Synthesis of macroporous polymers with radical scavenging properties by immobilization of polyphenolic compounds

Abstract

Solid phase radical scavengers have been prepared by the immobilization of antioxidant (AOX) compounds on macroporous polymers. Poly(glycidylmethacrylate- co-trimethylolpropane trimethacrylate) [poly(GMA-TRIM)] and poly(N-acryloyl- tris(hydroxymethyl)aminomethane-co-glycidylmethacrylate-co-N, N′-methylenebisacrylamide) [poly(NAT-GMA-BIS)] were prepared by free radical polymerization using a mixture of dimethylsulfoxide (DMSO)- poly(ethyleneglycol) 6000 (PEG 6000) as a porogenic solvent. The polymers were aminated with ethylenediamine (EDA) and the linkage of the polyphenolic compounds (gallic and caffeic acids) was carried out by two different approaches: through N,N′-dicyclohexylcarbodiimide/4-dimethylaminepyridine (DCC/DMAP) system (one-step method) or through the previous formation of the acyl chloride of the polyphenolic compounds and subsequent amidation reaction (two-step method). The available phenolic groups on the macroporous polymers were determined using the Folin-Ciocalteu method; the radical scavenging properties of the materials prepared were evaluated using the radical species 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) and 2,2′-azino-bis-[3- ethylbenzothiazoline-6-sulfonic acid] radical cation (ABTS +). From the results, higher antiradical capacities were obtained with the polymers in which the immobilization of the antioxidant molecules was performed through the two-step method. The polymeric networks prepared in this work yielded up to 13.2 μmol AOX/g of dry polymer, which allowed a quantitative removal of the radicals tested in less than 30 min. © 2012 Elsevier Ltd. All rights reserved.