Amine molecular cages as supramolecular fluorescent explosive sensors: a computational perspective

Zwijnenburg, M. A., Berardo, E., Peveler, W. J. and Jelfs, K. E. (2016) Amine molecular cages as supramolecular fluorescent explosive sensors: a computational perspective. Journal of Physical Chemistry B, 120(22), pp. 5063-5072. (doi: 10.1021/acs.jpcb.6b03059) (PMID:27149567)

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We investigate using a computational approach the physical and chemical processes underlying the application of organic (macro)molecules as fluorescence quenching sensors for explosives sensing. We concentrate on the use of amine molecular cages to sense nitroaromatic analytes, such as picric acid and 2,4-dinitrophenol, through fluorescence quenching. Our observations for this model system hold for many related systems. We consider the different possible mechanisms of fluorescence quenching: Förster resonance energy transfer, Dexter energy transfer and photoinduced electron transfer, and show that in the case of our model system, the fluorescence quenching is driven by the latter and involves stable supramolecular sensor–analyte host–guest complexes. Furthermore, we demonstrate that the experimentally observed selectivity of amine molecular cages for different explosives can be explained by the stability of these host–guest complexes and discuss how this is related to the geometry of the binding site in the sensor. Finally, we discuss what our observations mean for explosive sensing by fluorescence quenching in general and how this can help in future rational design of new supramolecular detection systems.

Item Type:Articles
Additional Information:M.A.Z. and K.E.J. acknowledge the U.K. Engineering and Physical Sciences Research Council (EPSRC) for a Career Acceleration Fellowship (Grant EP/I004424/1) and the Royal Society for a University Research Fellowship, respectively. K.E.J. further acknowledges the EPSRC for additional funding (EP/M017257/1). W.J.P. is grateful for an EPSRC Doctoral Prize Fellowship (EP/M506448/1). Finally, computational time on ARCHER, the U.K.’s national high-performance computing service (via our membership of the UK’s HPC Materials Chemistry Consortium, which is funded by EPSRC Grant EP/L000202/1), and the EPSRC National Service for Computational Chemistry Software is gratefully acknowledged.
Glasgow Author(s) Enlighten ID:Peveler, Dr William
Authors: Zwijnenburg, M. A., Berardo, E., Peveler, W. J., and Jelfs, K. E.
College/School:College of Science and Engineering > School of Engineering > Biomedical Engineering
Journal Name:Journal of Physical Chemistry B
Publisher:American Chemical Society
ISSN (Online):1520-5207
Published Online:05 May 2016
Copyright Holders:Copyright © 2016 American Chemical Society
First Published:First published in Journal of Physical Chemistry B 120(22): 5063-5072
Publisher Policy:Reproduced under a Creative Commons License

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