltd.

  14. 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.

  15. 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.

  16. 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. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

  17. 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.

  18. Electron Transfer Triggers Fast Dimer/Monomer Switching of Pyridinium and Quinolinium Cations

    Czech Academy of Sciences Publication Activity Database

    Teplý, Filip; Čížková, Martina; Slavíček, P.; Kolivoška, Viliam; Tarábek, Ján; Hromadová, Magdaléna; Pospíšil, Lubomír

    2012-01-01

    Roč. 116, č. 5 (2012), s. 3779-3786 ISSN 1932-7447 R&D Projects: GA ČR GA203/09/0705; GA ČR GA203/09/1614 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : electrochemical reduction * dimerization * radicals * mechanism * N-heteroaromatic cations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.814, year: 2012

  19. Plasma carotenoid concentrations of incubating American kestrels (Falco sparverius) show annual, seasonal, and individual variation and explain reproductive outcome

    Science.gov (United States)

    Sassani, Elizabeth C.; Sevy, Christeena; Strasser, Erin H.; Anderson, Alexandra M.; Heath, Julie A.

    2015-01-01

    In wild birds, the proximate and ultimate factors that affect circulating carotenoid concentrations remain poorly understood. We studied variation in plasma carotenoid concentrations across several scales: annual, seasonal, pair, territory and individual, and evaluated whether carotenoid levels explained reproductive outcome of wild American kestrels (Falco sparverius). We sampled plasma carotenoid concentrations of 99 female and 80 male incubating kestrels from April-June in 2008–2012. Plasma carotenoid concentrations were explained by an interaction between year and sex, date, and random effects for pair and individual identity. In general, plasma carotenoid concentrations of males were significantly higher than females, but this depended on year. Within a breeding season, earlier nesting kestrels had higher carotenoid concentrations than later nesting kestrels, a pattern that is coincident with seasonal trends in local fitness. Pair and individual identity explained variation in carotenoid concentrations suggesting that carotenoid concentrations of mated birds were correlated, and some individuals consistently maintained higher carotenoid levels than others. Male carotenoid concentrations were positively associated with number of young fledged per pair. These results are consistent with the hypothesis that higher quality individuals have higher carotenoid levels compared to lower quality individuals, despite annual variations in carotenoid availability. PMID:27041770

  20. Skin and plasma carotenoid response to a provided intervention diet high in vegetables and fruit: uptake and depletion kinetics.

    Science.gov (United States)

    Jahns, Lisa; Johnson, LuAnn K; Mayne, Susan T; Cartmel, Brenda; Picklo, Matthew J; Ermakov, Igor V; Gellermann, Werner; Whigham, Leah D

    2014-09-01

    Objective biomarkers are needed to assess adherence to vegetable and fruit intervention trials. Blood carotenoids are considered the best biomarker of vegetable and fruit intake, but collecting blood is invasive and the analyses are relatively expensive for population studies. Resonance Raman spectroscopy (RRS) is an innovative method for assessing carotenoids in skin noninvasively. Our objective was to compare blood carotenoid concentrations with skin carotenoid assessments by RRS during a controlled feeding intervention. Twenty-nine participants consumed low-carotenoid diets (6 wk, phases 1 and 3), a provided diet containing 6-cup equivalents (1046 g/d) of vegetables and fruit (8 wk, phase 2), and usual diet (final 8 wk, phase 4). At baseline, skin and plasma total carotenoid values were correlated (r = 0.61, P Skin and plasma carotenoid values decreased (P 200% at the end of phase 2. Plasma carotenoids returned to baseline concentrations by the middle of phase 3 and skin carotenoid concentrations by the middle of phase 4. Skin carotenoid status predicted plasma values by using a mixed linear model including all time points (r = 0.72, P skin carotenoid status closely follow changes in plasma across a broad range of intakes. At the individual level, skin carotenoids predicted plasma values (r = 0.70, P Skin carotenoid status assessed by resonance Raman spectroscopy is a noninvasive, objective biomarker of changes in vegetable and fruit intake. © 2014 American Society for Nutrition.

  1. 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.

  2. 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...

  3. 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

  4. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    International Nuclear Information System (INIS)

    Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

    2015-01-01

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe 3+ > Al 3+ > Cu 2+ >> Ca 2+ > K + > Na + , which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na + -smectite and K + -smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe 3+ , Al 3+ , and Cu 2+ are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O 2 − · , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation

  5. Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Hanzhong, E-mail: jiahz@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Li, Li [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Chen, Hongxia; Zhao, Yue [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); School of Geology and Mining Engineering, Xinjiang University, Urumqi 830046 (China); Li, Xiyou [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China); Wang, Chuanyi, E-mail: cywang@ms.xjb.ac.cn [Laboratory of Environmental Sciences and Technology, Xinjiang Technical Institute of Physics & Chemistry, Key Laboratory of Functional Materials and Devices for Special Environments, Chinese Academy of Sciences, Urumqi 830011 (China)

    2015-04-28

    Graphical abstract: Roles of exchangeable cations in PAHs photodegradation on clay surafces under visible light. - Highlights: • Photolysis rate are strongly dependent on the type of cations on clay surface. • The strength of “cation–π” interactions governs the photodegradation rate of PAHs. • Several exchangeable cations could cause a shift in the absorption spectrum of PAHs. • Exchangeable cations influence the type and amount of reactive intermediates. - Abstract: Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe{sup 3+} > Al{sup 3+} > Cu{sup 2+} >> Ca{sup 2+} > K{sup +} > Na{sup +}, which is consistent with the binding energy of cation–π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation–π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na{sup +}-smectite and K{sup +}-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe{sup 3+}, Al{sup 3+}, and Cu{sup 2+} are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O{sub 2}{sup −}· , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation.

  6. 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

  7. Identification and expression analysis of candidate genes involved in carotenoid biosynthesis in chickpea seeds

    Directory of Open Access Journals (Sweden)

    Mohammad Kazem Rezaei

    2016-12-01

    Full Text Available Plant carotenoids have a key role in preventing various diseases in human because of their antioxidant and provitamin A properties. Chickpea is a good source of carotenoid among legumes and its diverse germplasm and genome accessibility makes it a good model for carotenogenesis studies. The structure, location and copy numbers of genes involved in carotenoid biosynthesis were retrieved from the chickpea genome. The majority of the single nucleotide polymorphism (SNPs within these genes across five diverse chickpea cultivars was synonymous mutation. We examined the expression of the carotenogenesis genes and their association with carotenoid concentration at different seed development stages of five chickpea cultivars. Total carotenoid concentration ranged from 22 μg g-1 in yellow cotyledon kabuli to 44 μg g-1 in green cotyledon desi at 32 days post anthesis (DPA. The majority of carotenoids in chickpea seeds consists of lutein and zeaxanthin. The expression of the selected 19 genes involved in carotenoid biosynthesis pathway showed common pattern across five cultivars with higher expression at 8 and/or 16 DPA then dropped considerably at 24 and 32 DPA. Almost all genes were up-regulated in CDC Jade cultivar. Correlation analysis between gene expression and carotenoid concentration showed that the genes involved in the primary step of carotenoid biosynthesis pathway including carotenoid desaturase and isomerase positively correlated with various carotenoid components in chickpea seeds. A negative correlation was found between hydroxylation activity and provitamin A concentration in the seeds. The highest provitamin A concentration including β-carotene and β-cryptoxanthin were found in green cotyledon chickpea cultivars.

  8. Environmental stress affects the expression of a carotenoid-based sexual trait in male zebra finches.

    Science.gov (United States)

    Eraud, Cyril; Devevey, Godefroy; Gaillard, Maria; Prost, Josiane; Sorci, Gabriele; Faivre, Bruno

    2007-10-01

    Abiotic factors including thermal stress are suggested to exert constrains on sexual ornaments through trade-offs between sexual displays and physiological functions related to self-maintenance. Given the health properties of carotenoid pigments, carotenoid-based ornaments offer a relevant context in which to investigate the effect of environmental stress, such as ambient temperature, on the production and maintenance of secondary sexual traits and, also, to explore the proximate mechanisms shaping their expression. In this study, we exposed male zebra finches (Taeniopygia guttata) to environmental stress by exposing them to two temperature regimes (6 and 26 degrees C) over a 4 week period. Simultaneously, half of the males in each temperature group were supplemented with carotenoids, whereas the other half were not. The expression of a carotenoid-based sexual trait (bill colour) and the amount of circulating carotenoids were assessed before and at the end of the experiment. Carotenoid-supplemented males developed a redder bill, but the effect of supplementation was reduced under cold exposure. However, we found evidence that birds facing a cold stress were carotenoid limited, since supplemented males developed redder bills than the non-supplemented ones. Interestingly, while cold-exposed and non-supplemented males developed duller bills, they circulated a higher amount of carotenoids at the end of the experiment compared to the pre-experimental values. Together, these results suggest that ambient temperature might contribute to the modulation of the expression of carotenoid-based ornaments. Our findings suggest that carotenoids are a limiting resource under cold exposure and that they might be prioritized for self-maintenance at the expense of the ornament. The physiological functions related to self-maintenance that might have benefited from carotenoid saving are discussed.

  9. 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.

  10. Gamma and Ion-Beam Irradiation of DNA: Free Radical Mechanisms, Electron Effects, and Radiation Chemical Track Structure

    Science.gov (United States)

    Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

    2016-01-01

    The focus of our laboratory’s investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ−) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre−), and aqueous (or, solvated) electrons (eaq−)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species. PMID:27695205

  11. Cation-Coupled Bicarbonate Transporters

    OpenAIRE

    Aalkjaer, Christian; Boedtkjer, Ebbe; Choi, Inyeong; Lee, Soojung

    2014-01-01

    Cation-coupled HCO3− transport was initially identified in the mid-1970s when pioneering studies showed that acid extrusion from cells is stimulated by CO2/HCO3− and associated with Na+ and Cl− movement. The first Na+-coupled bicarbonate transporter (NCBT) was expression-cloned in the late 1990s. There are currently five mammalian NCBTs in the SLC4-family: the electrogenic Na,HCO3-cotransporters NBCe1 and NBCe2 (SLC4A4 and SLC4A5 gene products); the electroneutral Na,HCO3-cotransporter NBCn1 ...

  12. 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.

  13. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.

    2010-03-01

    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  14. 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.

  15. 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.

  16. 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

  17. Relationship between Carotenoids, Retinol, and Estradiol Levels in Older Women.

    Science.gov (United States)

    Maggio, Marcello; de Vita, Francesca; Lauretani, Fulvio; Bandinelli, Stefania; Semba, Richard D; Bartali, Benedetta; Cherubini, Antonio; Cappola, Anne R; Ceda, Gian Paolo; Ferrucci, Luigi

    2015-08-05

    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. 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. 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 ± 0.08, p = 0.0009), and E2 persisted whereas the

  18. Free radicals and polarized targets

    Science.gov (United States)

    Bunyatova, E. I.

    2004-06-01

    Many free radicals were added to organic compounds in search of high proton and deuteron polarizations. Few found practical application. A short review is presented, and special attention is given to some stable nitroxyl radicals which have lately been admixed to organic compounds solid at room temperature, in particular to scintillators.

  19. Free radicals and polarized targets

    Energy Technology Data Exchange (ETDEWEB)

    Bunyatova, E.I. E-mail: bunyatel@nusun.jinr.ru

    2004-06-21

    Many free radicals were added to organic compounds in search of high proton and deuteron polarizations. Few found practical application. A short review is presented, and special attention is given to some stable nitroxyl radicals which have lately been admixed to organic compounds solid at room temperature, in particular to scintillators.

  20. Hydroxyl radical reactivity with diethylhydroxylamine

    International Nuclear Information System (INIS)

    Gorse, R.A. Jr.; Lii, R.R.; Saunders, B.B.

    1977-01-01

    Diethylhydroxylamine (DEHA) reacts with gas-phase hydroxyl radicals on every third collision, whereas the corresponding reaction in aqueous solution is considerably slower. The high gas-phase reactivity explains the predicted inhibitory effect of DEHA in atmospheric smog processes. Results from the studies in the aqueous phase are helpful in predicting the mechanism of the reaction of DEHA with hydroxyl radicals

  1. Host-related factors explaining interindividual variability of carotenoid bioavailability and tissue concentrations in humans

    NARCIS (Netherlands)

    Bohn, Torsten; Desmarchelier, Charles; Dragsted, Lars O.; Nielsen, Charlotte S.; Stahl, Wilhelm; Rühl, Ralph; Keijer, Jaap; Borel, Patrick

    2017-01-01

    Carotenoid dietary intake and their endogenous levels have been associated with a decreased risk of several chronic diseases. There are indications that carotenoid bioavailability depends, in addition to the food matrix, on host factors. These include diseases (e.g. colitis), life-style habits (e.g.

  2. Evaluation of antigenotoxic effects of carotenoids from green algae Chlorococcum humicola using human lymphocytes.

    Science.gov (United States)

    Bhagavathy, S; Sumathi, P

    2012-02-01

    To identify the available phytochemicals and carotenoids in the selected green algae and evaluate the potential genotoxic/antigenotoxic effect using lymphocytes. 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). 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 (Palgae 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.

  3. Further insights on the carotenoid profile of the echinoderm Marthasterias glacialis L.

    Science.gov (United States)

    Mariutti, Lilian R B; Pereira, David M; Mercadante, Adriana Zerlotti; Valentão, Patrícia; Teixeira, Natércia; Andrade, Paula B

    2012-07-01

    In this study, the carotenoid profile of the echinoderm Marthasterias glacialis L. was established using HPLC-DAD-APCI-MS/MS equipped with a C(30) column. This approach rendered the identification of 20 compounds, eight of them reported for the first time in this marine organism. Differentiation of carotenoid isomers was also achieved.

  4. 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

  5. Predictors of adipose tissue carotenoid and retinol levels in nine countries: The EURAMIC study

    NARCIS (Netherlands)

    Virtanen, S.M.; Veer, P. van 't; Kok, F.; Kardinaal, A.F.M.; Aro, A.

    1996-01-01

    The adipose tissue carotenoid (alpha-carotene, beta-carotene, and lycopene) and retinol levels and their predictors were determined in 686 male and 339 female middle-aged and elderly subjects from eight European countries and Israel during the years 1991 to 1992. Adipose tissue carotenoid levels in

  6. Analysis of carotenoid composition in petals of calendula (Calendula officinalis L.).

    Science.gov (United States)

    Kishimoto, Sanae; Maoka, Takashi; Sumitomo, Katsuhiko; Ohmiya, Akemi

    2005-11-01

    Nineteen carotenoids were identified in extracts of petals of orange- and yellow-flowered cultivars of calendula (Calendula officinalis L.). Ten carotenoids were unique to orange-flowered cultivars. The UV-vis absorption maxima of these ten carotenoids were at longer wavelengths than that of flavoxanthin, the main carotenoid of calendula petals, and it is clear that these carotenoids are responsible for the orange color of the petals. Six carotenoids had a cis structure at C-5 (C-5'), and it is conceivable that these (5Z)-carotenoids are enzymatically isomerized at C-5 in a pathway that diverges from the main carotenoid biosynthesis pathway. Among them, (5Z,9Z)-lycopene (1), (5Z,9Z,5'Z,9'Z)-lycopene (3), (5'Z)-gamma-carotene (4), and (5'Z,9'Z)-rubixanthin (5) has never before been identified. Additionally, (5Z,9Z,5'Z)-lycopene (2) has been reported only as a synthesized compound.

  7. 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…

  8. Tetrapyrrole singlet excited state quenching by carotenoids in an artificial photosynthetic antenna

    NARCIS (Netherlands)

    Palacios, R.E.; Kodis, G.; Herrero, C.; Ochoa, E.M.; Gervaldo, M.; Gould, S.L.; Kennis, J.T.M.; Gust, D.; Moore, T.A.; Moore, A.L.

    2006-01-01

    Two artificial photosynthetic antenna models consisting of a Si phthalocyanine (Pc) bearing two axially attached carotenoid moieties having either 9 or 10 conjugated double bonds are used to illustrate some of the function of carotenoids in photosynthetic membranes. Both models studied in toluene,

  9. Process optimization for extraction of carotenoids from medicinal caterpillar fungus, Cordyceps militaris (Ascomycetes).

    Science.gov (United States)

    Yang, Tao; Sun, Junde; Lian, Tiantian; Wang, Wenzhao; Dong, Cai-Hong

    2014-01-01

    Natural carotenoids have attracted great attention for their important beneficial effects on human health and food coloring function. Cordyceps militaris, a well-known edible and medicinal fungus, is a potential source of natural carotenoids. The present study aimed to optimize the process parameters for carotenoid extraction from this mushroom. The effects of different methods of breaking the fungal cell wall and organic solvents were studied by the one-factor-at-a-time method. Subsequently, the process parameters including the duration of the extraction time, the number of extractions, and the solvent to solid ratio were optimized by using the Box-Behnken design. The optimal extraction conditions included using an acid-heating method to break the cell wall and later extracting three times, each for a 1 h duration, with a 4:1 mixture of acetone: petroleum ether and a solvent: solid ratio of 24:1. The carotenoid content varied from 2122.50 to 3847.50 µg/g dry weights in different commercially obtained fruit bodies of C. militaris. The results demonstrated that the C. militaris contained more carotenoid content in its fruit bodies than other known mushrooms. Stability monitoring by HPLC demonstrated that the carotenoids could be stored at 4°C for 40 d. It is suggested that the carotenoid content should be considered as the quality standard of commercial products of this valued mushroom. These findings will facilitate the exploration of carotenoids from C. militaris.

  10. 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.

  11. CAROTENOIDS DIGESTION IN AFRICAN STARGRASS (Cynodon plectostachyus DETERMINED WITH In Situ TECHNIQUES IN CATTLE

    Directory of Open Access Journals (Sweden)

    Efren Ramirez-Bribiesca

    2011-09-01

    Full Text Available Dry matter (DM and total carotenoids disappearane in the rumen and intestinal passage of African stargrass (AS were measured in 4 Holstein steers using rumen In situ and a mobile nylon bag technique in duodenum, respectively. A higher proportion of DM and total carotenoids (P

  12. 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.

  13. 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

  14. The interplay between gonadal steroids and immune defence in affecting a carotenoid-dependent trait

    NARCIS (Netherlands)

    Casagrande, Stefania; Groothuis, Ton G. G.; Rubenstein, D.

    2011-01-01

    The hypothesis that sexual ornaments are honest signals of quality because their expression is dependent on hormones with immune-depressive effects has received ambiguous support. The hypothesis might be correct for those signals that are carotenoid-dependent because the required carotenoid

  15. Carotenoids and their conversion products in the control of adipocyte function, adiposity and obesity.

    Science.gov (United States)

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

    2015-04-15

    A novel perspective of the function of carotenoids and carotenoid-derived products - including, but not restricted to, the retinoids - is emerging in recent years which connects these compounds to the control of adipocyte biology and body fat accumulation, with implications for the management of obesity, diabetes and cardiovascular disease. Cell and animal studies indicate that carotenoids and carotenoids derivatives can reduce adiposity and impact key aspects of adipose tissue biology including adipocyte differentiation, hypertrophy, capacity for fatty acid oxidation and thermogenesis (including browning of white adipose tissue) and secretory function. Epidemiological studies in humans associate higher dietary intakes and serum levels of carotenoids with decreased adiposity. Specifically designed human intervention studies, though still sparse, indicate a beneficial effect of carotenoid supplementation in the accrual of abdominal adiposity. The objective of this review is to summarize recent findings in this area, place them in physiological contexts, and provide likely regulatory schemes whenever possible. The focus will be on the effects of carotenoids as nutritional regulators of adipose tissue biology and both animal and human studies, which support a role of carotenoids and retinoids in the prevention of abdominal adiposity. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  16. Longitudinal Survey of Carotenoids in Human Milk from Urban Cohorts in China, Mexico, and the USA.

    Science.gov (United States)

    Lipkie, Tristan E; Morrow, Ardythe L; Jouni, Zeina E; McMahon, Robert J; Ferruzzi, Mario G

    2015-01-01

    Emerging evidence indicates that carotenoids may have particular roles in infant nutrition and development, yet data on the profile and bioavailability of carotenoids from human milk remain sparse. Milk was longitudinally collected at 2, 4, 13, and 26 weeks postpartum from twenty mothers each in China, Mexico, and the USA in the Global Exploration of Human Milk Study (n = 60 donors, n = 240 samples). Maternal and neonatal plasma was analyzed for carotenoids from the USA cohort at 4 weeks postpartum. Carotenoids were analyzed by HPLC and total lipids by Creamatocrit. Across all countries and lactation stages, the top four carotenoids were lutein (median 114.4 nmol/L), β-carotene (49.4 nmol/L), β-cryptoxanthin (33.8 nmol/L), and lycopene (33.7 nmol/L). Non-provitamin A carotenoids (nmol/L) and total lipids (g/L) decreased (pcarotenoids α- and β-cryptoxanthin and β-carotene did not significantly change (p>0.05) with lactation stage. Total carotenoid content and lutein content were greatest from China, yet lycopene was lowest from China (p0.3). This enhanced understanding of neonatal exposure to carotenoids during development may help guide dietary recommendations and design of human milk mimetics.

  17. A new energy transfer channel from carotenoids to chlorophylls in purple bacteria.

    Science.gov (United States)

    Feng, Jin; Tseng, Chi-Wei; Chen, Tingwei; Leng, Xia; Yin, Huabing; Cheng, Yuan-Chung; Rohlfing, Michael; Ma, Yuchen

    2017-07-10

    It is unclear whether there is an intermediate dark state between the S 2 and S 1 states of carotenoids. Previous two-dimensional electronic spectroscopy measurements support its existence and its involvement in the energy transfer from carotenoids to chlorophylls, but there is still considerable debate on the origin of this dark state and how it regulates the energy transfer process. Here we use ab initio calculations on excited-state dynamics and simulated two-dimensional electronic spectrum of carotenoids from purple bacteria to provide evidence supporting that the dark state may be assigned to a new A g + state. Our calculations also indicate that groups on the conjugation backbone of carotenoids may substantially affect the excited-state levels and the energy transfer process. These results contribute to a better understanding of carotenoid excited states.Carotenoids harvest energy from light and transfer it to chlorophylls during photosynthesis. Here, Feng et al. perform ab initio calculations on excited-state dynamics and simulated 2D electronic spectrum of carotenoids, supporting the existence of a new excited state in carotenoids.

  18. 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...

  19. Macular pigment carotenoids in the retina and occipital cortex are related in humans

    Science.gov (United States)

    Objectives: Lutein and zeaxanthin are dietary carotenoids that preferentially accumulate in the macular region of the retina. Together with mesozeaxanthin, a conversion product of lutein in the macula, they form the macular pigment. Lutein is also the predominant carotenoid in human brain tissue and...

  20. Carotenoid profiling of leaves of selected eggplant accessions subjected to drought stress

    Science.gov (United States)

    This study focused on the quantification of carotenoids of the leaves of African eggplants commonly consumed as leafy and fruit vegetables. The results gave comparative profiles of carotenoids at different growth and developmental stages and under drought stress. Stress was achieved by limiting irri...

  1. Carotenoids located in human lymphocyte subpopulations and Natural Killer cells by Raman microspectroscopy

    NARCIS (Netherlands)

    Puppels, G.J.; Puppels, G.J.; Garritsen, H.S.P.; 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

  2. Amount and qualities of carotenoids in fillets of fish species fed with ...

    African Journals Online (AJOL)

    Using column (CC), thin- layer (TLC) and high- performance liquid chromatography (HPLC), carotenoid content was examined in the fillets (muscles with skin) of 16 fish species from the fisheries of West African Coast. 15 carotenoids, including 6 ketocarotenoids (4'- hydroxyechinenone, canthaxanthin, phoenicopterone, ...

  3. Genetic dissection in a mouse model reveals interactions between carotenoids and lipid metabolism[S

    Science.gov (United States)

    Palczewski, Grzegorz; Widjaja-Adhi, M. Airanthi K.; Amengual, Jaume; Golczak, Marcin; von Lintig, Johannes

    2016-01-01

    Carotenoids affect a rich variety of physiological functions in nature and are beneficial for human health. However, knowledge about their biological action and the consequences of their dietary accumulation in mammals is limited. Progress in this research field is limited by the expeditious metabolism of carotenoids in rodents and the confounding production of apocarotenoid signaling molecules. Herein, we established a mouse model lacking the enzymes responsible for carotenoid catabolism and apocarotenoid production, fed on either a β-carotene- or a zeaxanthin-enriched diet. Applying a genome wide microarray analysis, we assessed the effects of the parent carotenoids on the liver transcriptome. Our analysis documented changes in pathways for liver lipid metabolism and mitochondrial respiration. We biochemically defined these effects, and observed that β-carotene accumulation resulted in an elevation of liver triglycerides and liver cholesterol, while zeaxanthin accumulation increased serum cholesterol levels. We further show that carotenoids were predominantly transported within HDL particles in the serum of mice. Finally, we provide evidence that carotenoid accumulation influenced whole-body respiration and energy expenditure. Thus, we observed that accumulation of parent carotenoids interacts with lipid metabolism and that structurally related carotenoids display distinct biological functions in mammals. PMID:27389691

  4. Genetic dissection in a mouse model reveals interactions between carotenoids and lipid metabolism.

    Science.gov (United States)

    Palczewski, Grzegorz; Widjaja-Adhi, M Airanthi K; Amengual, Jaume; Golczak, Marcin; von Lintig, Johannes

    2016-09-01

    Carotenoids affect a rich variety of physiological functions in nature and are beneficial for human health. However, knowledge about their biological action and the consequences of their dietary accumulation in mammals is limited. Progress in this research field is limited by the expeditious metabolism of carotenoids in rodents and the confounding production of apocarotenoid signaling molecules. Herein, we established a mouse model lacking the enzymes responsible for carotenoid catabolism and apocarotenoid production, fed on either a β-carotene- or a zeaxanthin-enriched diet. Applying a genome wide microarray analysis, we assessed the effects of the parent carotenoids on the liver transcriptome. Our analysis documented changes in pathways for liver lipid metabolism and mitochondrial respiration. We biochemically defined these effects, and observed that β-carotene accumulation resulted in an elevation of liver triglycerides and liver cholesterol, while zeaxanthin accumulation increased serum cholesterol levels. We further show that carotenoids were predominantly transported within HDL particles in the serum of mice. Finally, we provide evidence that carotenoid accumulation influenced whole-body respiration and energy expenditure. Thus, we observed that accumulation of parent carotenoids interacts with lipid metabolism and that structurally related carotenoids display distinct biological functions in mammals. Copyright © 2016 by the American Society for Biochemistry and Molecular Biology, Inc.

  5. Third-order nonlinear optical properties of open-shell supermolecular systems composed of acetylene linked phenalenyl radicals.

    Science.gov (United States)

    Nakano, Masayoshi; Kishi, Ryohei; Yoneda, Kyohei; Inoue, Yudai; Inui, Tomoya; Shigeta, Yasuteru; Kubo, Takashi; Champagne, Benoît

    2011-08-11

    The third-order nonlinear optical (NLO) properties, at the molecular level, the static second hyperpolarizabilities, γ, of supermolecular systems composed of phenalenyl and pyrene rings linked by acetylene units are investigated by employing the long-range corrected spin-unrestricted density functional theory, LC-UBLYP, method. The phenalenyl based superethylene, superallyl, and superbutadiene in their lowest spin states have intermediate diradical characters and exhibit larger γ values than the closed-shell pyrene based superpolyene systems. The introduction of a positive charge into the phenalenyl based superallyl radical changes the sign of γ and enhances its amplitude by a factor of 35. Although such sign inversion is also observed in the allyl radical and cation systems in their ground state equilibrium geometries, the relative amplitude of γ is much different, that is, |γ(regular allyl cation)/γ(regular allyl radical)| = 0.61 versus |γ(phenalenyl based superallyl cation)/γ(phenalenyl based superallyl radical)| = 35. In contrast, the model ethylene, allyl radical/cation, and butadiene systems with stretched carbon-carbon bond lengths (2.0 Å), having intermediate diradical characters, exhibit similar γ features to those of the phenalenyl based superpolyene systems. This exemplifies that the size dependence of γ as well as its sign change by introducing a positive charge on the phenalenyl based superpolyene systems originate from their intermediate diradical characters. In addition, the change from the lowest to the highest π-electron spin states significantly reduces the γ amplitudes of the neutral phenalenyl based superpolyene systems. For phenalenyl based superallyl cation, the sign inversion of γ (from negative to positive) is observed upon switching between the singlet and triplet states, which is predicted to be associated with a modification of the balance between the positive and negative contributions to γ. The present study paves the way

  6. Enzymatic formation of apo-carotenoids from the xanthophyll carotenoids lutein, zeaxanthin and b-cryptoxanthin by ferret carotene-9, 10-monooxygenase

    Science.gov (United States)

    Xanthophyll carotenoids, such as lutein, zeaxanthin and b-cryptoxanthin, may provide potential health benefits against chronic and degenerative diseases. Investigating pathways of xanthophyll metabolism are important to understanding their biological functions. Carotene-15,150-monooxygenase (CMO1) h...

  7. Chemistry of carbonization - I. A theoretical study of free radical formation from starting materials

    Energy Technology Data Exchange (ETDEWEB)

    Ruette, F.; Sierraalta, A.; Castells, V.; Laya, M. (Instituto Venezolano de Investigaciones Cientificas, Caracas (Venezuela). Laboratorio de Quimica Computacional)

    1993-01-01

    The effect of size, shape, and aromaticity in the formation of radicals from model polyaromatic hydrocarbons (PAH) was theoretically studied using the MINDO/3 method. The results were interpreted in terms of hydrogen transfer on carbonization and liquefaction processes of coal-related compounds. Additives that donate or withdraw electrons were modeled by calculating negatively or positively charged systems. The results show that the hydrogen donating properties of PAHs increase with the increase of their molecular weights. The formation of anionic [pi]-radicals is thermodynamically favoured, contrary to cationic [pi]-radicals. Negative charge favoured the formation of low molecular weight radicals, and therefore, the hydrogen transfer from light to heavy PAHs. Positive charges, in general, do not facilitate the hydrogen transfer. 42 refs., 2 figs., 4 tabs.

  8. 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...

  9. ADSORPTION METHOD FOR SEPARATING METAL CATIONS

    Science.gov (United States)

    Khym, J.X.

    1959-03-10

    The chromatographic separation of fission product cations is discussed. By use of this method a mixture of metal cations containing Zr, Cb, Ce, Y, Ba, and Sr may be separated from one another. Mentioned as preferred exchange adsorbents are resins containing free sulfonic acid groups. Various eluants, such as tartaric acid, HCl, and citric acid, used at various acidities, are employed to effect the selective elution and separation of the various fission product cations.

  10. Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

    International Nuclear Information System (INIS)

    Shkrob, I.A.; Trifunac, A.D.

    1995-01-01

    Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

  11. SOLANUM LYCOPERSICUM QUANTITATIVE THING LAYER CHROMATOGRAPHY FOR EVALUATION OF CAROTENOID COMPOSITION OF TOMATOES SOLANUM LYCOPERSICUM

    Directory of Open Access Journals (Sweden)

    N. A. Golubkina

    2017-01-01

    Full Text Available Qualitative and quantitative evaluation of tomatoes carote-noid composition is considered to be the basis of tomato selection. Among known methods of identification and carotenoid content determination thing layer chromatography (TLC is characterized by inexpensive, quick and availab-le method of analysis. Comparison of individual tomato carotenoid content data obtained using wellknown empirical formulas and based of TLC separation on chromatoraphic paper was achieved. Empirical formulas for the determination of lycopene and beta-carotene concentrations were shown to give high variations in beta-carotene content and decreased values of total carotenoids concentration values. Developed conditions of chromatographic separation and identification of selected carotenoids are based on different polarity of individual pigments and specific absorption spectra of the latter. Method of thin layer chromatography may serve as a quick and effective method for quality evaluation of tomato fruit of different color and determination of beta-carotene, ζ-carotene, neurosporene, lycopene and lutein content.

  12. Influence of sample processing on the analysis of carotenoids in maize.

    Science.gov (United States)

    Rivera, Sol; Canela, Ramon

    2012-09-21

    We performed a number of tests with the aim to develop an effective extraction method for the analysis of carotenoid content in maize seed. Mixtures of methanol-ethyl acetate (6:4, v/v) and methanol-tetrahydrofuran (1:1, v/v) were the most effective solvent systems for carotenoid extraction from maize endosperm under the conditions assayed. In addition, we also addressed sample preparation prior to the analysis of carotenoids by liquid chromatography (LC). The LC response of extracted carotenoids and standards in several solvents was evaluated and results were related to the degree of solubility of these pigments. Three key factors were found to be important when selecting a suitable injection solvent: compatibility between the mobile phase and injection solvent, carotenoid polarity and content in the matrix.

  13. Carotenogenic gene expression and carotenoid accumulation in three varieties of Cucurbita pepo during fruit development.

    Science.gov (United States)

    Obrero, Ángeles; González-Verdejo, Clara I; Die, Jose V; Gómez, Pedro; Del Río-Celestino, Mercedes; Román, Belén

    2013-07-03

    The control of gene expression is a crucial regulatory mechanism in carotenoid accumulation of fruits and flowers. We investigated the role of transcriptional regulation of nine genes involved in the carotenoid biosynthesis pathway in three varieties of Cucurbita pepo with evident differences in fruit color. The transcriptional levels of the key genes involved in the carotenoid biosynthesis were higher in flower-, leaf-, and fruit skin tissues than flesh tissues. This correlated with higher concentration of carotenoid content in these tissues. The differential expression among the colored and white cultivars detected for some genes, such as LCYe, in combination with other regulatory mechanisms, could explain the large differences found in terms of carotenoid content among the three varieties. These results are a first step to elucidate carotenogenesis in C. pepo and demonstrate that, in general, regulation of the pathway genes is a critical factor that determines the accumulation of these compounds.

  14. The Quest for Golden Bananas: Investigating Carotenoid Regulation in a Fe'i Group Musa Cultivar.

    Science.gov (United States)

    Buah, Stephen; Mlalazi, Bulukani; Khanna, Harjeet; Dale, James L; Mortimer, Cara L

    2016-04-27

    The regulation of carotenoid biosynthesis in a high-carotenoid-accumulating Fe'i group Musa cultivar, "Asupina", has been examined and compared to that of a low-carotenoid-accumulating cultivar, "Cavendish", to understand the molecular basis underlying carotenogenesis during banana fruit development. Comparisons in the accumulation of carotenoid species, expression of isoprenoid genes, and product sequestration are reported. Key differences between the cultivars include greater carotenoid cleavage dioxygenase 4 (CCD4) expression in "Cavendish" and the conversion of amyloplasts to chromoplasts during fruit ripening in "Asupina". Chromoplast development coincided with a reduction in dry matter content and fruit firmness. Chromoplasts were not observed in "Cavendish" fruits. Such information should provide important insights for future developments in the biofortification and breeding of banana.

  15. 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.

  16. New and rare carotenoids isolated from marine bacteria and their antioxidant activities.

    Science.gov (United States)

    Shindo, Kazutoshi; Misawa, Norihiko

    2014-03-24

    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. Carotenoids from Capsicum annuum fruits: Influence of spectral quality of radiation

    International Nuclear Information System (INIS)

    Lopez, M.; Candela, M.E.; Sabater, F.

    1986-01-01

    Capsicum annuum L. cv. Ramillete fruits grown in the field were covered 60 d after flowering with “white”, yellow, red and blue cellophane filters. Two other sets were left in full sunlight and under cover, respectively. After 30 d of treatment, during the ripening period, the contents of individual carotenoids were analyzed. The red radiation was the most effective to increase the carotenoid biosynthesis, but the green and blue radiations inhibited their production. Either class of filters inhibited the formation of capsanthin, the most important carotenoid in the production of red colour of the maturation, but capsorubin, the other carotenoid responsible for the maturation colour, was more enhanced in the shade and under red radiation. Neither type of radiation was so efficient in increasing the total carotenoids content as the full sun radiation

  18. 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...

  19. Role of structural barriers in the in vitro bioaccessibility of anthocyanins in comparison with carotenoids.

    Science.gov (United States)

    Carrillo, Celia; Buvé, Carolien; Panozzo, Agnese; Grauwet, Tara; Hendrickx, Marc

    2017-07-15

    Although natural structural barriers are factors limiting nutrient bioaccessibility, their specific role in anthocyanin bioaccessibility is still unknown. To better understand how natural barriers govern bioactive compound bioaccessibility, an experimental approach comparing anthocyanins and carotenoids was designed, using a single plant matrix. Initial results revealed increased anthocyanin bioaccessibility in masticated black carrot. To explain this observation, samples with increasing levels of bioencapsulation (free-compound, homogenized-puree, puree) were examined. While carotenoid bioaccessibility was inversely proportional to the level of bioencapsulation, barrier disruption did not increase anthocyanin bioaccessibility. This means that mechanical processing is of particular importance in the case of carotenoid bioaccessibility. While micelle incorporation is the limiting factor for carotenoid bioaccessibility, anthocyanin degradation under alkaline conditions in the gastrointestinal tract dominates. In the absence of structural barriers, anthocyanin bioaccessibility is greater than that of carotenoids. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. The effect of cellular carotenoid levels in micrococcus luteus on resistance to gamma radiation

    International Nuclear Information System (INIS)

    Al-Wandawi, K. H.

    2000-01-01

    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