On-line determination of 4-nitrophenol by combining molecularly imprinted solid-phase extraction and fiber-optic spectrophotometry.

In the present paper, we describe a new on-line SPE system where molecular imprinting, fiber-optic detection and flow injection analysis were combined for the first time. This new system has been applied for the on line detection of 4-nitrophenol (4-NP). Initially, molecularly imprinted polymers (MIP) have been prepared for the selective extraction of 4-NP using 4-vinylpyridine and ethylene glycol dimethacrylate as functional and cross-linking monomers, respectively. Selective extraction was achieved using the designed MIP with 97% of recovery on imprinted polymer and 10% on control polymer. The system provided a high degree of accuracy, with RSDs varying between 0.7 and 1.39%. In respect of accuracy, reproducibility, and rapidity, this system is comparable with HPLC. In short, the system allows simple, fast, and accurate analyte determination with the possibility of future automation.

Novel fluorescent membrane for metronidazole sensing prepared by covalent immobilization of a pyrenebutyric acid derivative.

In the present paper, we report the fabrication of a new sensing membrane for fluorescence detection of metronidazole (MNZ). Briefly, a pyrenebutyric acid derivative, 2-(methacryloyloxy) ethyl-4-(1-pyrenyl) butanoate (MPB) with a double bond, was synthesized and copolymerized with 2-hydroxyethylmethacrylate (HEMA) on the activated glass surface by thermal initiation in the presence of cross-linker. The sensor responds linearly to metronidazole in the concentration range of 1.23~35.48 mg.L(-1) in aqueous solution with a detection limit of 0.36 mg.L(-1). The lifetime is enhanced by covalently immobilizing the pyrenebutyric acid derivative on glass slide, which hinders leaching of the dye from the membrane. The sensor could be regenerated after use by washing in methanol (RSD = 2.42 %), and it shows sufficient stability, and selectivity. Interference of other pharmaceuticals on membrane performance is discussed. The developed membrane has been successfully applied for the direct determination of metronidazole in human serum sample without pretreatment.

Rational design of molecularly imprinted polymer: the choice of cross-linker.

The paper describes a rational approach for the selection of cross-linkers during the development of molecularly imprinted polymers (MIPs). As a model system for this research MIPs specific for the drug zidovudine (AZT) were designed and tested. Three cross-linkers trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) were studied. The analogue of zidovudine (AZT) ester (AZT-ES) was used as a dummy template. The imprinting factors for all of the polymers in the static adsorption experiments were calculated. The data on the AZT adsorption by control polymers (CP), which were prepared with different cross-linkers without a functional monomer, was also analyzed. DVB was found to be more inert towards zidovudine than EGDMA and TRIM, which was confirmed by both molecular modelling and adsorption experiments. It was demonstrated that DVB-based polymers had a higher imprinting factor (I = 1.85) compared with other tested cross-linked polymers. It was suggested that the selection of the cross-linker should be based on the strength of the interaction with the template: the cross-linker which displays lower binding of the template should be preferential because it generates MIPs with lower non-specific binding and a higher imprinting factor, and therefore specificity. Which cross-linker to use for the preparation of any particular MIP can be determined by analysis of the interactions between the cross-linker and template. This could be done either virtually using computational modelling or by template adsorption using a small library of polymers prepared using different cross-linkers.