Original scientific paper

https://doi.org/10.5562/cca4115

Complexation of Alkali and Alkaline Earth Metal Cations by Fluorescent Glycoconjugated Calix[4]arene Derivative: Thermodynamic and Computational Studies

Matija Modrušan ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Nikola Cindro ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia *
Andrea Usenik ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Katarina Leko ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Lucija Glazer ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Renato Tomaš ; Division of Chemistry, Faculty of Chemistry and Technology, University of Split, Ruđera Boškovića 35, 21000 Split, Croatia
Gordan Horvat ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Josip Požar ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia
Vladislav Tomišić ; Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia *

* Corresponding author.

Supplements: cca4115_supplement.pdf

Abstract

The affinity of novel, phenanthridine-based calix[4]arene glycoconjugate (L), bearing efficient cation-binding tertiary-amide functionalities in the coordination site, towards alkali and alkaline earth metal cations in methanol was investigated by means of spectrophotometry, microcalorimetry, and 1H NMR spectroscopy. Significant complexation-induced enhancement of the calixarene fluorescence was observed in all cases, allowing also the use of spectrofluorimetric titrations for quantitative monitoring of the complexation processes. The thermodynamic reaction parameters (complex stability constants, standard reaction enthalpies and entropies) were determined and discussed regarding the ligand structure and cation charge densities, as well as solvation effect on the studied equilibria. Compound L was found to be a considerably more efficient receptor for alkali relative to alkaline earth metal cations of similar sizes. This was mostly a consequence of stronger solvation of the latter compared to the former in methanol. Molecular dynamic simulations of L and its complexes were carried out as well, which provided additional information on their structural characteristics and the ligand cation-complexation properties.

Keywords

calixarenes; cation complexation; solvent effect; inclusion; fluorescence; thermodynamics; glicoconjugation

Hrčak ID:

322565

URI

https://hrcak.srce.hr/322565

Publication date:

21.11.2024.

Visits: 119 *