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Supramolecular Host/Guest Compounds and Their Prospects for Multifunctional Materials

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

Deadline for manuscript submissions: closed (30 April 2026) | Viewed by 4140

Special Issue Editors


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Guest Editor
Laboratory of Thermochemistry, School of Chemistry and Chemical Engineering, University of Surrey, Guildford GU2 7XH, UK
Interests: supramolecular chemistry; thermodynamics; water decontamination; ion selective electrodes

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Guest Editor Assistant
Department of Biological Sciences, Faculty of Science, Beirut Arab University, Beirut, Lebanon
Interests: supramolecular chemistry

Special Issue Information

Dear Colleagues,

The selective behaviour of synthetic (crown ethers and cryptands) and natural macrocycles for alkali–metal cations marked the beginning of Supramolecular Chemistry in the late sixties and early seventies. These discoveries provoked a remarkable expansion in this area of research leading to a huge number of papers, reviews, books and the Nobel Prize Award in 1987 to Pedersen (crown ethers), Lehn (cryptands) and Cram (spherands). Since then, Supramolecular Chemistry has captivated the interest of the scientific community to the extent that the initial and continuous interest in host–guest chemistry has extended to the formation of supramolecular assemblies resulting from non-covalent interactions between host and host–guest complex units containing auxiliary functional groups.

The field continues to develop rapidly, covering several disciplines. In fact, Supramolecular Chemistry has contributed significantly to the development of stable tridimensionality nanomaterials with ordered structures, supramolecular functional materials with electronic and transport properties and the use of the hosting properties of new supramolecular structures to encapsulate fullerenes. These statements in no way undermine the fact that it is the stability of host–ion complexes that leads to the production of a huge number of new salts for which their behaviour in solution and their applications have not received widespread interest.

The main aim of this volume is to highlight the latest developments in the following:

  1. Host–guest chemistry with particular emphasis on the design, synthesis and structural and physicochemical characterisation of new receptors and their complexes with neutral and ionic species in solution and in the solid state.
  2. Functional materials based on supramolecular assemblies resulting from a diverse range of interactions, their structural characterisation and multidisciplinary applications. An outlook of the prospects for multifunctional materials to impact further scientific and technological developments should be addressed.

Prof. Dr. Angela Danil De Namor
Guest Editor

Dr. Nawal Al Hakawati
Guest Editor Assistant

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Keywords

  • supramolecular chemistry
  • host-guest chemistry
  • macrocycles and cages
  • self-assembly
  • supramolecular materials

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Published Papers (3 papers)

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Research

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12 pages, 1583 KB  
Article
Interaction of Lysozyme with Sulfated β-Cyclodextrin: Dissecting Salt and Hydration Contributions
by Jacek J. Walkowiak
Molecules 2026, 31(2), 372; https://doi.org/10.3390/molecules31020372 - 20 Jan 2026
Viewed by 467
Abstract
This article investigates the thermodynamic driving force of the interaction between lysozyme (Lys) and sulfated β-cyclodextrin (β-CDS), with a particular emphasis on the elusive role of hydration during polyelectrolyte–protein binding. Using isothermal titration calorimetry (ITC), the binding affinity was quantified across varying temperatures [...] Read more.
This article investigates the thermodynamic driving force of the interaction between lysozyme (Lys) and sulfated β-cyclodextrin (β-CDS), with a particular emphasis on the elusive role of hydration during polyelectrolyte–protein binding. Using isothermal titration calorimetry (ITC), the binding affinity was quantified across varying temperatures and salt concentrations, employing a recently developed thermodynamic framework that explicitly separates the contributions from counterion release and hydration effects. The study reveals that while counterion release is minimal in the Lys/β-CDS system, hydration effects become a dominant factor influencing the binding free energy ΔGb, especially as experimental temperature deviates from the characteristic temperature T0. It demonstrates that hydration contributions can substantially weaken binding at increased salt concentration cs. The high characteristic temperature T0 and the salt-dependent heat capacity change indicate a complex interplay of water structure and ion association—significantly departing from commonly linear interpretations of ΔGb vs. log cs based solely on counterion release effects. This work advances the understanding of polyelectrolyte–protein interactions by providing the first direct quantification of the hydration effect in such complexes and may have an impact on the rational design of biomolecular assemblies and therapeutic carriers. Full article
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30 pages, 5237 KB  
Article
A Detailed Thermodynamic Description of Ion Pair Binding by a Calix[4]arene Derivative Containing Urea and Amide Functionalities
by Marija Cvetnić, Tamara Rinkovec, Robert Vianello, Gordan Horvat, Nikola Bregović and Vladislav Tomišić
Molecules 2025, 30(11), 2464; https://doi.org/10.3390/molecules30112464 - 4 Jun 2025
Cited by 2 | Viewed by 2257
Abstract
Receptors capable of binding both positive and negative ions are an important domain of supramolecular chemistry with valuable application potential. A Complete thermodynamic description of the equilibria related to ion pair recognition is beneficial in developing the optimized receptor systems, although it represents [...] Read more.
Receptors capable of binding both positive and negative ions are an important domain of supramolecular chemistry with valuable application potential. A Complete thermodynamic description of the equilibria related to ion pair recognition is beneficial in developing the optimized receptor systems, although it represents a difficult task that is rarely resolved due to various coupled processes. Here, we present a comprehensive study of ion pair (NaCl, NaHSO4, and NaH2PO4) binding by a ureido–amide calix[4]arene host in acetonitrile using a series of experimental techniques and molecular dynamics simulations. We devoted particular attention to characterizing the side processes (ion association and salt precipitation) and included them in the models describing ion pair complex formation. For this purpose, a multimethod approach (potentiometry, conductometry, ITC, flame AES) was employed, generating reliable data which provided insight into the thermodynamic effect of each included equilibrium. Positive cooperativity was observed in the context of NaCl and NaHSO4 binding by the studied calixarene. Computational results related to the NaCl complex in acetonitrile revealed that favorable Coulombic interactions, changes in affinity for solvent molecule inclusion, and intramolecular hydrogen bonding contributed to cation-induced cooperativity. Full article
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Review

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17 pages, 3179 KB  
Review
Host–Guest Chemistry as a Supramolecular Engine for Iontronic Transduction in Nanochannels
by L. Miguel Hernández Parra, Angel L. Huamani, Ignacio T. Matelo, M. Lorena Cortez, Matías Rafti, Gregorio Laucirica, Waldemar Marmisollé and Omar Azzaroni
Molecules 2026, 31(4), 713; https://doi.org/10.3390/molecules31040713 - 19 Feb 2026
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Abstract
Since the first synthetic macrocyclic receptors were shown to bind ions selectively, supramolecular host–guest chemistry has enabled the translation of molecular recognition events into physical signals. Early coupling of such receptors to ion-sensitive field-effect transistors established a bridge between supramolecular chemistry and solid-state [...] Read more.
Since the first synthetic macrocyclic receptors were shown to bind ions selectively, supramolecular host–guest chemistry has enabled the translation of molecular recognition events into physical signals. Early coupling of such receptors to ion-sensitive field-effect transistors established a bridge between supramolecular chemistry and solid-state electronics. Today, this bridge is rebuilt in iontronics, where ions carry information through nanoconfined media and ionic transport becomes highly sensitive to electrostatic gradients, surface charge, and surface molecular interactions. As a result, ionic flux can serve as an efficient transduction mechanism that responds precisely, reversibly, and rapidly to changes in the chemical environment. Within this regime, host–guest chemistry offers a powerful means to exert direct control over ionic behavior, allowing molecular recognition to modulate conductance, rectification, and ion selectivity, thereby conferring practical function to nanofluidic systems. This review highlights systems in which host molecules act as chemical actuators that modulate nanochannel surface chemistry, thereby regulating ionic flux and enabling reversible, tunable, and stimulus-responsive behaviors. We survey architectures in which crown ethers, calixcrowns, pillararenes, and related hosts are integrated into solid-state nanochannels, emphasizing representative achievements such as biological-level Na+/K+ selectivity in crown ether-based systems and nanomolar-level detection of ions using calixcrowns- and pillararene-functionalized nanochannels. Finally, we discuss how temperature, pH, light, and redox state act as external stimuli that reversibly switch between conductive states, yielding ion-selective platforms for sensing and ion sieving. Full article
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