Determination of trace 2,4-dinitrophenol in surface water samples based on hydrophilic molecularly imprinted polymers/nickel fiber electrode.

A rapid, sensitive and selective electrochemical method was proposed for the determination of 2,4-dinitrophenol (2,4-DNP) in surface water samples, using hydrophilic molecular imprinted polymers (MIPs) as the recognition element and nickel (Ni) fiber as the catalytic element. Hydrophilic MIPs were synthesized using 2,4-DNP as the template, acrylamide as the monomer, glycidilmethacrylate as the pro-hydrophilic co-monomer and acetonitrile as the solvent. Hydrophilic modification could enhance the accessibility of 2,4-DNP to the imprinted cavities and improve the selective recognition properties of traditional MIPs in water medium. Subsequently, hydrophilic MIPs/Ni fiber electrode was prepared to determine trace 2,4-DNP by cyclic voltammetry. The parameters affecting the analytical performance were investigated. Under optimized conditions, the linear range was 0.7-30 µg L⁻¹ and the detection limit was 0.1 µg L⁻¹. Finally, the proposed method was applied to measure 2,4-DNP in surface water samples. The spiked recoveries were changed from 91.3% to 102.6% and the RSD was not higher than 5.1%. There was no statistically significant difference between the results obtained by the proposed method and the traditional chromatographic method.

Online coupling of molecularly imprinted solid-phase extraction to HPLC for determination of trace tetracycline antibiotic residues in egg samples.

An automated system has been developed for the determination of trace tetracycline antibiotics (TCs) in egg samples, based on online molecularly imprinted solid-phase extraction (MISPE) coupling with high-performance liquid chromatography (HPLC). Oxytetracycline and chlortetracycline were chosen as mixed templates to synthesize highly selective molecularly imprinted polymers for online extraction. Under the optimal online MISPE-HPLC condition, 10 mL egg samples were injected into the MISPE column and then the matrix was washed out. By rotating the switching valve, TCs were transferred to the analytical column and then separated by HPLC. Because sample pretreatment and chromatographic separation were carried out simultaneously, the whole analytical time (18 min) was significantly shortened compared with conventional offline techniques. The detection limits ranged from 0.8 to 1.3 ng/g. The enhancement factors were in the range of 159-410. The spiked recoveries of TCs in real egg samples ranged from 91.6 to 107.6% and the relative standard deviations (RSDs) were not higher than 4.0%.

Magnetic molecularly imprinted nanoparticles for recognition of lysozyme.

Molecular imprinting is an attractive technique for preparing mimics of natural, biological receptors. Nevertheless, the imprinting of macromolecule remains a challenge due to their bulkiness and sensitivity to denaturation. In this work, we presented a method for preparing multifunctional lysozyme-imprinted nanoparticles (magnetic susceptibility, molecular recognition and environmental response). The magnetic susceptibility was imparted through the successful encapsulation of Fe3O4 nanoparticles. Selective lysozyme recognition depended on molecularly imprinted film. Moreover, it was also a hydrophilic stimuli-responsive polymer, which could undergo a reversible change of imprinted cavity in response to a small change in the environmental conditions. Thus, magnetic molecularly imprinted nanoparticles had high adsorption capacity (0.11 mg mg(-1)), controlled selectivity and direct magnetic separation (22.1 emicro g(-1)) in crude samples. After preconcentration and purification with magnetic MIPs nanoparticles, a sensitive chemiluminescence method was developed for determination of lysozyme in human serum samples. The results indicated that the spiked recoveries were changed from 92.5 to 113.7%, and the RSD was lower than 11.8%.

Preparation of mixed-templates molecularly imprinted polymers and investigation of the recognition ability for tetracycline antibiotics.

We developed in the present study a set of molecularly imprinted polymers (MIPs) by precipitation polymerization, using four members of tetracycline antibiotics (TCs) as templates (Oxytetracycline, Tetracycline, Chlortetracycline and Doxycycline). Then, based on the imprinting effect of different MIPs (TCs), Oxytetracycline and Chlortetracycline were chosen as mixed-templates to synthesize high selective MIPs for recognition of a family of analytes. And the characterization of obtained MIPs was analyzed by FESEM analysis, Brunauer-Emmett-Teller (BET) method, polymer size analysis, and determination of swelling ratio and COOH capacity. It was shown that the optimal imprinting factors of TCs on mixed-templates MIPs were more than 6.0 and the maximum binding amount of TCs were about 27 micromol g(-1) (Oxytetracycline), 35 micromol g(-1) (Tetracycline), 35 micromol g(-1) (Chlortetracycline) and 39 micromol g(-1) (Doxycycline), respectively. Finally, the mixed-templates MIPs were shown to be promising for on-line solid-phase extraction-HPLC-UV determination of trace TCs in foodstuffs. With a sample loading volume of 10 mL, the enhancement factors were in the range of 159-410.

Determination of trace tetracycline antibiotics in foodstuffs by liquid chromatography-tandem mass spectrometry coupled with selective molecular-imprinted solid-phase extraction.

A rapid, specific, and sensitive method has been developed using molecularly imprinted polymers (MIPs) as solid-phase extraction sorbents for extraction of trace tetracycline antibiotics (TCs) in foodstuffs. MIPs were prepared by precipitation polymerization using tetracycline as the template. Under the optimal condition, the imprinting factors for MIPs were 4.1 (oxytetracycline), 7.0 (tetracycline), 7.4 (chlortetracycline), 7.7 (doxycycline), respectively. Furthermore, the performance of MIPs as solid-phase extraction sorbents was evaluated and high extraction efficiency of molecularly imprinted solid-phase extraction (MISPE) procedure was demonstrated. Compared with commercial sorbents, MISPE gave a better cleanup efficiency than C18 cartridge and a higher recovery than Oasis HLB cartridge. Finally, the method of liquid chromatography-tandem mass spectrometry coupled with molecular-imprinted solid-phase extraction was validated in real samples including lobster, duck, honey, and egg. The spiked recoveries of TCs ranged from 94.51% to 103.0%. The limits of detection were in the range of 0.1-0.3 microg kg(-1).