Study of Model Systems for Bilirubin and Bilin Chromophores: Determination and Modification of Thermal and Photochemical Properties

  1. García-Iriepa, C. 3
  2. Ernst, H.A. 2
  3. Liang, Y. 2
  4. Unterreiner, A.-N. 2
  5. Frutos, L.M. 3
  6. Sampedro, D. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 Karlsruhe Institute of Technology
    info

    Karlsruhe Institute of Technology

    Karlsruhe, Alemania

    ROR https://ror.org/04t3en479

  3. 3 Universidad de Alcalá
    info

    Universidad de Alcalá

    Alcalá de Henares, España

    ROR https://ror.org/04pmn0e78

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Revista:
Journal of Organic Chemistry

ISSN: 0022-3263

Año de publicación: 2016

Volumen: 81

Número: 15

Páginas: 6292-6302

Tipo: Artículo

DOI: 10.1021/ACS.JOC.6B00892 SCOPUS: 2-s2.0-84981203572 WoS: WOS:000381236000015 GOOGLE SCHOLAR

Otras publicaciones en: Journal of Organic Chemistry

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Sistemas fotoactivos: aplicaciones biológicas y de almacenamiento de energía. Photoactive systems: biological applications and energy storage.

2015/00065/001

Resumen

Bilin chromophores and bilirubin are involved in relevant biological functions such as light perception in plants and as protective agents against Alzheimer and other diseases. Despite their extensive use, a deep rationalization of the main factors controlling the thermal and photochemical properties has not been performed yet, which in turn hampers further applications of these versatile molecules. In an effort to understand those factors and allow control of the relevant properties, a combined experimental and computational study has been carried out for diverse model systems to understand the interconversion between Z and E isomers. In this study, we have demonstrated the crucial role of steric hindrance and hydrogen-bond interactions in thermal stability and the ability to control them by designing novel compounds. We also determined several photochemical properties and studied the photodynamics of two model systems in more detail, observing a fast relaxation of the excited state shorter than 2 ps in both cases. Finally, the computational study allowed us to rationalize the experimental evidence. © 2016 American Chemical Society.