Simultaneous enrichment and sequential elution of cis-diol containing molecules and deoxyribonucleotides with bifunctional boronate and titanium (â £) ion modified-magnetic nanoparticles prior to quantitation by high performance liquid chromatography.

Some diseases can cause abnormal concentrations of catecholamines (CAs), nucleosides (NSs) and nucleotides (NTs) in patients. Previous studies normally focused on the detection of the three types of substances separately. In this work, a bifunctional boronate and titanium (Ⅳ) ion affinity magnetic adsorbent with high-capacity was prepared. The adsorbent can simultaneously enrich CAs, NSs and NTs in a single extraction process, and the adsorbed analytes can be sequentially eluted by 1.0% trifluoroacetic acid and 20.0 mmol L-1 Na3PO4. An analytical method of the analytes has been established by coupling the adsorbent with RP-HPLC. The method has low detection limits (0.039-0.708 ng mL-1) and good reproducibility (inter- and intra-day of assay RSDs less than 15.0%). Serum sample from healthy volunteer was successfully quantified for two CAs, four NSs and five NTs. Compared with the reported methods, the proposed method is simpler to operate, consume less samples, and has enough accurate and sensitivity to obtain comprehensive information on the concentrations of analytes in a single extraction process.

Effect of stereoconfiguration of aromatic ligands on retention and selectivity of terphenyl isomer-bonded stationary phases.

The structure of ligands has a significant influence on the separation properties of alkyl and aromatic phases in reversed-phase liquid chromatography. Compared with alkyl phases, the effect of stereoconfiguration of aromatic ligands on the retention and selectivity of stationary phases has rarely been addressed. To illustrate the issue, three terphenyl isomer-bonded stationary phases were prepared via the coupling chemistry of isocyanate with terphenyl amine isomers, 3,4-diphenylaniline, 2,4-diphenylaniline and 4-amino-p-terphenyl, respectively. The retention behaviors of stationary phases were assessed in terms of retention strength, selectivity, hydrophobic and π-π interaction by five kinds of solutes. It is found that the selectivity towards the solutes is slightly larger on the branched m-terphenyl-bonded phase (m-π3) than o-terphenyl-bonded phase (o-π3) but is significantly improved on the chain p-terphenyl-bonded phase (p-π3). The results can be interpreted by the ease self-adjustment of the conformation of the chain p-terphenyl ligand and the smaller steric effect of p-π3 towards the insertion of solutes into the ligand brushes. In addition, the p-π3 yields excellent selective separation towards aromatic solutes. These findings are of significance in the design of aromatic stationary phases.

Effect of phenyl numbers in polyphenyl ligand on retention properties of aromatic stationary phases.

Aromatic phase, as one type of reversed-phase stationary phases, shows complementary selectivity to the n-alkyl counterparts especially for certain challenging separation tasks. However, effect of phenyl numbers in aromatic ligands on retention behaviors has rarely been addressed compared with the alkyl stationary phases. To illustrate the issue, a series of polyphenyl stationary phases were facially prepared via the coupling chemistry of isocyanate with amine, including aniline (π1), 4-aminobiphenyl (π2), 4-amino-p-terphenyl (π3) and [1,1':4',1'':4'',1'''-quaterphenyl]-4-amine (π4), respectively. The chromatographic behaviors of the new stationary phases as well as the traditional C18 were systematically compared in terms of retention mode, hydrophobic and aromatic selectivity, shape selectivity and π-π interaction by various analytes, including alkylbenzenes, polycyclic aromatic hydrocarbons congeners and substituted benzenes with electron-withdrawing groups. Due to the homologous structure of four polyphenyl ligands, the hydrophobic selectivity, aromatic selectivity and shape selectivity of stationary phases increase with phenyl numbers in the bonded polyphenyl ligands, whereas the increment becomes insignificant from U-π3 to U-π4. This phenomenon is explained by the insertion degree of analytes in the polyphenyl ligand brushes. Compared with the homemade C18, the polyphenyl phases indicate insignificant changes of shape selectivity with temperature. Notably, the new polyphenyl phases demonstrate the great selective separation towards the electron-deficient compounds through the π-π interaction. These findings make up for the understanding of the retention behavior of aromatic stationary phases.

Novel metal-organic framework combining with restricted access molecularly imprinted nanomaterials for solid-phase extraction of gatifloxacin from bovine serum.

Novel restricted access molecularly imprinted nanomaterials (RAMIPs) were successfully prepared on the surface of metal-organic frameworks (NH2-MIL-125) by surface-initiated atom transfer radical polymerization (SI-ATRP) technology. Then it was applied as a solid phase extraction (SPE) material in analysis of quinolones in bovine serum by HPLC detection. NH2-MIL-125@RAMIPs was empolyed as a sorbent for gatifloxacin (GTFX) and the resulted material has a good binding amounts (86.1 mg g-1), rapid binding kinetic (36 min). The results indicated that the prepared NH2-MIL-125@RAMIPs possess excellent specific recognition for GTFX. Combined with high-performance liquid chromatography (HPLC), the SPE column filled with NH2-MIL-125@RAMIPs was applied to selectively enrich GTFX antibiotic from bovine serum. The recovery of GTFX is between 96.8% and 105.6%, with relative standard deviations of 1.7-3.2% (n = 3). The research results illustrate that the method is successfully applied to the selective enrichment of GTFX in bovine serum. It provides a simple and efficient method for the direct detection of GTFX in bovine serum.

Restricted access media-imprinted nanomaterials based on a metal-organic framework for highly selective extraction of fluoroquinolones in milk and river water.

A new type of restricted access media-imprinted nanomaterials (RAM-MIPs) were successfully prepared on the surface of metal-organic framework by reversible addition fragmentation chain transfer polymerization technology. Then it was applied as a dispersed solid phase extraction (DSPE) material in analysis of fluoroquinolones (ofloxacin, pefloxacin, norfloxacin, enrofloxacin and gatifloxacin) in untreated milk and river water by HPLC-UV detection. The resulted material has a good binding amounts (60.81 mg g-1), rapid binding kinetic (15 min) and satisfactory selectivity as well as has a good ability to eliminate matrix interference. Several major factors affecting DSPE efficiency, pH of sample solution, dosage of RAM-MIPs, adsorption time and volume ratios of elution solvent were primarily optimized. In optimization conditions, RAM-MIPs-DSPE was combined with HPLC-UV to enrich fluoroquinolones in untreated milk and river water, achieving satisfactory linear correlation (R2 > 0.9988), good limits of detection (LOD, 1.02-3.15 µg L-1 for milk and 0.93-2.87 µg L-1 for river water) and better recoveries (80.7-103.5% and 85.1-105.9% with relative standard deviation (RSD) of not higher than 5.3% and 4.7% for milk and river water samples, respectively). The research results illustrate that it provides a simple and efficient method for the direct detection of FQs in complex samples.

Monodisperse restricted access material with molecularly imprinted surface for selective solid-phase extraction of 17ß-estradiol from milk.

In this study, novel monodisperse restricted access media-molecularly imprinted polymers were successfully prepared by surface initiated reversible addition-fragmentation chain transfer polymerization using monodisperse crosslinked poly (glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres as the carrier and acryloyl chloride-modified ß-cyclodextrin as the hydrophilic functional monomer. The surface morphology, protein exclusion, and adsorption properties of the molecularly imprinted polymers were investigated. The results show that the material has excellent monodispersity and hydrophilicity, and simultaneously exhibit high adsorption capacity, fast binding kinetics, high selectivity, and significant thermal stability. The molecularly imprinted polymers as dispersive solid-phase extraction adsorbent combined with reversed-phase high-performance liquid chromatography was used to selectively enrich, separate, and analyze trace 17ß-estradiol in milk samples. The recovery of 17ß-estradiol is 88-95% with relative standard deviation of <4%, and the limits of detection and quantification of this method are 2.08 and 9.29 µg/L, respectively. The novel restricted access media-molecularly imprinted polymer adsorbents provide an effective method for the selective extraction and detection of 17ß-estradiol directly from complex samples.

Preparation of high-capacity magnetic polystyrene sulfonate sodium material based on SI-ATRP method and its adsorption property research for sulfonamide antibiotics.

A novel polystyrene sulfonate sodium (PSS) magnetic material was prepared by surface-initiated atom transfer radical polymerization (SI-ATRP). The starting materials were brominated magnetic material as the carrier and macroinitiator, sodium styrene sulfonate (NaSS) as the monomer, and cuprous bromide/2,2'-dipyridyl as the catalyst system. The PSS material was characterized by Fourier transform infrared spectroscopy (FT-IR), elemental analysis, transmission electron microscope (TEM), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and a vibrating sample magnetometer (VSM). The adsorption properties of the material were then investigated on sulfa antibiotics. The kinetic and thermodynamic parameters were determined in adsorption of sulfamethazine (the smallest molecular-weight sulfonamide). The adsorption amount of sulfamerazine free acid (SMR) was found to increase with the initial concentration and temperature of SMR in solution. The adsorption effect was maximized at an initial concentration of 0.6 mmol/L. The static saturation adsorption capacity of the material was 33.53 mg/g, Langmuir and Freundlich equations exhibited good fit. The thermodynamic equilibrium equation is calculated as ΔG < 0, ΔH = 38.29 kJ/mol, ΔS > 0, which proves that the adsorption process is a process of spontaneous, endothermic and entropy increase. Kinetic studies show that the quasi-second-order kinetic equation can better fit the kinetic experimental results, which is consistent with the quasi-second-order kinetic model. The experimental results of kinetic studies were well fitted to a quasi-second-order kinetic equation. High performance liquid chromatography (HPLC) of an actual milk sample treated by the PSS magnetic material confirmed the strong adsorption of SMR from milk.

Restricted access magnetic imprinted microspheres for directly selective extraction of tetracycline veterinary drugs from complex samples.

A novel restricted access media-magnetic molecularly imprinted polymers (RAM-MMIPs) was prepared as magnetic-solid phase extraction (M-SPE) material for tetracyclines (TCs). The RAM-MMIPs can not only specifically adsorb target molecules in samples, but also effectively eliminate the interference of protein macromolecules. The protein exclusion rate is 99.4%. Besides, RAM-MMIPs have a uniform imprinted and hydrophilic layer (600 nm), rapid binding kinetic (35 min), high selectivity and larger adsorption capacity. The M-SPE was coupled with HPLC/UV to extract TCs from untreated milk and egg samples, and several major factors affecting M-SPE efficiency were optimized. Under optimized conditions, the developed method achieved good linearity (R2>0.9989), lower limits of detection (LOD) and higher recoveries of TCs. For milk samples, the LOD is 1.03-1.31 µg L-1 and the recovery is 86.7% to 98.6% with relative standard deviation (RSD) of 1.4-5.7%. For the egg samples, the LOD, recovery and RSD are 2.21-2.67 µg L-1, 84.2-96.5% and 1.7-5.9%, respectively. Consequently, this work provides an improved strategy for the selective extraction and detection of target molecules directly from complex samples with proteins.

Molecularly imprinted polymer coating on metal-organic frameworks for solid-phase extraction of fluoroquinolones from water.

In this work, a novel surface molecularly imprinted polymer with high adsorption capacity, high adsorption rate, and high selectivity for fluoroquinolones was prepared on the surface of UiO-66-NH2 , which is a kind of metal-organic framework. The surface morphology and adsorption properties of this molecularly imprinted polymer were investigated. The maximum adsorption capacity was 99.19 mg/g, and adsorption equilibrium was achieved within 65 s. Combined with reversed-phase high-performance liquid chromatography, the molecularly imprinted polymer was used to selectively enrich, separate and analyze fluoroquinolones present in lake water. The results showed that the recoveries of the four fluoroquinolones were 92.6-100.5%, and the relative standard deviations were 2.9-6.4% (n = 3). The novel molecularly imprinted polymer is an excellent adsorbent and has broad application prospects in the enrichment and separation of trace analytes in complex samples.

Preparation of restricted access media molecularly imprinted polymers for efficient separation and enrichment ofloxacin in bovine serum samples.

We prepared ofloxacin restricted access media molecularly imprinted polymers using surface-initiated atom transfer radical polymerization on the surface of brominated silica gel using ofloxacin as a template molecule, methacrylic acid as a functional monomer, and ethylene glycol dimethacrylate as a crosslinking agent. We then characterized and studied the surface morphology and adsorption properties of the polymer. Experimental results show that saturation is reached within 25 min, and that the saturated adsorption capacity was 80.67 mg/g and the imprinting factor was 1.94. Our findings also showed that the polymer surface had good hydrophilicity and an excellent protein exclusion rate, which was 98.49%. The restricted access media molecularly imprinted polymers were then successfully applied to the enrichment and separation of ofloxacin in bovine serum. When combined with high-performance liquid chromatography, and the average recovery of ofloxacin was 95.6%, and the relative standard deviation was in the range of 2.47-3.38%. In a word, the restricted access media molecularly imprinted polymers is a method that involves a simple preparation procedure that results in excellent performance, which is a great improvement in the speed of detection of antibiotics. These qualities are what bestow upon this method its great potential for broad application.

A restricted access molecularly imprinted polymer coating on metal-organic frameworks for solid-phase extraction of ofloxacin and enrofloxacin from bovine serum.

A restricted access molecularly imprinted polymer (RAMIP) crosslinked with bovine serum albumin (BSA) was prepared on the surface of the mesoporous UiO-66-NH2 metal-organic framework (MOF). The surface morphology, imprinting behavior, and protein exclusion properties of UiO-66-NH2@RAMIP@BSA were investigated. The maximum adsorption capacity was 50.55 mg g-1 for ofloxacin, with a 99.4% protein exclusion rate. Adsorption equilibrium was reached in 9 min. Combined with RP-HPLC, a solid-phase extraction column filled with UiO-66-NH2@RAMIP@BSA was used to selectively enrich and analyze ofloxacin and enrofloxacin antibiotics from bovine serum with recoveries of 93.7-104.2% with relative standard deviations of 2.0-4.5% (n = 3). The linear range and the limit of detection were 0.1-100 µg mL-1 and 15.6 ng mL-1, respectively. These results suggest that UiO-66-NH2@RAMIP@BSA is an efficient pretreatment adsorbent for biological sample analysis.

Preparation of Restricted Access Media-Molecularly Imprinted Polymers for the Detection of Chloramphenicol in Bovine Serum.

Chloramphenicol- (CAP-) restricted access media-molecularly imprinted polymers (CAP-RAM-MIPs) were prepared by precipitation polymerization using CAP as a template molecule, 2-diethylaminoethyl methacrylate (DEAEM) as a functional monomer, ethylene glycol dimethyl acrylate (EDMA) as a crosslinking agent, glycidyl methacrylate (GMA) as an outer hydrophilic functional monomer, and acetonitrile as a pore former and solvent. The CAP-RAM-MIPs were successfully characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The adsorption performance was investigated in detail using static, dynamic, and selective adsorption experiments. Adsorption equilibrium could be reached within 11 min. The CAP-RAM-MIPs had a high adsorption rate and good specific adsorption properties. Scatchard fitting curves indicated there were two binding sites for CAP-RAM-MIPs. Adsorption was Freundlich multilayer adsorption and consistent with the quasi-second kinetic model. Using CAP-RAM-MIPs for selective separation and enrichment CAP in bovine serum in combination with high-performance liquid chromatography (HPLC), CAP recovery ranged from 94.1 to 97.9% with relative standard deviations of 0.7-1.5%. This material has broad application prospects in enrichment and separation.

Preparation of Ampicillin Surface Molecularly Imprinted Polymers for Its Selective Recognition of Ampicillin in Eggs Samples.

Surface-imprinted polymers (MIPs) microspheres with the ability to specifically recognize water-soluble molecules were prepared using self-made monodisperse porous poly(chloromethylstyrene-co-divinylbenzene) beads as the solid-phase matrix and ampicillin (AMP) as the template molecule. MIPs were synthesized using different template molecule: monomer: crosslinker ratios and the optimum preparation ratio were obtained by measuring adsorption. The maximum equilibrium amount of adsorption by the MIPs reached 115.62 mg/g. Scatchard analysis indicated that the MIPs contained two types of recognition sites: specific and nonspecific. Based on the adsorption kinetics, adsorption equilibrium was reached after 30 minutes. Penicillin G, amoxicillin, and sulbactam acid were used as competitive molecules to research the selective adsorption capacity of the MIPs. The imprinted material was found to have good selectivity with selectivity coefficients for penicillin G, amoxicillin, and sulbactam acid of 5.74, 6.83, and 7.25, respectively. The MIPs were used as solid-phase extraction filler, resulting in successful enrichment and separation of ampicillin residue from egg samples. Standard addition recovery experiments revealed that recovery was good with recoveries from the spiked samples ranging from 91.5 to 94.9% and relative standard deviations from 3.6 to 4.2%. The solid-phase extraction MIPs microcolumn was reused 10 times, where it maintained a recovery rate of over 80%. This work presents a sensitive, fast, and convenient method for the determination of trace ampicillin in food samples.

Preparation of Imazethapyr Surface Molecularly Imprinted Polymers for Its Selective Recognition of Imazethapyr in Soil Samples.

A novel strategy based on imazethapyr (IM) molecular-imprinting polymers (MIPs) grafted onto the surface of chloromethylation polystyrene resin via surface-initiated atom transfer radical polymerization (SI-ATRP) for specific recognition and sensitive determination of trace imazethapyr in soil samples was developed. The SI-ATRP was performed by using methanol-water (4 : 1, v/v) as the solvent, acrylamide as the functional monomer, trimethylolpropane trimethacrylate (TRIM) as the cross-linker, imazethapyr as the template, and CuBr/2,2'-bipyridine as the catalyst. The resulting MIPs were characterized by elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Then, the binding selectivity, adsorption capacity, and reusability of the MIPs were evaluated. The results indicated that the prepared MIPs exhibited specific recognition and high selectivity for imazethapyr. The MIPs were further used as solid-phase extraction (SPE) materials coupled with high-performance liquid chromatography (HPLC) for selective extraction and detection of trace imazethapyr from soil samples. The results showed that good linearity was observed in the range of 0.10-5.00 µg/mL, with a correlation coefficient of 0.9995. The limit of detection (LOD) of this method was 15 ng/g, and the extraction recoveries of imazethapyr from real samples were in the range of 91.1-97.5%, which proved applicable for analysis of trace imazethapyr in soils. This work proposed a sensitive, rapid, and convenient approach for determination of trace imazethapyr in soil samples.

[Preparation of magnetic surface molecularly imprinted polymers for melamine and its application in milk samples].

By using melamine (MEL) as the template molecule, magnetic surface molecularly imprinted polymers (MMIPs) were prepared. Methacrylic acid (MAA) was chosen as the functional monomer, and ethyleneglycol dimethacrylate (EGDMA) was chosen as the cross-linker, and Fe3O4@SiO2 was used as the magnetic supporter. Transmission electron microscope (TEM), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) analysis and a vibrating sample magnetometer (VSM) were used to characterize the polymers. An imprinted polymer layer was found on the surface of the Fe3O4@SiO2 nanomaterials. MMIPs were applied to extract and enrich melamine in milk samples. The specific recognition capability of the material was confirmed by high performance liquid chromatographic (HPLC) analysis. Thus, a simple and selective method was successfully established using MMIPs as sorbents to detect melamine in milk with satisfactory results.

[Determination of lead in grape wine by graphite furnace atomic absorption spectrometry with ammonium dihydric phosphate as modifier].

Ammonium dihydric phosphate (NH4H2PO4), palladium chloride, nickelous nitrate and magnesium nitrate were used as modifiers respectively, to directly detect lead in grape wine with graphite furnace atomic absorption spectrometry(GFAAS). The results showed that NH4H2PO4 might be the best modifier. It was found that the organic matter in grape wine interfere with the determination. To remove the interference and detect lead directly with GFAAS, not only did samples need to be diluted with 4 to 10 times sample volumes of de-ionized water, but also the standard addition method was used. The method had good precision and accuracy when concentration of lead was above 10 micrograms.L-1, the relative standard deviations of lead were between -5.4% and 6.2%.