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Characterization and reactivity of photodimers of dihydroneopterin and dihydrobiopterin

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Abstract

7,8-Dihydrobiopterin (H2Bip) and 7,8-dihydroneopterin (H2Nep) belong to a class of heterocyclic compounds present in a wide range of living systems. H2Bip accumulates in the skin of patients suffering from vitiligo, whereas H2Nep is secreted by human macrophages when the cellular immune system is activated. We have investigated the photochemical reactivity of both compounds upon UV-A irradiation (320-400 nm), the chemical structures of the products and their thermal stability. The study was performed in neutral aqueous solutions. The reactions were followed by UV/Visible spectrophotometry and HPLC and the products were analyzed by means of electrospray ionization mass spectrometry and 1H-NMR. Excitation of H2Bip and H2Nep leads to the formation, in each case, of two main isomeric dimers. The latter compounds undergo a thermal process that may consist in a retro [2 + 2]-cycloaddition and hydrolysis to yield the reactant (H2Bip or H2Nep) and a product that has incorporated a molecule of H2O.

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Authors and Affiliations

  1. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CCT La Plata-CONICET, Casilla de Correo 16 Sucursal 4, 1900, La Plata, Argentina

    Mariana Vignoni, Carolina Lorente & Andrés H. Thomas

  2. Instituto de Investigaciones Biotecnológicas-Instituto Tecnológico de Chascomús (IIB-INTECH), Universidad Nacional de San Martín, CONICET, Intendente Marino Km 8.2, CC 164, 7130, Chascomús, Argentina

    Franco M. Cabrerizo

  3. CIHIDECAR-CONICET, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2 3p Ciudad Universitaria, 1428, Buenos Aires, Argentina

    Rosa Erra-Balsells

  4. Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP), UMR CNRS 5623, Université Paul Sabatier (Toulouse III), 118 route de Narbonne, F-31062, Toulouse cédex 9, France

    Esther Oliveros

Authors
  1. Mariana Vignoni
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  2. Carolina Lorente
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  3. Franco M. Cabrerizo
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  4. Rosa Erra-Balsells
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  5. Esther Oliveros
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  6. Andrés H. Thomas
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Corresponding authors

Correspondence to Esther Oliveros or Andrés H. Thomas.

Additional information

This article is published as part of a themed issue in honour of Professor Kurt Schaffner on the occasion of his 80th birthday.

Electronic supplementary information (ESI) available. See DOI: 10.1039/c2pp05363b

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Vignoni, M., Lorente, C., Cabrerizo, F.M. et al. Characterization and reactivity of photodimers of dihydroneopterin and dihydrobiopterin. Photochem Photobiol Sci 11, 979–987 (2012). https://doi.org/10.1039/c2pp05363b

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  • DOI: https://doi.org/10.1039/c2pp05363b

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