Recent developments of molecularly imprinted polymer in CEC.

This review focuses on developments in the field of molecularly imprinted polymer (MIP) for CEC since August 2006. New technique of CEC-based MIP, e.g. covalent approach through the formation of Schiff base, miniemulsion polymerization, non-hydrolytic sol-gel methodology, MIP-derivatized silica monolithic column, are discussed from the view of MIP preparation. Some thoughts on potential future directions are also expressed in this review.

Molecularly imprinted polymers as a tool for separation in CEC.

Molecularly imprinted polymers (MIPs) are synthesized in the presence of a template which results in the formation of specific recognition cavities complementary to the template in shape and chemical functionality. One of the most successful application areas of MIPs is chromatographic sorbents, which are tailor-made synthetic polymers for a given analyte. However, low efficiency of MIP columns is often observed because of slow kinetics of the template. CEC-based MIPs are thought to improve efficiency of MIP-based separation due to the enhanced flow dynamics of CEC. Another attractive feature is the miniaturized format of CEC, so that fewer templates or monomers for the molecular imprinting are consumed, a characteristic desired for 'green chemistry'. The small dimensions of a capillary demand the development of novel polymer formats that can be applied to a miniaturized system. This review discusses the various formats, i.e., the micro- or nanoparticle, the coating and the monolith, for application in CEC as well as the use in MIP syntheses and characteristics.

(S)-Ibuprofen-imprinted polymers incorporating gamma-methacryloxypropyl-trimethoxysilane for CEC separation of ibuprofen enantiomers.

In this report, a novel preparation method of molecularly imprinted polymers (MIPs) for CEC was developed. Molecularly imprinted monolithic columns for (S)-ibuprofen were prepared and evaluated, in which charged entities responsible for establishing EOF have been derived from gamma-methacryloxypropyltrimethoxysilane (gamma-MAPS), which was hydrolyzed following copolymerization with 4-vinylpyridine (4-VPY) and ethylene glycol dimethacrylate (EDMA). The EOF and molecular recognition of the stationary phase were investigated in aqueous and nonaqueous media, respectively. The experimental results indicated that the material showed a reasonably stable EOF and the prepared separation materials were capable of separating racemic ibuprofen, a task that could not be accomplished by MIPs prepared in parallel, using methacrylic acid (MAA) as a functional monomer. The efficiency at pH 3.2 for the first-eluted enantiomer and the last-eluted enantiomer (the imprinted analyte) were 128,700 and 2100 plates/m, respectively.

Mechanism of molecular recognition on molecular imprinted monolith by capillary electrochromatography.

The recognition mechanism of molecularly imprinted polymer (MIP) in capillary electrochromatography (CEC) is complicated since it possesses a hybrid process, which comprises the features of chromatographic retention, electrophoretic migration and molecular imprinting. For an understanding of the molecular recognition of MIP in CEC, a monolithic MIP in a capillary with 1,1'-binaphthyl-2,2'-diamine (BNA) imprinting was prepared by in situ copolymerization of imprinted molecule, methacrylic acid and ethylene glycol dimethacrylate in porogenic solvent, a mixture of toluene-isooctane. Strong recognition ability and high column performance (theory plates was 43,000 plates/m) of BNA were achieved on this monolithic MIP in CEC mode. In addition, BNA and its structural analogue, 1,1'-bi-2, 2'-naphthol, differing in functional groups, were used as model compounds to study imprinting effect on the resultant BNA-imprinted monolithic column, a reference column without imprinting of BNA and a open capillary. The effects of organic modifier concentration, pH value of buffer, salt concentration of buffer and column temperature on the retention and recognition of two compounds were investigated. The results showed that the molecular recognition on MIP monolith in CEC mode mainly derived from imprinting cavities on BNA-imprinted polymer other than chromatographic retention and electrophoretic migration.

Chiral recognition ability of an (S)-naproxen- imprinted monolith by capillary electrochromatography.

The racemic naproxen was selectively recognized by capillary electrochromatography (CEC) on an (S)-naproxen-imprinted monolith, which was prepared by an in situ thermal-initiated polymerization. The recognition selectivity of a selected monolith strictly relied on the CEC conditions involved. The factors that influence the imprinting selectivity as well as the electroosmotic flow (EOF), including the applied voltage, organic solvent, salt concentration and pH value of the buffer, column temperature, and surfactant modifiers were systematically studied. Once the column was prepared, the experiment results showed that the successful chiral recognition was dependent on CEC variables. For example: the recognition could be observed in acetonitrile and ethanol electrolytes, while methanol and dimethyl sulfoxide (DMSO) electrolytes had no chiral recognition ability. The buffer with pH values of 2.6 or 3.0 at a higher salt concentration had chiral recognition ability. Column temperatures of 25-35 degrees C were optimal. Three surfactants, sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and polyoxyethylene sorbitan monolaurate (Tween 20), can improve the recognition. Baseline resolution was obtained under optimized conditions and the column efficiency of the later eluent (S)-naproxen was 90 000 plates/m.

Chiral separation of binaphthol enantiomers on molecularly imprinted polymer monolith by capillary electrochromatography.

A novel enantioseparational monolithic stationary phase for binaphthol based on a molecular imprinting method was introduced and evaluated in capillary electrochromatography (CEC). The monolithic stationary was prepared by the in situ copolymerization of methacrylic acid and ethylene glycol dimethacrylate in a porogenic solvent (toluene or toluene-isooctane) in the presence of an imprinting molecule, (R)-1,1'-bi-2,2'-naphthol. Such stationary phases could separate the enantiomers of binaphthol. The influence of several parameters on the column permeability was investigated. These parameters included the polymerization time, the molar ratio of the functional monomer to the imprinting molecule and the content of porogen. The influence of the polymerization condition and the electrochromatographic parameters on the enantiomer separation was also studied. Initial studies showed that a higher molecular ratio of the imprinted molecule to the functional monomer, a higher content of porogen, a higher content of acetonitrile, a higher pH, as well as the addition of Tween 20, gave a higher enantiomer selectivity.

Stereo- and enantioselective determination of pesticides in soil by using achiral and chiral liquid chromatography in combination with matrix solid-phase dispersion.

The separation of enantiomers and diastereomers of 8 commonly used pesticides was investigated by liquid chromatography (LC) using a Chiralcel OD column (cellulose tris-3,5-dimethylphenylcarbamate as the chiral stationary phase) and a Pirkle-type Chirex 3020 column (urea derivative from the reaction of (R)-1-(alpha-naphthyl)ethylamine with (S)-tert-leucine, chemically bonded to 3-aminopropylsilanized silica as the chiral stationary phase). The pesticides studied included one organophosphorus insecticide (phenthoate), 3 triazole fungicides (uniconazole, diniconazole, and propiconazole), and 4 pyrethroids (fenpropathrin, beta-cypermethrin, beta-cyfluthrin, and alpha-fenvalerate). The enantiomers were separated within 20 min with a resolution of > or = 1.5 using a mixture of n-hexane and 2-propanol as the mobile phase for all the pesticides studied except propiconazole, for which only the 2 diastereomers were baseline separated. This method allows determination of the enantiomers or stereoisomers of the above pesticides in soil. The strategy was as follows: (1) First, the total concentration(s) of the enantiomer pair(s) of a chiral pesticide in soil was (were) determined by a newly developed matrix solid-phase dispersion (MSPD) procedure, followed by silica-based LC quantification. The recoveries ranged from 76.5 to 93.6% with relative standard deviations of 6.0%. (2) Second, the enantiomeric ratio(s) (ER(s)) of the chiral pesticide was (were) determined by LC with a chiral stationary phase after fractionation of the MSPD extract by silica-based LC. The determined ERs or stereoisomeric ratio(s) (SR(s); for propiconazole, only the SR of the 2 diastereomers was determined) in soil samples spiked with the above 8 racemic pesticides agreed with those of the corresponding standard solutions. (3) Third, based on the total concentrations and the corresponding ERs, the concentration of each enantiomer in soil was calculated. The proposed method is rapid, precise, and sensitive, and is appropriate for the investigation of the stereo- and enantioselective degradation of pesticides in environmental media.

Fast and precise determination of phenthoate and its enantiomeric ratio in soil by the matrix solid-phase dispersion method and liquid chromatography.

A fast and precise method was developed for the determination of phenthoate and its enantiomeric ratio (ER) in three soil samples. A recently developed sample pretreatment technology--matrix solid-phase dispersion (MSPD) was used to extract phenthoate simply and effectively. MSPD conditions, i.e. solid-phase Florisil amount, water content of Florisil-soil mixture, the constituent and volume of the eluting solvent, were optimized stepwise. The MSPD extract was directly used for quantitative determination of phenthoate by silica-based high-performance liquid chromatography (HPLC) with UV detection. The recoveries of phenthoate from three different types of soils fortified at three levels of 0.1, 1, 10 microg/g ranged from 75 to 94% with RSDs of 1.5-6.5%. On this basis, phenthoate was further isolated from the remainder of MSPD extract by silica-based HPLC and then ER determined on HPLC with cellulose tris-3, 5-dimethylphenylcarbamate as chiral stationary phase. The ERs determined in the soils spiked with racemic or enantiomer-enriched phenthoate agreed sufficiently well with those in the corresponding standard solutions. Finally, the proposed method was successfully applied to the study of enantioselective degradation of phenthoate in the three soils under laboratory conditions. High enantioselectivity was observed in the two alkaline soils with (+)-enantiomer degrading faster than the (-)-enantiomer, while there was little to no enantioselectivity in the acidic soil. The methodology can be used to study the enantioselective environmental behavior of chiral pollutants.

[Advances in the chiral resolution of organophosphorus compounds by liquid chromatography].

The developments in the chiral resolution of organophosphorus compounds by liquid chromatography in recent years are reviewed. Two different approaches of separation: indirect resolution (chiral derivatization reagent method) and direct resolution (chiral mobile phase additive and chiral stationary phase), focusing on several chiral stationary phases--Pirkle type, cyclodextrin, cellulose, ligand exchange and other chiral stationary phases are presented. The possible mechanism of chiral recognition is discussed. Eighty-five references are involved.