Dynamics of ion-regulated photoinduced electron transfer in BODIPY-BAPTA conjugates

Autor: Gediminas Jonusauskas, Ren-Wei Chang, Guillaume Vives, Pinar Batat, Brice Kauffmann, Robin Bofinger, Reiko Oda, Nathan D. McClenaghan
Přispěvatelé: Laboratoire Ondes et Matière d'Aquitaine (LOMA), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Imagerie Moléculaire et Nanobiotechnologies - Institut Européen de Chimie et Biologie (IECB), Université Sciences et Technologies - Bordeaux 1-Centre National de la Recherche Scientifique (CNRS), European Project: 208702,EC:FP7:ERC,ERC-2007-StG,COMMOTION(2008), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Bordeaux (UB)-École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Sciences et Technologies - Bordeaux 1 (UB)-Centre National de la Recherche Scientifique (CNRS)
Jazyk: angličtina
Rok vydání: 2012
Předmět:
Zdroj: Photochemical & Photobiological Sciences
Photochemical & Photobiological Sciences, Royal Society of Chemistry, 2012, 11 (11), pp.1666-1674. ⟨10.1039/C2PP25130B⟩
Photochemical & Photobiological Sciences, 2012, 11 (11), pp.1666-1674. ⟨10.1039/C2PP25130B⟩
ISSN: 1474-905X
1474-9092
DOI: 10.1039/C2PP25130B⟩
Popis: International audience; Efficient Ca2+-switched fluorescent sensors, where fluorescence output is governed by a light-activated ion-gated electron transfer pathway, can be obtained on combining BODIPY chromophores with a readily oxidized biocompatible and selective BAPTA receptor. Herein we report the synthesis and studies of two such conjugates, which vary in the nature of the spacer separating the two electroactive components, namely none (1) or phenyl (2). Single crystal X-ray crystallography and molecular modelling structures and calculations give information on molecular and electronic structure, while steady-state fluorescence experiments show high Ca2+-induced fluorescence enhancement factors of 122 and 23 and Kd values of 0.50 μM and 0.13 μM for 1 and 2, respectively. Notably, studies of the ultrafast photoinduced processes (through transient absorption spectroscopy) give access to electron transfer dynamics in pseudophysiological media as well as in a polar non-protic solvent and information about the fate of the excited molecules in the presence and absence of calcium. In water, electron transfer rates as high as 3.3 × 1012 s−1 and 8.3 × 1011 s−1 are measured for the ion-free, directly connected conjugate and the variant incorporating a phenyl spacer, respectively. This electron transfer pathway is efficiently blocked by the presence of an ion, restoring fluorescence.
Databáze: OpenAIRE
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