The key features of calixarene derivatives as multivalent ligands for biomacromolecules and as multifunctional catalysts are reviewed herein. The ease of functionalization and the possibility to control the regio- and stereochemical disposition of multiple ligating units around a central core allow to obtain ligands with high affinity and selectivity especially for proteins and nucleic acids. The hydrophilic/lipophilic character can also be finely tuned, allowing to obtain monomeric hybrid derivatives or amphiphiles able to self-assemble alone or in co-formulation with lipids to give nanoparticles and liposomes that incorporate calixarenes. The knowledge acquired up to now sheds light on the future applications of calixarenes in bionanotechnology and nanomedicine.
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