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Issue 9, 2016
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A biomimetic molecular switch at work: coupling photoisomerization dynamics to peptide structural rearrangement

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Abstract

In spite of considerable interest in the design of molecular switches towards photo-controllable (bio)materials, few studies focused on the major influence of the surrounding environment on the switch photoreactivities. We present a combined experimental and computational study of a retinal-like molecular switch linked to a peptide, elucidating the effects on the photoreactivity and on the α-helix secondary structure. Temperature-dependent, femtosecond UV-vis transient absorption spectroscopy and high-level hybrid quantum mechanics/molecular mechanics methods were applied to describe the photoisomerization process and the subsequent peptide rearrangement. It was found that the conformational heterogeneity of the ground state peptide controls the excited state potential energy surface and the thermally activated population decay. Still, a reversible α-helix to α-hairpin conformational change is predicted, paving the way for a fine photocontrol of different secondary structure elements, hence (bio)molecular functions, using retinal-inspired molecular switches.

Graphical abstract: A biomimetic molecular switch at work: coupling photoisomerization dynamics to peptide structural rearrangement

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Publication details

The article was received on 09 Dec 2015, accepted on 03 Feb 2016 and first published on 03 Feb 2016


Article type: Paper
DOI: 10.1039/C5CP07599H
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2016,18, 6742-6753
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    A biomimetic molecular switch at work: coupling photoisomerization dynamics to peptide structural rearrangement

    C. García-Iriepa, M. Gueye, J. Léonard, D. Martínez-López, P. J. Campos, L. M. Frutos, D. Sampedro and M. Marazzi, Phys. Chem. Chem. Phys., 2016, 18, 6742
    DOI: 10.1039/C5CP07599H

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