Aminomethylated Calix[4]resorcinarenes as Modifying Agents for Glycidyl Methacrylate (GMA) Rigid Copolymers Surface

Abstract

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.

Experimental Comparative Study of Dynamic Behavior in Solution Phase of C-Tetra(phenyl)resorcin[4]arene and C-Tetra(phenyl)pyrogallol[4]arene

“…Continuing with our studies of the structure of polyhydroxylated platforms [12,33,40,41], we found that the bulky aromatic substituents on the lower rim of polyhydroxylated platforms in cone conformation exhibited a dynamic behavior, which stimulated interest in examining the conformational preferences. For this purpose, in this article, the comparative behavior of Ctetra(phenyl)-resorcin [4]arene (1) and C-tetra(phenyl)pyrogallol [4]arene (2) compounds is studied using 1 H-NMR and 13 C-NMR data and dynamic 1 H-NMR spectra.…”

“…A field where they have been widely used is host-guest systems [19][20][21], since the electron-rich cavity of cone-type isomers allows different types of interactions with molecules [22] to be established, especially with tetraalkylammonium-type salts or metal cations [23,24]. This has led to different areas of applications, such as sensors [25], catalysis [26,27], heavy metal complexes for purification of water tributaries [28][29][30] and chemical separations by modification of Hight Performance Liquid Chromatography (HPLC) columns [31][32][33][34], among others.…”

Obtaining an immunoaffinity monolithic material: poly(GMA-co-EDMA) functionalized with an HPV-derived peptide using a thiol–maleimide reaction

“…This signal is characteristic of the maleimide group. 25 The IR spectra of the functionalized monolith suggest the presence of peptide 2 attached to the material. In order to corroborate this result, the interaction between poly(GMA- co -EDMA)- Mhx -C-Ahx-SPINNTKPHEAR material and polyclonal anti-SPINNTKPHEAR antibodies (1–12) was determined via ELISA assays, since this technique has high sensitivity and specificity.…”

“…The preparation of the copolymer was performed following the protocol reported by ref. 17 , 25 and 31 . Briefly, first the monomer inhibitor (hydroquinone monomethyl ether, MEHQ) was removed from monomers glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EDMA), using a silica gel column (0.5 g mL −1 of monomer).…”

Methodologies for the Derivatization of Resorcin[4]arenes at the Upper Rim ortho‐Positions

“…Most intriguing was the formation of inherently chiral oxazine resorcina[4]arenes 7 a – c through a domino ring closing reaction with one of the adjacent hydroxyl groups when employing secondary amines, realizing up to 70 % product yields. Several other authors have successfully utilized this synthetic protocol to achieve architectural designs suitable for a number of applications [70,71] …”