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Physicochemical and Structural Aspects of Calixarene Chemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (30 June 2022) | Viewed by 9075

Special Issue Editors

Department of Chemistry, Faculty of Science, University of Zagreb, Zagreb, Croatia
Interests: physical supramolecular chemistry; thermodynamics and kinetics of coordination reactions; solvation phenomena; electrolyte solutions; chemometrics
Special Issues, Collections and Topics in MDPI journals
Department of Chemistry, Faculty of Science, University of Zagreb, Zagreb, Croatia
Interests: thermodynamics of coordination reactions (calixarenes, cucurbiturils, cyclodextrins); polyelectrolytes; solute-solvent interactions; calorimetry

Special Issue Information

Calixarenes are widely used as templates for the synthesis of a variety of ionophores and molecular receptors. This is due to the relatively simple functionalization of their lower and/or upper rim, resulting in compounds with high affinity and notable selectivity towards a variety of guests. Calixarene-based derivatives are thus suitable for numerous applications, from sensoring and the removal of environmentally relevant species to catalysis and their use as biomimetic receptors. The design of calixarene receptors should involve comprehensive thermodynamic, kinetic, structural, solution, solid-state, and computational investigations of the corresponding complexation reactions. Apart from the compatibility of the guest and the receptor, the extent of the host–guest reactions is often quite strongly influenced by the solvation of the reactants and products, and therefore this important phenomenon deserves to be investigated in detail. The effects of intra- and intermolecular hydrogen bonds and other specific solute–solvent interactions can play a very important role as well.

The aim of this Special Issue is to highlight recent advances in our understanding of calixarene coordination reactions based on the results of experimental and theoretical physicochemical studies.

Prof. Dr. Vladislav Tomisic
Dr. Josip Pozar
Guest Editors

Manuscript Submission Information

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Keywords

  • calixarene
  • complexation
  • inclusion
  • solvation
  • structure determination
  • computational studies
  • thermodynamics
  • kinetics.

Published Papers (4 papers)

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Research

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14 pages, 7584 KiB  
Article
Targeting Colorectal Cancer Cells with a Functionalised Calix[4]arene Receptor: Biophysical Studies
by Angela F Danil de Namor, Nawal Al Hakawati and Sami Y Farhat
Molecules 2022, 27(2), 510; https://doi.org/10.3390/molecules27020510 - 14 Jan 2022
Cited by 3 | Viewed by 1680
Abstract
Colorectal cancer (CRC) is a disease which is causing a high degree of mortality around the world. The present study reports the antiproliferative impact of the thioacetamide calix[4]arene, CAII receptor on a highly differentiated Caco-2 cell line. This statement is corroborated by the [...] Read more.
Colorectal cancer (CRC) is a disease which is causing a high degree of mortality around the world. The present study reports the antiproliferative impact of the thioacetamide calix[4]arene, CAII receptor on a highly differentiated Caco-2 cell line. This statement is corroborated by the MTT assay results which revealed a reduction in the cell viability with an IC50 value of 19.02 ± 0.04 µM. Microscopic results indicated that at the starting amount of 10 µM of CAII, a decrease in cells confluency can already be observed in addition to changes in cells morphology. Cell metabolic pathway changes were also investigated. 1H NMR findings showed downregulation in lactate, pyruvate, phosphocholine, lipids, and hydroxybutyrate with the upregulation of succinate, indicating a decline in the cells proliferation. Some biochemical alterations in the cells as a result of the CAII treatment were found by Raman spectroscopy. Full article
(This article belongs to the Special Issue Physicochemical and Structural Aspects of Calixarene Chemistry)
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21 pages, 3682 KiB  
Article
The Role of Triazole and Glucose Moieties in Alkali Metal Cation Complexation by Lower-Rim Tertiary-Amide Calix[4]arene Derivatives
by Josip Požar, Marija Cvetnić, Andrea Usenik, Nikola Cindro, Gordan Horvat, Katarina Leko, Matija Modrušan and Vladislav Tomišić
Molecules 2022, 27(2), 470; https://doi.org/10.3390/molecules27020470 - 12 Jan 2022
Cited by 4 | Viewed by 1598
Abstract
The binding of alkali metal cations with two tertiary-amide lower-rim calix[4]arenes was studied in methanol, N,N-dimethylformamide, and acetonitrile in order to explore the role of triazole and glucose functionalities in the coordination reactions. The standard thermodynamic complexation parameters were determined microcalorimetrically and [...] Read more.
The binding of alkali metal cations with two tertiary-amide lower-rim calix[4]arenes was studied in methanol, N,N-dimethylformamide, and acetonitrile in order to explore the role of triazole and glucose functionalities in the coordination reactions. The standard thermodynamic complexation parameters were determined microcalorimetrically and spectrophotometrically. On the basis of receptor dissolution enthalpies and the literature data, the enthalpies for transfer of reactants and products between the solvents were calculated. The solvent inclusion within a calixarene hydrophobic basket was explored by means of 1H NMR spectroscopy. Classical molecular dynamics of the calixarene ligands and their complexes were carried out as well. The affinity of receptors for cations in methanol and N,N-dimethylformamide was quite similar, irrespective of whether they contained glucose subunits or not. This indicated that sugar moieties did not participate or influence the cation binding. All studied reactions were enthalpically controlled. The peak affinity of receptors for sodium cation was noticed in all complexation media. The complex stabilities were the highest in acetonitrile, followed by methanol and N,N-dimethylformamide. The solubilities of receptors were greatly affected by the presence of sugar subunits. The medium effect on the affinities of calixarene derivatives towards cations was thoroughly discussed regarding the structural properties and solvation abilities of the investigated solvents. Full article
(This article belongs to the Special Issue Physicochemical and Structural Aspects of Calixarene Chemistry)
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10 pages, 2225 KiB  
Article
Anthocyanin Color Stabilization by Host-Guest Complexation with p-Sulfonatocalix[n]arenes
by Johan Mendoza, Luis Cruz, Victor de Freitas, Fernando Pina and Nuno Basílio
Molecules 2021, 26(17), 5389; https://doi.org/10.3390/molecules26175389 - 04 Sep 2021
Cited by 5 | Viewed by 1773
Abstract
Flavylium-based compounds in their acidic and cationic form bring color to aqueous solutions, while under slightly acidic or neutral conditions they commonly bring discoloration. Selective host-guest complexation between water-soluble p-sulfonatocalix[n]arenes (SCn) macrocycles and the flavylium cationic species can increase the stability of [...] Read more.
Flavylium-based compounds in their acidic and cationic form bring color to aqueous solutions, while under slightly acidic or neutral conditions they commonly bring discoloration. Selective host-guest complexation between water-soluble p-sulfonatocalix[n]arenes (SCn) macrocycles and the flavylium cationic species can increase the stability of the colored form, expanding its domain over the pH scale. The association constants between SCn and the cationic (acid) and neutral basic forms of flavylium-based compounds were determined through UV-Vis host-guest titrations at different pH values. The affinity of the hosts for synthetic chromophore was found to be higher than for a natural anthocyanin (Oenin). The higher affinity of SC4 for the synthetic flavylium was confirmed by 1H NMR showing a preferential interaction of the flavylium phenyl ring with the host cavity. In contrast with its synthetic counterpart, the flavylium substitution pattern in the anthocyanin seems to limit the inclusion of the guest in the host’s binding pocket. In this case, the higher affinity was observed for the octamer (SC8) likely due to its larger cavity and higher number of negatively charged sulfonate groups. Full article
(This article belongs to the Special Issue Physicochemical and Structural Aspects of Calixarene Chemistry)
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Review

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29 pages, 9961 KiB  
Review
1,3-Diketone Calix[4]arene Derivatives—A New Type of Versatile Ligands for Metal Complexes and Nanoparticles
by Sergey N. Podyachev, Rustem R. Zairov and Asiya R. Mustafina
Molecules 2021, 26(5), 1214; https://doi.org/10.3390/molecules26051214 - 24 Feb 2021
Cited by 25 | Viewed by 3072
Abstract
The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. [...] Read more.
The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure–property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging. Full article
(This article belongs to the Special Issue Physicochemical and Structural Aspects of Calixarene Chemistry)
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