Supramolecular Chemistry Supramolecular Chemistry

Supramolecular chemistry is the branch of chemistry associated with the study of complex molecular systems formed from several discrete chemical components. The general field of this research is a host-guest supramolecular chemistry, which covers several specific topics including design at the molecular level to synthesize hosts with high affinities for specific guest molecules or ions and self-assembly processes leading to non-covalently complex systems.

 

Calixarene systems

Calixarenes are cavity-shaped macrocyclic ligands obtained from the condensation of p-alkylphenols with formaldehyde under alkaline conditions. The synthesis of calixarenes and their derivatives is a key area of this research topic. We are mainly focused on the design and preparation of calixarene derivatives exhibiting selective cation recognition, such as amide, thioamide and hydroxamate-appended calixarenes. More recently, lower-rim and upper-rim functionalized calixarenes appended with carboxylate or sulfonate groups were used for the construction of organic-inorganic hybrid materials, among them, coordination polymers.

 

Selected publications:

  • Viana, R. S., Oliveira, C. A. F., Chojnacki, J., Barros, B. S., Alves-Jr, S., & Kulesza, J. Structural and spectroscopic investigation of new luminescent hybrid materials based on calix[4]arene-tetracarboxylate and Ln3+ ions (Ln = Gd, Tb or Eu). Journal of Solid State Chemistry, 251 (2017), 26–32. https://doi.org/10.1016/j.jssc.2017.04.002

  • Marcos, P. M., Fonseca, J. D., Proença, C. S., Ascenso, J. R., Bernardino, R. J., Kulesza, J., & Bochenska, M. Experimental and computational studies of the binding properties of lower rim tetra- and di-substituted calix[4]arene amide derivatives with metal ions. Supramolecular Chemistry, 28 (2016), 367–376. https://doi.org/10.1080/10610278.2015.1093631

 

Cation recognition

This research work is directed towards studies of host-guest interactions between calixarene derivatives and metal cations by diverse methods such as liquid-liquid extraction, UV-Vis spectroscopy and microcalorimetry. Special attention is focused on heavy metal cations (Pb2+, Cd2+). The goal of our research is to find the structure-binding property relationship with a view to increase the understanding of molecular recognition processes in such systems. Selective binding of particular guest species is of a great importance for applications such as extraction agents for the purification of the industrial effluent, waste and soil water from toxic metals, or molecular sensor devices.

 

Selected publications:

  • Kulesza, J., Guzinski, M., Bochenska, M., Hubscher-Bruder, V., & Arnaud-Neu, F. Lower rim substituted p-tert-butyl-calix[4]arene. Part 17. Synthesis, extractive and ionophoric properties of p-tert-butylcalix[4]arene appended with hydroxamic acid moieties. Polyhedron, 77 (2014), 89–95. https://doi.org/10.1016/j.poly.2014.04.009
  • Bochenska, M., Kulesza, J., Chojnacki, J., Arnaud-Neu, Françoise, Hubscher-Bruder, Véronique, Lower rim substituted p-tert-butyl calix[4]arene; Part 14. Synthesis, structures and binding studies of calix[4]arene thioamides. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 68 (2010), 75-83. https://doi.org/10.1007/s10847-010-9735-2

 

Ion-selective electrodes

Nowadays, environmental contamination by heavy metals is one of the main concern of the society. The monitoring of these metals in waters is important to ensure that their concentrations remain below the acceptable level. This research work focuses on the fabrication of potentiometric membrane sensors based on calixarene derivatives exhibiting remarkable selectivity, especially for Pb2+ cations.

 

Selected publications:

  • Kulesza, J., Guzinski, M., Hubscher-Bruder, V., Arnaud-Neu, F., Bochenska, M. Lower rim substituted p-tert-butyl-calix[4]arene. Part 16. Synthesis of 25,26,27,28-tetrakis(piperidinylthiocarbonylmethylene)-p-tert-butylcalix[4]arene and its interaction with metal ions. Polyhedron, 30 (2011) 98-105. https://doi.org/10.1016/j.poly.2010.09.038
  • Bochenska, M., Guzinski, M., Kulesza, J. Lower Rim Substituted p-tert-Butyl-Calix[4]arene. Part 15. Pb(II)-Ion-Selective Electrodes Based on p-tert-Butyl-calix[4]arene Thioamides. Electroanalysis, 21 (2009) 2054-2060. https://doi.org/10.1002/elan.200904638

 

Recognition of volatile organic compounds

Volatile organic compounds such as benzene, toluene, ethylbenzene, and xylenes (BTEX) are very important materials in organic industrial chemistry. These compounds, however, often coexist with their aliphatic or aromatic analogues, and most of them have very similar physicochemical properties such as boiling points. Therefore, the separation of these organic species is of high value, although it is a technical challenge. Our group develops efficient and selective platforms based on organic and inorganic-organic hybrid materials for the separation of BTEX. The goal of our studies is to investigate the host-guest interactions between BTEX components and an adsorbent system.