IP-2024-05-3012

Project duration: 9. 12. 2024. − 8. 12. 2027.

Funding

CROATIAN SCIENCE FOUNDATION

PRINCIPAL INVESTIGATOR: prof. dr. sc. Vladislav Tomišić

INSTITUTIONS

Prirodoslovno-matematički fakultet, Sveučilište u Zagrebu

Institut Ruđer Bošković

University of Surrey, United Kingdom

Faculty of Science, University of Zagreb

Ruđer Bošković Institute

University of Surrey, United Kingdom

PROJECT TITLE

Termodinamički, spektroskopski i strukturni aspekti koordinacijskih reakcija kaliksarena

Coordination Reactions of Macrocyclic Ligands in Solution

ABSTRACT

Efficient and selective macrocyclic receptors for ions and neutral molecules have played an important role in the development of supramolecular chemistry. Among the most important ones are calixarenes, which prompted us to devote research to the design, synthesis, and physicochemical characterization of these compounds and their complexation reactions. A series of derivatives with varying number of functionalized phenolic subunits will be prepared to obtain receptors with exceptional binding affinities towards monoatomic and molecular ions and neutral species. Some of these are aimed to be highly sensitive fluorescent sensors. With this respect, our recent findings regarding the intrinsic fluorescence of calixarenes will be implemented and this phenomenon will be studied in detail. Water-soluble derivatives and their binding abilities in aqueous medium will be especially addressed. An important objective will be development of calixarene capsules and polymers as well as functionalization of surfaces with complementary calixarenes. Particular attention will be paid to the solvation effects on binding reactions, with the emphasis on the inclusion of solvent molecules into the calixarene cavity. Furthermore, calixarene derivatives will be probed as potential receptors for various hydrophobic and (super)chaotropic compounds. Integrated thermodynamic, structural, and computational studies of complexation and solvation processes will be carried out. Several experimental (ITC, fluorimetry, UV-Vis and NMR spectroscopy, potentiometry, conductometry, X-ray diffraction) and computational (MD, DFT) methods will be employed. That will enable reliable determination of thermodynamic quantities (stability constants, reaction and solution Gibbs energies, enthalpies, and entropies) as well as structural characteristics of the receptors and their complexes. The obtained information will provide a detailed insight into the key factors determining the studied complexation equilibria.

PROJECT TEAM

PMF, Sveučilište u Zagrebu / Faculty of Science, University of Zagreb: Vladislav Tomišić (PI), Nikola Bregović, Marija Cvetnić, Gordan Horvat, Katarina Leko, Matija Modrušan, Vladimir Stilinović, Andrea Usenik

Institut Ruđer Bošković / Ruđer Bošković Institute: Leo Frkanec, Mladen Žinić

University of Surrey: Angela F. Danil de Namor

For the full list of publications, conferences, PhD/diploma/master theses, as well as awards visit www.pmf.unizg.hr/chem/znanost/hrzz_calixcore.