Since the discovery of polyphenolic resins 150 years ago, the study of polymeric compounds named calix[n]arene has continued to progress, and those skilled in the art perfectly know now how to modulate this phenolic ring. Consequently, calix[n]arenes are now used in a large range of applications and notably in therapeutic fields. In particular, the calix[4]arene exhibits multiple possibilities for regioselective polyfunctionalization on both of its rims and offers researchers the possibility of precisely tuning the geometry of their structures. Thus, in the crucial research of new antibacterial active ingredients, the design of calixarenes finds its place perfectly. This review provides an overview of the work carried out in this aim towards the development of intrinsically active prodrogues or metallic calixarene complexes. Out of all the work of the community, there are some excellent activities emerging that could potentially place these original structures in a very good position for the development of new active ingredients.

The tetrathiafulvalene has been coupled via an imine bond to the p-(tert-butyl)calix[4]arene upper rim.

The antibacterial tetracationic tetra-p-guanidinoethylcalix[4]arene developed by our team has been anchored through bottom-up or top-down pathways to the surface of Merrifield and Wang benzaldehyde resins; the attachment involved either a pyridinium linker or an imine/amine one. The grafting yields were evaluated by elemental analysis through the nitrogen content. Their sequestering properties towards bacteria were evaluated, using E. coli as a model, by capillary electrophoresis (CE) which showed their efficiencies and their bacteriophilic behaviors. All the new materials were compared to two pyridinium-derived Merrifield resins in terms of effective capture, efficiency, and removal coefficients, showing that some of these calixarene-derived resins are good bacteriophilic materials. Confirmation of such behavior has been provided by microscopy.