Synthesis and Characterization of Ammonium Functionalized Porous Poly(glycidyl methacrylate-co-ethylene dimethacrylate) Monoliths for Microscale Analysis and Its Application to DNA Purification

Abstract

International audienceA systematic study of parameters affecting the nucleophilic addition of secondary and tertiary amines on reactive epoxy groups was conducted on porous polymer monoliths. Reaction of small amines like diethylamine (DEA) or triethylamine (TEA) on poly(glycidyl methacrylate-co-ethylene dimethacrylate) monoliths (poly(GMA-co-EDMA)) allows to prepare anion exchange media. This study aimed to determine optimal and suitable conditions to prepare anion-exchange porous monolith inside 100 tun internal diameter capillary. The reaction kinetic of amine nucleophilic addition on porous poly(GMA-co-EDMA) monoliths was followed by FTIR-ATR spectroscopy. The reactivity of such epoxy-functionalized porous polymers was first determined through a study in pure amine solutions. Thereafter, conditions of reactions (i.e., temperature and time of reaction, solvent composition, concentration of amine) with respect to its further implementation at nanoscale, were optimized through a factorial analysis. The optimization allowed extending conversion yields of epoxy groups up to more than 90% in dilute amine solution within less than 4 hours of reaction for TEA addition. This ion-exchange support with respect to the in-situ light-addressable process of elaboration is specifically designed to be incorporated as biomolecular sample preparation module in microsystem devices. The high loading capacity obtained for the preconcentration of DNA demonstrate the attractivity of this functionalized polymeric porous monolith as solid-phase support to improve the quantity and the efficiency of DNA extraction applied into microscale format like capillaries or lab-on-chip

Improved chromatographic performances of glycidyl methacrylate anion‐exchange monolith for fast nano‐ion exchange chromatography

“…Here, we showed that the transfer of well‐established thermally induced polymerization to photo‐induced polymerization can be a relevant way to enhance the IEC of glycidyl‐based monolith. Using the efficient mixture defined by Ueki et al 11 and our previously published functionalization procedure 44, the present study demonstrates the potential of this strategy to obtain monoliths with unmatched chromatographic performances.…”

“…30 min irradiation) in 100 μm id Teflon‐coated capillaries. Single‐step preparation of quaternary ammonium functionalized monolith has been carried out according to a previously published procedure 44. Briefly, monolithic capillary columns were filled with a solution of TEA in 50:50 v/v EtOH/water.…”

“…UV‐transparent Teflon‐coated fused‐silica capillaries were first pretreated with 3‐(trimethoxysilyl)‐propyl methacrylate according to a previously published procedure 44. Thereafter, polymerization mixture was introduced under the gas pressure of 500 mbar for 1–2 min and the capillary ends were sealed with silicon.…”

Photografting as a versatile, localizable, and single‐step surface functionalization of silica‐based monoliths dedicated to microscale separation techniques

“…The more convenient way to insert solid stationary phases inside microchannels relies on the in situ synthesis of porous materials such as organic or inorganic monoliths. Photopolymerized organic monoliths can be in situ synthesized using a large variety of monomers (mainly acrylate and methacrylate ones) that allow covering a wide range of interaction mechanisms from ion exchange to popular RP mode . However, each modification in the polymerization mixture implies a time‐consuming reoptimization of the entire polymerization process.…”

“…The more convenient way to insert solid stationary phases inside microchannels relies on the in situ synthesis of porous materials such as organic or inorganic monoliths. Photopolymerized organic monoliths can be in situ synthesized [8][9][10][11][12][13] using a large variety of monomers (mainly acrylate and methacrylate ones) that allow covering a wide range of interaction mechanisms from ion exchange to popular RP mode [14]. However, each modification in the polymerization mixture implies a timeconsuming reoptimization of the entire polymerization pro-Correspondence: Dr. Racha El Debs, Université Claude Bernard Lyon1, 5 rue de la doua, Villeurbanne 69100, France E-mail: racha.debs@hotmail.com Fax: +33(0)472448319 Abbreviations: AIBN, 2,2 -azobisisobutyronitrile; BME, benzoin methyl ether; ␥-MAPS, [␥-(methacryloyloxy)propyl]trimethoxysilane; META, [2-(methacryloyloxy) ethyl]trimethylammonium chloride; ODS, octadecyldimethylchlorosilane; TEA, triethylamine cess.…”