Surface modification of poly(GMA-co-EDMA-co-MMA), whose synthesis was performed by copolymerization of 2,3-epoxypropyl methacrylate (GMA), methyl methacrylate (MMA), and ethylene glycol dimethacrylate (EDMA), was compared between aliphatic and aromatic substituted resorcarenes. The copolymer surface was modified by reacting with resorcarenes, and the vibrational properties of the modified copolymers were investigated via attenuated total reflectance Fourier transform infrared (ATR-FTIR) and Raman spectroscopies in dry state at room temperature. Those analysis showed that only tetra(p-hydroxyphenyl)resorcarene was linked to the copolymer, the reaction was regioselective with the crown conformer. Additionally, quantification of incorporated macrocyclic was performed, specifically, the maximum fixation of resorcarene in the copolymer was 95% when employing two molar resorcarene excesses per glycidyl residue.The modification was carried out in both acidic and basic medium and it was established that the polymer is modified with the aromatic resorcarene only in basic medium, while the reaction in basic medium with aliphatic resorcarenes produces their corresponding tetrasodium salt.

Functionalization of tetrapropylcalix[4]resorcinarene, tetrapentylcalix[4]resorcinarene, tetranonylcalix[4]resorcinarene, and tetra-(4-hydroxyphenyl)calix[4]resorcinarene by means of aminomethylation reactions with the amino acids β-alanine and l-proline in the presence of aqueous formaldehyde was carried out. When β-alanine was used, the reaction products were tetrabenzoxazines. The reaction with tetra-(4-hydroxyphenyl)calix[4]resorcinarene did not proceed under the experimental conditions; therefore, l-proline was used, and the corresponding tetra-Mannich base was regio- and diasteroselectively formed. The products were characterized via FT-IR, 1H NMR, 13C NMR, and elemental analysis. With these aminomethylated-calix[4]resorcinarenes, the chemical surface modification of the copolymers poly(GMA–co–EDMA) and poly(BMA–co–EDMA–co–MMA) in a basic medium was studied. The results were quite satisfactory, obtaining the corresponding copolymers functionalized by nucleophilic substitution reaction and ring-opening between the carboxyl group of the upper rim of aliphatic calix[4]resorcinarenes and the hydroxyl group of the lower rim in the aromatic calix[4]resorcinarene and the epoxy group of the glycidyl methacrylate residue of each copolymer. The modified copolymers were characterized via FT-IR, scanning electron microscopy imaging, and elemental analysis. Finally, the modified copolymer surfaces exhibited interaction with peptides, showing their potential application in chromatographic separation techniques such as high-performance liquid chromatography.