Reactions of glycidyl methacrylate with the crown and chair conformers of tetra(4-hydroxyphenyl)calix[4]resorcinarene were studied. The reactions were done over epoxide groups present in the ester, which can easily undergo an opening reaction with hydroxyl groups in the macrocyclic system. Initially, epoxidation reactions were carried out with pure conformers, and it was observed that the reaction between tetra(4-hydroxyphenyl)calix[4]resorcinarene fixed in the chair conformation does not occur, while for the molecule fixed in the crown conformation only one tetraalkylated derivative was obtained. The obtained product was characterized using IR, ¹H-NMR, ¹³C-NMR, COSY, HMQC and HMBC techniques. An exhaustive NMR study showed that the reaction is selective at the hydroxyl groups in the lower rim, without affecting the hydroxyl groups in the upper rim. In addition, the RP–HPLC analysis of the epoxidation reaction mixture, using both crown and chair conformers, showed that only the crown conformer reacted under tested conditions. Finally, a comparative study of the reactivity of tetranonylcalix[4]resorcinarene with glycidyl methacrylate showed that the reaction does not take place. Instead, the formation of the tetranonylcalix[4]resorcinarene tetrasodium salt was observed, which confirms that the hydroxyl groups in the upper rim are unreactive under these conditions.

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.

Aminomethylation reactions between chiral amino compounds (S)-(-)-1-phenylethylamine and l-proline with tetranonylresorcinarene and tetra-(4-hydroxyphenyl)resorcinarene in presence of formaldehyde were studied. The reaction between l-proline and resorcinarenes generated regioselectively chiral tetra-Mannich bases, due to the molecular incorporation of the fragment of the chiral amino acid. On the other hand, tetranonylresorcinarene and (S)-(-)-1-phenylethylamine formed regio- and diasteroselectively chiral tetrabenzoxazines, both by chiral auxiliary functionalization and by the transformation of the molecular structure that confers inherent chirality. The products obtained were characterized using IR, ¹H-NMR, ¹³C-NMR, COSY, HMQC, and HMBC techniques. The reaction of (S)-(-)-1-phenylethylamine with tetra-(4-hydroxyphenyl)resorcinarene did not proceed under the experimental conditions. Once the chiral aminomethylated tetra-(4-hydroxyphenyl)resorcinarene was obtained, the chemical modification of poly(GMA–co–EDMA) was studied, and the results showed an efficient incorporation of the aminomethylated compound. For the physical modification, chiral aminomethylated tetranonylresorcinarenes were employed, finding that the incorporation of modified resorcinarenes occurs, but with less efficiency than that observed using chemical modification. The modified polymers were characterized via FT-IR, scanning electron microscopy imaging, and elemental analysis. Finally, polymers modified with chiral resorcinarenes were used as sorbents in norepinephrine microextraction; for practical purposes, artificial urine was prepared and used. To perform the microextraction, the decision was made to use the modern rotating-disk sorptive extraction technique (RDSE), because of its analytical attributes as a green, or eco-friendly, technique. According to the results, the method preliminarily validated for the determination of norepinephrine in artificial urine shows that the modified polymer with chiral derivative of tetra-(4-hydroxyphenyl)resorcinarene worked effectively as a new sorbent phase for the quantitative microextraction of norepinephrine, exhibiting high stability and homogeneity of composition and structure within the working range.

A copolymer of poly(BuMA–co–EDMA) modified with C-tetra(nonyl)calix[4]resorcinarene was obtained via the impregnation method. The formation of the modified copolymer was confirmed and investigated using various techniques; in this way, the presence of calix[4]resorcinarene was confirmed by FT-IR spectroscopy and by high resolution transmission electron microscopy. The modified copolymer was used for the removal of highly toxic cations (Pb²⁺, Hg²⁺, and Cd²⁺) from aqueous solutions. To perform the removal, we used the batch sorption technique and the effects of time of contact, pH, and volume of sample on the effective sorption were determined. The best results were observed for Pb²⁺ extraction, which was comparatively more efficient. Adsorption–desorption experiments revealed that the modified copolymer could be used for several cycles without significant loss of adsorption capacity. Finally, the results showed that the modified copolymer application is highly efficient for the removal of lead ions from aqueous solutions.

C-tetra(4-methoxyphenyl)calix[4]resorcinarene was synthesized by hydrochloric acid-catalysed cyclocondensation of resorcinol and 4-methoxybenzaldehyde. Under these conditions, the reaction produces a conformational mixture of crown and chair structural conformers, which were separated and characterized by chromatographic and spectroscopic techniques. The antioxidant activity of both conformers was measured by using the DPPH assay, through which it was observed that the chair conformer showed greater antioxidant activity (IC₅₀ = 47.46 ppm) than the crown conformer (IC₅₀ = 78.46 ppm). Additionally, it was observed that the mixture of both conformers presented lower antioxidant activity than either conformer in isolation. The results found suggest that the chair conformer has efficient antioxidant activity that makes it a potential target for further research.