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Calixarenes: Versatile molecules as molecular sensors for ion recognition study

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Abstract

This article presents a brief account on designing of calixarene-based molecular sensor for recognition of various metal ions and anions and also different analytical techniques to monitor the recognition event. This review focuses only on calix[4]arene derivatives, in which mainly the lower rim is modified incorporating either crown moiety to make calix–crown hybrid ionophore to encapsulate metal ions or some fluoregenic inorganic and organic moieties to use it as signalling unit. In order to investigate effect of conformation of the calixarene unit and steric crowding on ion selectivity, designing of these molecules have been made using both the cone and 1,3-alternate conformations of the calixarene unit and also incorporating bulky ter-butyl group in few cases to impose controlled steric crowding. Among various ions, here focuses are mainly on biologically and commercially important alkali metal ion such as K + , toxic metal ions such as Hg2 + , Pb2 + , Cd2 + , important transition metal ion such as Cu2 +  and toxic anion like F − . The techniques used to monitor the recognition event and also to determine binding constants with strongly interacting ions are fluorescence, UV-vis and 1H NMR spectroscopy. Most of the ionophores reported in this review have been characterized crystallographically, however no structural information (except one case) are incorporated in this article, as it will occupy space without significant enhancement of chemistry part. Different factors such as size of the ionophore cavity, size of metal ion, coordination sites/donor atoms, steric crowding and solvents, which determine selectivity have been discussed. Response of ion recognition process to different analytical techniques is another interesting factor discussed in this article.

Ion-recognition property of a large variety of calix[4]arenes incorporating crown moiety to make hybrid ionophore, substituents to impose steric crowding and fluoregenic moieties as signalling unit has been reported. This report demonstrates how factors such as sizes of the ionophore and metal ions, donor atoms, steric crowding and solvents, influence ion-selectivity.

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Acknowledgements

Authors are grateful to the Department of Science and Technology (DST), New Delhi, Government of India, for financial support. They thank the Council of Scientific and Industrial Research (CSIR), New Delhi for generous support towards infrastructures and core competency development. SP and DM gratefully acknowledge the CSIR for awarding Senior Research Fellowship (SRF). Thanks are also due to Dr. E Suresh and Dr. B Ganguly for their contributions in crystallography and computational studies, respectively. Authors thank Mr. A K Das, Dr. V P Boricha and Mr. V Agrawal for recording mass, NMR and IR spectra, respectively.

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Authors and Affiliations

  1. Analytical Science Division, Central Salt and Marine Chemicals Research Institute (constituents of CSIR, New Delhi), G B Marg, Bhavnagar, 364 002, India

    SUBRATA PATRA, DEBDEEP MAITY, RAVI GUNUPURU, PRAGATI AGNIHOTRI & PARIMAL PAUL

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  1. SUBRATA PATRA
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  2. DEBDEEP MAITY
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Correspondence to PARIMAL PAUL.

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Appendix: Drawings of the chemical structures of the receptors and complexes (1–15).

Appendix: Drawings of the chemical structures of the receptors and complexes (1–15).

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PATRA, S., MAITY, D., GUNUPURU, R. et al. Calixarenes: Versatile molecules as molecular sensors for ion recognition study. J Chem Sci 124, 1287–1299 (2012). https://doi.org/10.1007/s12039-012-0329-y

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