Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions

In this research we have synthesized and evaluated five calix[4]arene-based receptors functionalized with thiosemicarbazone or thiourea groups, incorporating pyridinyl naphthalene or triazolopyridine chromophores in 1,3-<i>alternate</i>, pinched <i>cone</i> and <i>cone&...

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Main Authors: Andrés Ochoa, Belén Hernández-Arancibia, José Herrera-Muñoz, Horacio Gómez-Machuca, Claudio Saitz
Format: Article
Language:English
Published: MDPI AG 2025-02-01
Series:Chemosensors
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Online Access:https://www.mdpi.com/2227-9040/13/2/48
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author Andrés Ochoa
Belén Hernández-Arancibia
José Herrera-Muñoz
Horacio Gómez-Machuca
Claudio Saitz
author_facet Andrés Ochoa
Belén Hernández-Arancibia
José Herrera-Muñoz
Horacio Gómez-Machuca
Claudio Saitz
author_sort Andrés Ochoa
collection DOAJ
description In this research we have synthesized and evaluated five calix[4]arene-based receptors functionalized with thiosemicarbazone or thiourea groups, incorporating pyridinyl naphthalene or triazolopyridine chromophores in 1,3-<i>alternate</i>, pinched <i>cone</i> and <i>cone</i> conformations. The ion recognition capabilities of these receptors were investigated using UV-visible and fluorescence spectroscopy. Receptor (<b>I</b>), which adopts a pinched <i>cone</i> conformation with thiosemicarbazone groups, demonstrated bifunctional sensing abilities by detecting both cations and anions. Receptors (<b>II</b>) and (<b>III</b>) showed remarkable selectivity and sensitivity for Cu<sup>2+</sup> ions. Receptors (<b>IV</b>) and (<b>V</b>), in <i>cone</i> and 1,3-<i>alternate</i> conformations, respectively, where functionalized with a triazolo[1,5-a]pyridine fluorophore and exhibited highly sensitive ON-OFF fluorescence sensing for Co<sup>2+</sup>, Cu<sup>2+</sup> and Ni<sup>2+</sup> ions, with significant fluorescence quenching upon binding and a low detection limit of 2.94 µg/L for the Co<sup>2+</sup> ion in receptor (<b>IV</b>). Ion receptor (<b>I</b>) demonstrates a strong performance in broad-spectrum ion detection, whereas the structural conformations of receptors (IV) and (V) play a pivotal role in their remarkable selectivity and sensitivity for specific transition metals in fluorescence-based sensing.
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spelling doaj-art-4a6526e33adb47cfb68e983b97d6f3eb2025-08-20T02:44:52ZengMDPI AGChemosensors2227-90402025-02-011324810.3390/chemosensors13020048Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of IonsAndrés Ochoa0Belén Hernández-Arancibia1José Herrera-Muñoz2Horacio Gómez-Machuca3Claudio Saitz4Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Olivos 1007, Independencia, Santiago 8380492, ChileFacultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Olivos 1007, Independencia, Santiago 8380492, ChileInstituto Universitario de Investigación y Desarrollo Tecnológico (IDT), Universidad Tecnológica Metropolitana, Ignacio Valdivieso 2409, San Joaquín, Santiago 8940577, ChileFacultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Olivos 1007, Independencia, Santiago 8380492, ChileFacultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Olivos 1007, Independencia, Santiago 8380492, ChileIn this research we have synthesized and evaluated five calix[4]arene-based receptors functionalized with thiosemicarbazone or thiourea groups, incorporating pyridinyl naphthalene or triazolopyridine chromophores in 1,3-<i>alternate</i>, pinched <i>cone</i> and <i>cone</i> conformations. The ion recognition capabilities of these receptors were investigated using UV-visible and fluorescence spectroscopy. Receptor (<b>I</b>), which adopts a pinched <i>cone</i> conformation with thiosemicarbazone groups, demonstrated bifunctional sensing abilities by detecting both cations and anions. Receptors (<b>II</b>) and (<b>III</b>) showed remarkable selectivity and sensitivity for Cu<sup>2+</sup> ions. Receptors (<b>IV</b>) and (<b>V</b>), in <i>cone</i> and 1,3-<i>alternate</i> conformations, respectively, where functionalized with a triazolo[1,5-a]pyridine fluorophore and exhibited highly sensitive ON-OFF fluorescence sensing for Co<sup>2+</sup>, Cu<sup>2+</sup> and Ni<sup>2+</sup> ions, with significant fluorescence quenching upon binding and a low detection limit of 2.94 µg/L for the Co<sup>2+</sup> ion in receptor (<b>IV</b>). Ion receptor (<b>I</b>) demonstrates a strong performance in broad-spectrum ion detection, whereas the structural conformations of receptors (IV) and (V) play a pivotal role in their remarkable selectivity and sensitivity for specific transition metals in fluorescence-based sensing.https://www.mdpi.com/2227-9040/13/2/48calix[4]areneconformationsreceptorbifunctional
spellingShingle Andrés Ochoa
Belén Hernández-Arancibia
José Herrera-Muñoz
Horacio Gómez-Machuca
Claudio Saitz
Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions
Chemosensors
calix[4]arene
conformations
receptor
bifunctional
title Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions
title_full Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions
title_fullStr Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions
title_full_unstemmed Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions
title_short Thiosemicarbazone- and Thiourea-Functionalized Calix[4]arenes in <i>cone</i> and 1,3-<i>alternate</i> Conformations: Receptors for the Recognition of Ions
title_sort thiosemicarbazone and thiourea functionalized calix 4 arenes in i cone i and 1 3 i alternate i conformations receptors for the recognition of ions
topic calix[4]arene
conformations
receptor
bifunctional
url https://www.mdpi.com/2227-9040/13/2/48
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