Hanqi Zhang

Preparation of magnetic molecularly imprinted polymer for the separation of tetracycline antibiotics from egg and tissue samples

Magnetic molecularly imprinted polymers were prepared using hydrophobic Fe(3)O(4) magnetite as the magnetically susceptible component, oxytetracycline as template molecule, methacrylic acid as functional monomer, and styrene and divinylbenzene as polymeric matrix components. The polymers were applied to the separation of tetracycline antibiotics from egg and tissue samples. The extraction and clean-up procedures were carried out in a single step by blending and stirring the sample, extraction solvent and polymers. The analytes can be transferred from the sample matrix to the polymers directly or through the extraction solvent as medium. When the extraction was complete, the polymers adsorbing the analytes were easily separated from the sample matrix by an adscititious magnet. The analytes eluted from the polymers were determined by liquid chromatography-tandem mass spectrometry. The recoveries ranging from 72.8% to 96.5% were obtained with relative standard deviations in the range of 2.9-12.3%. The limit of detection was less than 0.2 ng g(-1). The feasibility of this method was validated by analysis of incurred egg and tissue samples, and the results were compared with those obtained by the classical method in which solvent extraction, centrifugation, and subsequent clean-up and concentration by solid-phase extraction were applied. The proposed method reduced the complicacy of classical method and improved the reliability of method.

Study on the interaction mechanism between DNA and the main active components in Scutellaria baicalensis Georgi

Abstract Binding of baicalein, wogonin and baicalin to fish sperm DNA was studied by using ethidium bromide dye as a fluorescence probe. To study the binding mechanism, the absorption, fluorescence, melting temperature and viscosity measurement were carried out. The experimental results indicated that the planar of flavonoids intercalated to the DNA helix. When bound to DNA, flavonoids showed hyperchromic and blue shift in the absorption spectra and fluorescence quenching (>50%) in the fluorescence spectra. Furthermore, the intercalative binding was consistent with the red shift in the position of λ max in the fluorescence spectra. It was also found that ionic strength had little or no effect on the binding of flavonoids and DNA. Stern–Volmer plots at 25 and 37°C showed that the quenching of fluorescence by flavonoids was a combined quenching process. The binding site number n, apparent binding constant K A at 25 and 37°C, and the corresponding thermodynamic parameters ΔG, ΔH, ΔS at 25°C were obtained. The interaction of flavonoid–metal complexes with DNA was also studied by spectral methods, and the results suggested that the complexes intercalated into DNA.

Determination of fluoroquinolone antibiotics in environmental water samples based on magnetic molecularly imprinted polymer extraction followed by liquid chromatography-tandem mass spectrometry.

A simple method based on magnetic separation for selective extraction of fluoroquinolones (FQs) from environmental water samples has been developed using magnetic molecularly imprinted polymer (MMIP) as sorbent. The MMIP has been prepared using ciprofloxacin as template molecule, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross-linking agent and Fe(3)O(4) magnetite as magnetic component. The polymer has been characterized by scanning electron microscopy, Fourier-transform infrared spectrometry and vibrating sample magnetometry. Various parameters affecting the extraction efficiency were evaluated in order to achieve optimal concentration and reduce non-specific interactions. The analytes desorbed from the polymers were determined by liquid chromatography-tandem mass spectrometry. The matrix effect was evaluated by using different washing solvents for removing interfering compounds from the MMIPs after sample loading. Under the optimal conditions, the linearity of the method obtained is in the range of 20-2000 ng L(-1). The detection limits of FQs are in the range of 3.2-6.2 ng L(-1). The relative standard deviations of intra- and inter-day tests ranging from 2.5 to 7.2% and from 3.6 to 9.1% are obtained. In all three spiked levels (20, 100 and 200 ng L(-1)), the recoveries of FQs are in the range of 76.3-94.2%. The proposed method was successfully applied to determine FQs including ciprofloxacin, enrofloxacin, lomefloxacin, levofloxacin, fleroxacin and sparfloxacin in different water samples, such as lake water, river water, primary and final sewage effluent. Ciprofloxacin and fleroxacin were found in primary and final sewage effluent samples with the contents in the range of 26-87 ng L(-1).

Determination of triazines in honey by dispersive liquid–liquid microextraction high-performance liquid chromatography☆

Dispersive liquid-liquid microextraction (DLLME) high-performance liquid chromatography (HPLC) was developed for extraction and determination of triazines from honey. A room temperature ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate [C(6)MIM][PF(6.)], was used as extraction solvent and Triton X 114 was used as dispersant. A mixture of 175 microL [C(6)MIM][PF(6)] and 50 microL 10% Triton X 114 was rapidly injected into the 20 mL honey sample by syringe. After extraction, phase separation was performed by centrifugation and the sedimented phase was analyzed by HPLC. Some experimental parameters, such as type and volume of extraction solvent, concentration of dispersant, pH value of sample solution, salt concentration and extraction time were investigated and optimized. The detection limits for chlortoluron, prometon, propazine, linuron and prebane are 6.92, 5.84, 8.55, 8.59 and 5.31 microg kg(-1), respectively. The main advantages of the proposed method are simplicity of operation, low cost, high enrichment factor and extraction solvent volume at microliter level. Honey samples were analyzed by the proposed method and obtained results indicated that the proposed method provides acceptable recoveries and precisions.

Fast and Selective Extraction of Sulfonamides from Honey Based on Magnetic Molecularly Imprinted Polymer

A fast and selective method was developed for the determination of sulfonamides (SAs) in honey based on magnetic molecularly imprinted polymer. The extraction was carried out by blending and stirring the sample, extraction solvent and polymers. When the extraction was complete, the polymers, along with the captured analytes, were easily separated from the sample matrix by an adscititious magnet. The analytes eluted from the polymers were determined by liquid chromatography-tandem mass spectrometry. Under the optimal conditions, the detection limits of SAs are in the range of 1.5-4.3 ng g(-1). The relative standard deviations of intra- and interday ranging from 3.7% to 7.9% and from 4.3% to 9.9% are obtained, respectively. The proposed method was successfully applied to determine SAs including sulfadiazine, sulfamerazine, sulfamethoxydiazine, sulfamonomethoxine, sulfadimethoxine, sulfamethoxazole and sulfaquinoxaline in different honey samples. The recoveries of SAs in these samples from 67.1% to 93.6% were obtained.

Ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma

The ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0-110.8, 95.4-106.3, 95.0-108.3, and 95.7-107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n=5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination of SAs in liquid samples.

Determination of phenylurea and triazine herbicides in milk by microwave assisted ionic liquid microextraction high-performance liquid chromatography.

The determination of phenylurea and triazine herbicides in milk based on microwave assisted ionic liquid microextraction (MAILME) coupled with high-performance liquid chromatographic separation was described. The experimental parameters of the MAILE, including type and amount of ionic liquid, microwave extraction power, extraction time and salt concentration in sample, were evaluated by a univariate method and orthogonal screening. When 60 microL of [C(6)MIM][PF(6)] was used as extraction solvent the target compounds can be isolated from the 4 mL of milk. The MAILME is quick (7 min) and simple. The detection limits for isoproturon, monolinuron, linuron, propazine, prometryne, terbutryn and trietazine are 0.46, 0.78, 1.00, 1.21, 1.96, 0.84 and 1.28 microg L(-1), respectively. The proposed method was applied to the analysis of milk samples and the recoveries of the analytes ranged from 88.4 to 117.9% and relative standard deviations were lower than 7.43%.

Application of microwave techniques in analytical chemistry

Abstract The latest developments in the application of microwave techniques to analytical chemistry are reviewed. Some applications of microwave techniques to sample digestion, solvent extraction, sample drying, the measurement of moisture, analyte desorption and adsorption, sample clean-up, chromogenic reaction, speciation and nebulization of analytical samples are presented.

Analysis of ginsenosides in Panax ginseng in high pressure microwave-assisted extraction

High pressure microwave assisted extraction (HPMAE) was applied to extract the ginsenosides from Panax ginseng root. The influences of extraction solvent, extraction pressure and extraction time were individually investigated. HPMAE has been compared with other extraction methods, including Soxhlet extraction, ultrasound-assisted extraction and heat reflux extraction. The determination of ginsenosides was performed by HPLC-ESI-MS. The results indicated that the HPMAE not only took a shorter time but also afforded higher extraction yields of ginsenosides, especially ginsenoside Rb1, Rc, Rb2 and Rd. Furthermore, the neutral ginsenosides and malonyl ginsenosides in Panax ginseng root extracts by HPMAE were investigated. The malonyl ginsenoside m-Rb1, m-Rc, m-Rb2 and m-Rd degraded in HPMAE at 400kPa (109-112°C) in 70%(v/v) ethanol-water and at 600kPa (112-115°C) in methanol, and transformed into corresponding neutral ginsenoside Rb1, Rc, Rb2 and Rd. Using water as extraction solution, the neutral ginsenosides degraded under HPMAE at 400kPa (135-140°C), and transformed into less polarity rare ginsenosides.

Ultrasonic extraction and separation of anthraquinones from Rheum palmatum L.

The ultrasonic nebulization extraction (UNE) was developed and applied to extract anthraquinones (emodin, aloe-emodin and rhein) from Rheum palmatum L. Several parameters of UNE, including type of extraction solvent, concentration of extraction solvent, volume of extraction solvent, extraction time and ultrasonic power, were studied and the optimized parameters were selected. The operation conditions of micellar electrokinetic capillary chromatography (MEKC) were also studied. Under the selected conditions, contents of emodin, aloe-emodin and rhein obtained from different cultivated areas of R. palmatum L. were 1.08-2.04 mg/g, 0.65-1.16 mg/g and 0.70-2.90 mg/g, respectively. The relative standard deviations (RSDs) for emodin, aloe-emodin and rhein were 1.3-2.4%, 1.9-4.7% and 1.3-3.9%, respectively. Compared with maceration extraction (ME), reflux extraction (RE), stirring extraction (SE) and ultrasonic extraction (UE), the proposed method was more efficient, faster and easier to be operated and lower equipment costs and lower extraction temperature were required. The results indicated that UNE was a good alternative method for extracting anthraquinones from R. palmatum L. Compared with traditional extractions, the proposed extraction has a potential in on-line sampling, especially when the gas is used as the carrier of sample.