MURAL - Maynooth University Research Archive Library



    Highly Selective Fluorimetric Turn-Off Detection of Copper(II) by Two Different Mechanisms in Calix[4]arene-Based Chemosensors and Chemodosimeters


    O'Sullivan, Justine and Colleran, John and Twamley, Brendan and Heaney, Frances (2019) Highly Selective Fluorimetric Turn-Off Detection of Copper(II) by Two Different Mechanisms in Calix[4]arene-Based Chemosensors and Chemodosimeters. ChemPlusChem, 84 (10). pp. 1610-1622. ISSN 2192-6506

    [img]
    Preview
    Download (2MB) | Preview


    Share your research

    Twitter Facebook LinkedIn GooglePlus Email more...



    Add this article to your Mendeley library


    Abstract

    Isoxazolo-pyrene tethered calix[4]arenes selectively detect copper(II) ions without interference from related perchlorate ions. The fluorescence emission of the probes, synthesised by nitrile oxide alkyne cycloaddition, and characterised by spectroscopic and crystallographic data, is rapidly reduced by Cu(II) ions. Detection limits are in the micromolar or sub-micromolar range (0.3–3.6 μM) based on a 1:1 sensor:analyte interaction. Voltammetric behaviour and 1 H NMR data provide new insights into the sensing mechanism which is dependent on the calixarene substitution pattern. When the calixarene lower rim is fully substituted, Cu(II) detection occurs through a traditional chelation mechanism. In contrast, for calixarenes 1,3-disubstituted on the lower rim, detection takes place through a chemodosimetric redox reaction. The isolation of a calix[4] diquinone from the reaction with excess Cu(ClO4)2 provides confirmation that the sensor–analyte interaction culminates in irreversible sensor oxidation.

    Item Type: Article
    Additional Information: Cite as: J. O'Sullivan, J. Colleran, B. Twamley, F. Heaney, ChemPlusChem 2019, 84, 1610.
    Keywords: Highly Selective; Fluorimetric; Turn-Off Detection; Copper; Mechanisms; Calix[4]arene-Based; Chemosensors; Chemodosimeters;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 14161
    Identification Number: https://doi.org/10.1002/cplu.201900448
    Depositing User: Dr. Frances Heaney
    Date Deposited: 11 Mar 2021 14:35
    Journal or Publication Title: ChemPlusChem
    Publisher: Wiley
    Refereed: Yes
    URI:

    Repository Staff Only(login required)

    View Item Item control page

    Downloads

    Downloads per month over past year