Spectroscopy and Quantum Chemical Modeling Reveal a Predominant Contribution of Excitonic Interactions to the Bathochromic Shift in α-Crustacyanin, the Blue Carotenoprotein in the Carapace of the Lobster Homarus gammarus.

To resolve the molecular basis of the coloration mechanism of α-crustacyanin, we used C- labeled astaxanthins as chromophores for solid-state C NMR and resonance Raman spectroscopy of [6,6',7,7']-C α-crustacyanin and [8,8',9,9',10,10',11,11',20,20']-C α-crustacyanin. We complement the experimental d...

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Publicado en:Journal of the American Chemical Society Vol. 127; no. 5; pp. 1438 - 1446
Autores principales: van Wijk, Arjan A. C., Spaans, Arnold, Uzunbajakava, Natallia, Otto, Cees, De Groot, Huub J. M., Lugtenburg, Johan, Buda, Francesco
Formato: Artículo
Publicado: American Chemical Society 2/9/2005
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 2/9/2005
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        atl: Spectroscopy and Quantum Chemical Modeling Reveal a Predominant Contribution of Excitonic Interactions to the Bathochromic Shift in α-Crustacyanin, the Blue Carotenoprotein in the Carapace of the Lobster Homarus gammarus.
      aug:
        au:
          van Wijk, Arjan A. C.
          Spaans, Arnold
          Uzunbajakava, Natallia
          Otto, Cees
          De Groot, Huub J. M.
          Lugtenburg, Johan
          Buda, Francesco
        affil:
          Leiden University.
          University of Twente.
          Philips Research Laboratories, 5656 AA Eindhoven, The Netherlands.
      su:
        Homarus gammarus
        Spectrum analysis
        Raman spectroscopy
        Density functionals
        Electron distribution
        Proteins
      sug:
        subj:
          Homarus gammarus
          Spectrum analysis
          Raman spectroscopy
          Density functionals
          Electron distribution
          Proteins
      ab: To resolve the molecular basis of the coloration mechanism of α-crustacyanin, we used C- labeled astaxanthins as chromophores for solid-state C NMR and resonance Raman spectroscopy of [6,6',7,7']-C α-crustacyanin and [8,8',9,9',10,10',11,11',20,20']-C α-crustacyanin. We complement the experimental data with time-dependent density functional theory calculations on several models based on the structural information available for β-crustacyanin. The data rule out major changes and strong polarization effects in the ground-state electron density of astaxanthin upon binding to the protein. Conformational changes in the chromophore and hydrogen-bond interactions between the astaxanthin and the protein can account only for about one-third of the total bathochromic shift in α-crustacyanin. The exciton coupling due to the proximity of two astaxanthin chromophores is found to be large, suggesting that aggregation effects in the protein represent the primary source of the color change.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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