Analyses of sulfonamide antibiotics by a successive anion- and cation-selective injection coupled to microemulsion electrokinetic chromatography.

In this study, an MEEKC was used to detect and analyze nine sulfonamide antibiotics. Owing to an insufficient sensitivity of on-column UV detection, a field-amplified sample injection, successive anion- and cation-selective injection, was used for the on-line concentration of the nine antibiotics. In the successive anion- and cation-selective injection mode, a leading water plug was introduced prior to anion injection, and then an acidic plug followed by a terminal water plug had to be used before subsequent cation injection. The results indicated some sulfonamides (sulfamonomethoxine, sulfamethazine, sulfamerazine and sulfadiazine) were determined as split signals in pairs, and this was likely due to the use of a longer acid plug (360 s) which caused the sulfonamide anions and cations to be stacked in two distinct zones of the leading water and acid plugs. Meanwhile, all the sulfonamides that were introduced either by anion or cation injection were stacked within the leading water plug when a shorter acid plug (210 s) was used. As a result, the nine sulfonamides were determined as single and symmetrical peaks with low LODs (0.9-4.2 microg/L). Furthermore, the MEEKC method was successfully applied for the detection of trace sulfonamide residues in several food and water samples.

Analyses of sulfonamide antibiotics by CEC using poly(divinylbenzene-1-octadecene-vinylbenzyl trimethyl ammonium chloride) monolithic columns.

In this study, a series of novel polymeric monolithic columns prepared by single-step in situ copolymerization of 1-octadecene (OD), divinylbenzene (DVB) and/or styrene (S), were developed as separation columns for the sulfonamide analyses. On the CEC method, the composition of monomer mixtures (i.e. the ratio of S versus OD), content of charge-bearing monomer (vinylbenzyl trimethylammonium chloride) and volume fraction ratio of ACN in the mobile phase, was found to be the predominant influences for sulfonamide separation. Furthermore, an online sample concentration step, field-amplified sample injection, was used to enhance the detection sensitivity of sulfonamides. Sample matrix's pH had a significant effect on the sulfonamide sensitivity. For the eight sulfonamides, the proposed poly(DVB-OD) monolithic stationary phase coupled with field-amplified sample injection step could achieve a reproducible baseline separation within 15 min and LODs in the range of 8.1-28.2 microg/L.

Development of capillary electrochromatography with poly(styrene-divinylbenzene-vinylbenzenesulfonic acid) monolith as the stationary phase.

A new polystyrene-based monolithic stationary phase, which was prepared by single step in situ copolymerization of styrene, divinylbenzene and vinylbenzenesulfonic acid (VBSA), was developed as a separation column for capillary electrochromatography, in which VBSA was employed as the charge-bearing monomer. Polymerization time of the polystyrene-based monolith had slightly influenced the separation time of the tested analytes, but it effectively altered their separation resolutions. Furthermore, baseline separation for a wider range of acetonitrile levels of mobile phase was achieved when a monolithic column prepared by a longer polymerization time was used. This novel polystyrene-based monolithic column provided an adequate electroosmotic flow either in basic or acidic mobile phase when VBSA level was maintained at 2.6% (w/w). Finally, this proposed polystyrene-based column allowed seven tested analytes to achieve a reproducible baseline separation within 2.2 min with theoretical plate numbers higher than 164 000 plates/m.

Analyses of polycyclic aromatic hydrocarbons in seafood by capillary electrochromatography-atmospheric pressure chemical ionization/mass spectrometry.

In this work, an on-line preconcentration capillary electrochromatographic (CEC) separation coupled with atmospheric pressure chemical ionization-mass spectrometry (APCI-MS) was used for 16 PAHs analyses, in which poly(stearyl methacrylate-divinylbenzene) (poly(SMA-DVB)) monolith was used as the separation column. With variations in the effective length of poly(SMA-DVB) monolith as well as the volume fraction of acetonitrile (ACN) in the mobile phase, both separation and resolution were improved. A poly(SMA-DVB) monolith of 50-cm effective length (i.e. 50-cm column length filled with polymer) and a two-step step-gradient elution (by changing the ACN levels of the mobile phase starting with an initial of 70% up to 80% with 30-min time interval), which provided baseline separation for PAHs solutes (except for chrysene and benzo[a]anthracene) within 50 min, were employed as the optimal chromatographic conditions. In contrast to the other mass spectrometer parameters (nebulizer gas pressure, vaporizer temperature, corona current) as well as on-line preconcentration parameter (the ACN level in the sample matrix), the sheath liquid composition (methanol/water in the ratio of 3:1) and the sample injection time (40 min) were found as the predominant factors that control the sensitivity of PAHs determination. Finally, this on-line preconcentration CEC-APCI-MS method determined PAH residues in seafood samples successfully with as low as 10 ng/g level.

Metal organic framework-organic polymer monolith stationary phases for capillary electrochromatography and nano-liquid chromatography.

In this study, metal organic framework (MOF)-organic polymer monoliths prepared via a 5-min microwave-assisted polymerization of ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) with the addition of various weight percentages (30-60%) of porous MOF (MIL-101(Cr)) were developed as stationary phases for capillary electrochromatography (CEC) and nano-liquid chromatography (nano-LC). Powder X-ray diffraction (PXRD) patterns and nitrogen adsorption/desorption isotherms of these MOF-organic polymer monoliths showed the presence of the inherent characteristic peaks and the nano-sized pores of MIL-101(Cr), which confirmed an unaltered crystalline MIL-101(Cr) skeleton after synthesis; while energy dispersive spectrometer (EDS) and micro-FT-IR spectra suggested homogenous distribution of MIL-101(Cr) in the MIL-101(Cr)-poly(BMA-EDMA) monoliths. This hybrid MOF-polymer column demonstrated high permeability, with almost 800-fold increase compared to MOF packed column, and efficient separation of various analytes (xylene, chlorotoluene, cymene, aromatic acids, polycyclic aromatic hydrocarbons and trypsin digested BSA peptides) either in CEC or nano-LC. This work demonstrated high potentials for MOF-organic polymer monolith as stationary phase in miniaturized chromatography for the first time.

Poly(triallyl isocyanurate-co-ethylene dimethacrylate-co-alkyl methacrylate) stationary phases in the chromatographic separation of hydrophilic solutes.

This study describes the ability of triallyl isocyanurate (TAIC)-co-methacrylate ester polymer monoliths as stationary phases for the separation of hydrophilic compounds (phenolic acids, amino acids and catecholamines) in capillary electrochromatography (CEC) and ultra high pressure liquid chromatography (UHPLC). Several TAIC-co-methacrylate ester polymer monoliths prepared by single-step in situ copolymerization of TAIC, ethylene dimethacrylate (EDMA) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS), with or without alkyl methacrylates were characterized by examining the SEM image, surface area, contact angle, and the thermal decomposition temperature. Compared to the conventional methacrylate ester-based monoliths, these proposed monoliths possessed hydrophilic character thus increased wettability which improved chromatographic separation selectivity of polar phenolic acids. Among the proposed TAIC-co-methacrylate monoliths, poly(TAIC-co-EDMA-AMPS-co-stearyl methacrylate (SMA)) showed separation selectivity with an increased analyte resolution from 0.0 to 0.92 for 4-hydroxybenzoic acid and vanillic acid, which were consistently difficult to resolve in the reversed-phase chromatographic mechanism of these monoliths in aqueous mobile phases. Moreover, stable ionization efficiencies were observed when this monolith was combined with ESI-MS detector possibly because an organic solvent-rich sheath liquid was used in the CEC-MS. This study demonstrates the potentiality of novel TAIC-co-methacrylate polymer monoliths in hydrophilic solute separation either in CEC or UHPLC mode.

Capillary electrochromatography-mass spectrometry determination of melamine and related triazine by-products using poly(divinyl benzene-alkene-vinylbenzyl trimethylammonium chloride) monolithic stationary phases.

In this study, a capillary electrochromatography (CEC) method coupled either with UV or mass spectrometric detection was developed for the detection of trace-amounts of melamine and its related by-products (ammeline, ammelide, and cyanuric acid). A series of poly(divinyl benzene-alkene-vinylbenzyl trimethylammonium chloride) monolithic columns, which were prepared by a simple in situ polymerization with divinyl benzene (DVB), vinylbenzyl trimethylammonium chloride (VBTA) and different types of alkene monomers such as 1-octene, 1-dodecene or 1-octadecene were used as separation columns, with the poly(DVB-1-dodecene-VBTA) monolith as the optimal chromatographic material because it provided a better separation. The detection limits of four melamine derivatives were in the ranged of 0.6-2.18 mg L(-1) by the optimal CEC-UV mode, and were reduced from 2.2 to 19.4 µg L(-1) by the optimal CEC-MS mode. Finally, the proposed CEC methods successfully determined melamine contaminations (0.1 mg L(-1) per analyte) in several dairy products as test samples with analyte recovery range of 69-85% (intra-day) and 68-75% (inter-day), and with peak area reproducibility range of 4.3-8.6% and 8.7-15.6% for intra-day and inter-day, respectively. This is the first report for CEC separation coupled with MS detection applied in trace melamine residue analyses with a faster separation and comparable or even better detection ability than previous GC-MS, CE-MS, as well as LC-MS methods.

Ionic liquids as porogens in the microwave-assisted synthesis of methacrylate monoliths for chromatographic application.

Several imidazolium-based ionic liquids (ILs) with varying cation alkyl chain length (C(4)-C(10)) and anion type (tetrafluoroborate ([BF(4)](-)), hexafluorophosphate ([PF(6)](-)) and bis(trifluoromethylsulfonyl)imide ([Tf(2)N](-))) were used as reaction media in the microwave polymerization of methacrylate-based stationary phases. Scanning electron micrographs and backpressures of poly(butyl methacrylate-ethylene dimethacrylate) (poly(BMA-EDMA)) monoliths synthesized in the presence of these ionic liquids demonstrated that porosity and permeability decreased when cation alkyl chain length and anion hydrophobicity were increased. Performance of these monoliths was assessed for their ability to separate parabens by capillary electrochromatography (CEC). Intra-batch precision (n=3 columns) for retention time and peak area ranged was 0.80-1.13% and 3.71-4.58%, respectively. In addition, a good repeatability of RSD(Retention time)=<0.30% and ~1.0%, RSD(Peak area)=<1.30% and <4.3%, and RSD(Efficiency)=<0.6% and <11.5% for intra-day and inter-day, respectively exemplify monolith performance reliability for poly(BMA-EDMA) fabricated using 1-hexyl-3-methylimidazolium tetrafluoroborate ([C(6)mim][BF(4)]) porogen. This monolith was also tested for its potential in nanoLC to separate protein digests in gradient mode. ILs as porogens also fabricated different alkyl methacrylate (AMA) (C4-C18) monoliths. Furthermore, employing binary IL porogen mixture such as 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF(4)]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(4)mim][Tf(2)N]) successfully decreased the denseness of the monolith, than when using [C(4)mim][Tf(2)N] IL alone, enabling a chromatographic run to be performed with 1:1 ratio produced baseline separation for the analytes. The combination of ILs and microwave irradiation made polymer synthesis very fast (~10min), entirely green (organic solvent-free) and energy saving process.

Analyses of sulfonamide antibiotics in meat samples by on-line concentration capillary electrochromatography-mass spectrometry.

In this work, a series of poly(divinylbenzene-alkyl methacrylate) monolithic stationary phases, which were prepared by single step in situ polymerization of divinylbenzene and various alkyl methacrylates (butyl-, octyl-, lauryl- or stearyl methacrylate), were developed as separation columns of nine common sulfonamide antibiotics for capillary electrochromatography (CEC) coupled to mass spectrometry (MS). Results indicated that the sulfonamide's retention became weak with increased carbon chain length of alkyl methacrylate monomer (for example, t(R)=68 min and 21 min for butyl- and lauryl methacrylate, respectively). Among them, the poly(divinylbenzene-octyl methacrylate) (poly(DVB-OMA)) monolith was regarded as the optimal separation column as this provided better resolution within the shortest retention time. Moreover, the cross-sectional roughness of the monolithic column-end, that was used to couple to the ESI interface, strongly influenced the electrospray stability in the CEC-MS. Before the column was connected to the ESI-MS, a simple polishing was done to reduce the roughness of the column end that resulted to a great improvement in the signal stability. The relative standard deviations (RSDs) of the peak areas for the unpolished and polished ends of the poly(DVB-OMA) columns (n=5) were in the range of 46.1-60.2% and 8.9-16.4%, respectively. Furthermore, optimization of the mobile phase composition and the gradient elution strategy successfully determined the sulfonamide antibiotics in meat samples with as low as 10 µg/L level.

Analyses of non-steroidal anti-inflammatory drugs by on-line concentration capillary electrochromatography using poly(stearyl methacrylate-divinylbenzene) monolithic columns.

This study describes the ability of on-line concentration capillary electrochromatography (CEC) coupled with UV or mass spectrometry (MS) for the determination of nine common non-steroidal anti-inflammatory drugs (NSAIDs) in water samples. A series of poly(stearyl methacrylate-divinylbenzene) (poly(SMA-DVB)) monolithic columns, which were prepared by single step in situ polymerization of divinylbenzene (DVB), stearyl methacrylate (SMA) and vinylbenzenesulfonic acid (VBSA, charged monomer), were developed as separation columns for the first time. The effects of polymerization condition of monolithic columns on analyte separations were examined, and the results indicated that separation performances were markedly improved in monolithic columns prepared with short reaction time (3 h) and low SMA:DVB ratio (40/60 ratio of SMA:DVB). Subsequently, an on-line concentration step of step-gradient elution was combined to this CEC system, and by optimizing the difference in eluent strength between the sample matrix and mobile phase, all NSAIDs detection sensitivity were improved (limit of detection (LOD) was 3.4-10 µg/L for UV, and 0.01-0.19 µg/L for MS). When compared to the best CE and LC reports on NSAIDs analyses so far, this on-line concentration CEC method provided better detection ability within shorter separation time (12 min) when either UV or MS detector was employed. This is the first report for on-line concentration CEC with MS detection applied in trace solute analyses of real samples.

Analyses of synthetic antioxidants by capillary electrochromatography using poly(styrene-divinylbenzene-lauryl methacrylate) monolith.

In this study, several organic polymer-based monoliths prepared by single step in situ copolymerization of styrene- and methacrylate ester-based monomers (styrene (S), divinylbenzene (DVB) and lauryl methacrylate (LMA)) were developed as stationary phases of capillary electrochromatography (CEC) for the analyses of synthetic antioxidants. These monoliths were characterized by examining the SEM image, IR spectrum, and measuring the pore size, surface area, conversion yield, and thermal decomposition temperature. The polymerization procedure was optimized by varying the reaction temperature, the reaction time, and the LMA-styrene ratio. The LMA-styrene ratio had the most significant influence on the peak symmetry of butylated hydroxyanisole (BHA) and 2, 6-di-tert-butyl-4-methyl phenol (BHT), the latter being greatly affected by excessive peak tailing in the poly(S-DVB) monolith. It showed that the interaction between the poly(S-DVB) monolith and the antioxidant (BHT or BHA) was significantly altered by the insertion of LMA. Compared with the best HPLC and CE methods previously reported, this proposed CEC method provides a comparable separation ability for the five antioxidants analyzed. This study demonstrates that the potentiality of poly(S-DVB-LMA) monolith as stationary phase, especially for CEC system, because of high thermal stability and good column reproducibility.

Poly(divinylbenzene-alkyl methacrylate) monolithic stationary phases in capillary electrochromatography.

In this study, a series of poly(divinylbenzene-alkyl methacrylate) monolithic stationary phases, which were prepared by single step in situ polymerization of divinylbenzene and various alkyl methacrylates (butyl-, octyl-, or lauryl-methacrylate), were developed as separation columns of benzophenone compounds for capillary electrochromatography (CEC). In addition to the presence of plenty of benzene moieties, the stationary phases contained long and flexible alkyl groups on the surface. With an increase in the molecular length of alkyl methacrylate, the polymeric monolith, which had higher hydrophobicity, effectively reduced the peak tailing of benzophenones, but a weaker retention was observed. The unusual phenomenon was likely due to the pi-pi interaction between the aromatic compound and the polymeric material. The usage of longer alkyl methacrylate as reaction monomer limited the retention of aromatic compounds on the stationary phase surface, thus the pi-pi interaction between them was possibly reduced. Consequently, the retention time of aromatic compounds was markedly decreased with an increase in carbon length of alkyl methacrylate that was carried on the polymeric monolith. Compared to previous reports on polystyrene-based columns in which the peak-tailing problem was reduced by decreasing the benzene moieties on the stationary phase, this study demonstrated that the undesirable retention (peak-tailing) could also be improved by the inclusion of long alkyl methacrylate to the polystyrene-based columns.