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A Solid-State Fluorescence Sensor for Nitroaromatics and Nitroanilines Based on a Conjugated Calix[4]arene Polymer

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Abstract

A new conjugated polymer possessing calix[4]arene-oxacyclophane units wired-in-series by phenyleneethynylene linkers was synthesized by a Sonogashira-Hagihara cross-coupling method in high yield. The polymer was structurally characterized by FTIR and 1H/13C/HSQC NMR techniques, and its average Mn (38.5 kDa) retrieved from GPC analysis. The polymer is highly emissive (ΦF = 0.55) and exhibits a longer-than-usual excited-state lifetime (1.80 ns) for a phenyleneethynylene type polymer. Similar photophysical properties (absorption and fluorescence emission) were observed in solution and in solid-state. This stems from the presence of bulky calixarene moieties along the polymer chains which prevent interchain staking and the formation of ground-state aggregates and/or non-emissive exciplexes, both deleterious to solid-state materials envisioned for fluorescence sensing applications. Moreover, the intrinsic molecular recognition capabilities of its two rigid inner cavities (calixarene and cyclophane sub-units), allied with the high three-dimensionality of the macromolecule that creates additional interstitial voids around the molecular receptors, can boost its sensory responses towards specific analytes. A high sensitive response was observed in the detection of nitroaromatics and nitroanilines in neat vapour phases by casted films of the polymer. The largest sensitivities were obtained for 2,4-dinitrotoluene (a taggant for the explosive TNT; > 85% of fluorescence quenching upon 1 min exposure) and ortho-nitroaniline (90% of emission reduction in 30 s). The sensory responses attained in solid-state are discussed on the basis of the electron affinities of the analytes and their electrostatic interactions with polymer films.

Sensing the threats! A high sensitive response was observed in the detection of explosives and noxious nitroanilines in neat vapour phases by thinfilms of a calixarene-based polymer

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Acknowledgements

We are grateful to Fundação para a Ciência e a Tecnologia/Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES) for financial support (UID/QUI/00616/2019) of this work. We also thank Prof. M. N. Berberan-Santos (Instituto Superior Técnico/Universidade de Lisboa) for providing access to fluorescence lifetime equipment and Dr. A. Fedorov for his assistance with the measurements.

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Authors and Affiliations

  1. Departamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1, 1959-007, Lisbon, Portugal

    José V. Prata, Alexandra I. Costa & Carlos M. Teixeira

  2. Centro de Química-Vila Real, Universidade de Trás-os-Montes e Alto Douro, 5000-801, Vila Real, Portugal

    José V. Prata & Alexandra I. Costa

  3. Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001, Lisbon, Portugal

    Carlos M. Teixeira

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  1. José V. Prata
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Correspondence to José V. Prata.

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Prata, J.V., Costa, A.I. & Teixeira, C.M. A Solid-State Fluorescence Sensor for Nitroaromatics and Nitroanilines Based on a Conjugated Calix[4]arene Polymer. J Fluoresc 30, 41–50 (2020). https://doi.org/10.1007/s10895-019-02466-1

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