Surface Modification of Poly(GMA-co-EDMA-co-MMA) with Resorcarenes

Abstract

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.

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

“…The preparation of calix[4]resorcinarenes has been reported elsewhere [30,34]. Hydrochloric acid (10 mL) was carefully added to a solution of resorcinol (10 mmol) and aldehyde (10 mmol), in a 1:1 ethanol/water mixture (40 mL).…”

“…The functionalization process was adapted from the methodology previously proposed by us [30]. A mixture of ( 1 ) (0.2 mmol) in DMF/DMSO and sodium hydroxide (0.2 mmol) was added to triturated copolymer poly(GMA– co –EDMA– co –MMA) (500 mg).…”

“…An example is the modification of a RP-C18 column, to which a calix[4]resorcinarene spaced with an undecyl group was covalently linked at the lower rim, observing acceptable selectivity in the separation of cis and trans isomers of flupentixol, clopenthixol, chlorprothixene, and doxepin [28]. Currently, copolymer materials based on methacrylates have experienced a great upsurge [29], mainly because of the possibility of chemical modification on the epoxy group, when the monomer glycidyl methacrylate is present in the copolymer [30]. In addition, the methacrylate copolymers have the great advantage of being monolithic materials; therefore, they possess high porosity and a large surface area, attributes that are satisfactorily applied in their use as stationary phases.…”

“…Continuing with our research on the synthesis and functionalization of calix[4]resorcinarenes [31,32,33,34,35] and on the modification of polymeric surfaces [30], in this article we study the synthesis and use of aminomethylated-calix[4]resorcinarenes in the functionalization of glycidyl methacrylate copolymers and their application in the interaction with peptides.…”

Analysis by RP-HPLC and Purification by RP-SPE of the C-Tetra(p-hydroxyphenyl)resorcinolarene Crown and Chair Stereoisomers

“…The many possible structural variations or resorcinarenes fixed in crown conformation and substituted with aromatic ring in the lower rim lead to potential applications as chemical receptors for molecules and ions [17, 24–27], in absorption of heavy metal ions [28], in lithographic processes [29], and as photoresistant materials for glasses [30] and are used for modification of polymeric surfaces with potential applications as stationary phase in chromatographic methods [31]. Despite the importance of this type of molecules, in terms of their applications, there is only one method reported for their separation, which includes successive crystallizations [32].…”