Core-shell magnetic porous organic polymer for magnetic solid-phase extraction of fluoroquinolone antibiotics in honey samples followed by high-performance liquid chromatography with fluorescence detection.

By monomer-mediated in-situ growth synthesis strategy, with hydroquinone and 1,3,5-tris(4-aminophenyl)benzene as monomers, a core-shell magnetic porous organic polymer was synthesized through a simple azo reaction. Based on this, a magnetic solid-phase extraction-high-performance liquid chromatography-fluorescence detection method was proposed for the analysis of fluoroquinolones in a honey sample. With ofloxacin, ciprofloxacin, enrofloxacin, lomefloxacin, and difloxacin as target analytes, factors affecting the extraction efficiency had been optimized. The LODs were 1.5-5.4 ng/L (corresponding to 0.23-0.81 µg/kg in honey). The linear range was 0.005-20 µg/L for difloxacin, 0.01-20 µg/L for ofloxacin, ciprofloxacin and lomefloxacin, and 0.02-20 µg/L for enrofloxacin. The enrichment factor was 84.4-91.7-fold with a high extraction efficiency of 84.4-91.7%. The method was assessed by the analysis of target fluoroquinolones in honey samples, and the recoveries for the spiked samples were 79.3-95.8%. The results indicated that the established magnetic solid-phase extraction-high-performance liquid chromatography-fluorescence detection method is efficient for the analysis of trace fluoroquinolones in honey.

Sustainable method towards magnetic ordered mesoporous polymers for efficient Methylene Blue removal.

The difficulty in achieving high removal efficiency for contaminants in textile wastewater over a wide range of pH impedes the progress of its treatment technique greatly. Herein, a facile and sustainable strategy was adopted for constructing magnetic ordered mesoporous polymers (M-OMPs) without the assistance of organic solvent and catalyst. The prepared M-OMPs were endowed with high special surface area and good superparamagnetism simultaneously, and exhibited high removal efficiency (>99%) for Methylene Blue (MB) within a short time (10 min) at a concentration of 50 mg/L. What's more, high removal efficiency was achieved over a wide range of pH 2-12 and the adsorption capacity for MB on M-OMPs was substantially retained even after 5 adsorption-desorption cycles, further demonstrating the application potential of M-OMPs in the decontamination of textile wastewater.

Spiral stir bar sorptive extraction with polyaniline-polydimethylsiloxane sol-gel packings for the analysis of trace estrogens in environmental water and animal-derived food samples.

A spiral stir bar was proposed by using stainless steel spring as the extraction phase carrier to avoid the extraction phase friction and increase the amount of extraction phase for improving extraction efficiency. The extraction phase is filled in the cavity of the spring, resulting in a larger amount of the extraction phase than that conventionally coated on glass stir bar or stainless steel wire. Polyaniline-polydimethylsiloxane sol-gel packed spiral stir bar was prepared and evaluated for the extraction of five estrogens. The prepared spiral stir bar presented good extraction efficiency/preparation reproducibility and long lifetime (more than 150 reused times) for target estrogens. Based on it, a method of spiral stir bar sorptive extraction combined with high performance liquid chromatography coupled with ultra-violet detection was developed for the analysis of trace estrogens in environmental and food samples. The detection limit for five estrogens was 0.11-.31 µg/L, with the enrichment factors of 83.0-118-fold (maximal enrichment factor: 200-fold). The reproducibility evaluated with each estrogen of 5 µg/L (n = 5) was 5.8-8.9%. The method was successfully applied for the determination of estrogens in environmental water and animal-derived food samples.

Microfluidic array surface ion-imprinted monolithic capillary microextraction chip on-line hyphenated with ICP-MS for the high throughput analysis of gadolinium in human body fluids.

A novel method by hyphenating chip-based array ion-imprinted monolithic microextraction with inductively coupled plasma mass spectrometry (ICP-MS) was proposed for the online analysis of trace Gd in biological samples in this work. The poly(γ-methacryloxypropyltrimethoxysilane@Gd3+-surface ion-imprinted polymer) [poly(γ-MAPS@Gd3+-SIIP)] monolithic capillary was prepared via in situ polymerization on the vinyl-modified surface of poly(γ-MAPS) using Eu3+ as the mimic template. The prepared ion-imprinted monolithic capillary possessed higher selectivity and adsorption capacity to Gd3+ than the non-imprinted monolithic capillary. Eight poly(γ-MAPS@Gd3+-SIIP) monolithic capillaries were embedded in the channels of a microfluidic chip to fabricate a chip-based array microextraction device. Factors affecting the selectivity of the prepared ion-imprinted monolithic capillary including imprinted time and the composition of the prepolymerization solution, and extraction conditions for the fabricated chip-based array ion-imprinted monolithic capillary microextraction platform were optimized. A sample throughput of 18 h-1 was achieved along with a low detection limit of 1.27 ng L-1 for Gd3+. The proposed chip-based array poly(γ-MAPS@Gd3+-SIIP) monolithic microextraction-ICP-MS method was used for the analysis of trace Gd in human urine and serum, and the recovery for spiking experiments was in the range of 88.1-96.7%. The developed integrated analysis platform possesses good interference resistance, high automation, high sensitivity and low consumption of the sample/agent, which makes it very suitable for the analysis of trace elements in complicated biological samples.

Fe3O4 nanoparticles coated with double imprinted polymers for magnetic solid phase extraction of lead(II) from biological and environmental samples.

Double imprinted polymer coated magnetic nanoparticles were fabricated with 4-nm size ZnO nanoparticles acting as the sacrifice templates, which were co-imprinted with template Pb(II) ions. After template removal, abundant transfer pores derived from ZnO nanoparticles were left around the selective adsorption sites derived from Pb(II) ions. The magnetic sorbent exhibit good selectivity, rapid adsorption kinetic and large adsorption capacity for Pb(II). They were used to extract trace Pb(II) followed by graphite furnace atomic absorption spectrometry detection. After the optimization of extraction conditions, following merits are found: (a) rapid extraction (10 min), (b) high preconcentration factor (100 fold), (c) sensitive detection with the detection limit of 9.4 ng·L-1, and (d) low relative standard deviation (6.9%) at a level of 50 ng·L-1 of Pb(II) analyzed 7 times. The method was employed in extraction and quantification of trace Pb in biological and environmental samples with satisfactory recoveries of 87.5-104%. Graphical abstractDouble imprinted polymer coated magnetic nanoparticles (MNPs@DIP) were fabricated and used for extraction of Pb(II) followed by graphite furnace atomic absorption spectrometry (GFAAS) detection. The method was successfully applied for the determination of Pb in environmental and biological samples.

Membrane supported liquid-liquid-liquid microextraction combined with field-amplified sample injection CE-UV for high-sensitivity analysis of six cardiovascular drugs in human urine sample.

An effective dual preconcentration method involving off-line membrane supported liquid-liquid-liquid microextraction (MS-LLLME) and on-line field-amplified sample injection (FASI) was proposed for the extraction of six cardiovascular drugs, including mexiletine, xylocaine, propafenone, propranolol, metoprolol, and carvedilol from aqueous solution prior to CE-UV. In MS-LLLME, the analytes were extracted from 9 mL sample solution into toluene, and then back extracted into a drop of acceptor phase of 10 µL 20 mmol/L acetic acid. After that, the acceptor phase was directly introduced into CE for FASI without any modification. In FASI process, water plug was hydrodynamically injected (50 mbar, 3 s) into the capillary prior to sample injection (+6 kV, 18 s). Six target analytes were separated in less than 10 min at 25°C with a BGE consisting of 70 mmol/L Tris-H3 PO4 (pH 2.2) containing 10% v/v methanol. Under the optimized conditions, LODs obtained by the proposed MS-LLLME-FASI-CE-UV method were in the range of 0.02-0.82 µg/L (based on S/N = 3) with enrichment factors of 546- to 7300-fold for the target analytes. The RSDs of the developed method were in the range of 6.7-12.9% (n = 7). Good linearity (R(2) = 0.9928-0.9997) was obtained in concentration range of 0.1-100 µg/L for mexiletine and propranolol, 0.2-100 µg/L for xylocaine and metoprolol, 0.5-100 µg/L for propafenone and 2.0-100 µg/L for carvedilol, respectively. The developed method was successfully applied for real-time determination of metoprolol in human urine samples within 26 h after uptake.

Restricted accessed nanoparticles for direct magnetic solid phase extraction of trace metal ions from human fluids followed by inductively coupled plasma mass spectrometry detection.

Herein, restricted accessed magnetic nanoparticles were synthesized by self-assembly of a non-ionic surfactant (Tween-20) onto the 4-(2-pyridylazo)resorcinol (PAR) functionalized magnetic nanoparticles (MNPs). A series of analytical techniques were employed for the characterization of the as-prepared restricted accessed Fe3O4@SiO2@PAR, and it was found that the as-prepared restricted accessed Fe3O4@SiO2@PAR nanoparticles have a porous structure with a BET surface area of around 99.4 m(2) g(-1), an average pore size of about 6.14 nm and a pore volume of 0.47 cm(3) g(-1). Besides, the prepared restricted accessed Fe3O4@SiO2@PAR showed good size exclusion properties toward proteins, providing application potential for the direct analysis of biological samples. Based on this, a novel method of restricted accessed magnetic solid phase extraction (MSPE) combined with inductively coupled plasma-mass spectrometry (ICP-MS) was developed for the direct determination of trace metal ions in human fluids. The parameters affecting the extraction of the target metals by MSPE were studied and the optimized conditions were established. Under the optimum conditions, the adsorption capacity of Cr(III), Cd(II), La(III), Nd(III) and Pb(II) on the as-prepared restricted accessed Fe3O4@SiO2@PAR was 62.9, 56.6, 33.7, 36.9 and 43.3 mg g(-1), respectively. With an enrichment factor of 30, the limits of detection for Cr(III), Cd(II), La(III), Nd(III) and Pb(II) were as low as 11.9, 0.8, 0.7, 1.6 and 4.1 ng L(-1), and the relative standard deviations were 7.6, 8.7, 8.4, 8.1 and 5.0 (C(Cr, Pb) = 0.05 µg L(-1), C(Cd, La) = 0.005 µg L(-1), C(Nd) = 0.01 µg L(-1), n = 7), respectively. The developed method was successfully applied for the direct analysis of free metal ions in human urine and serum samples, and has the advantages of good anti-interference ability, high sensitivity and exhibits great application potential in the direct analysis of trace metals in biological fluids.

Cyromazine imprinted polymers for selective stir bar sorptive extraction of melamine in animal feed and milk samples.

In this work, a molecularly imprinted polymer (MIP) coated stir bar was prepared using a self-designed polytetrafluoroethylene (PTFE) mold and in situ polymerization, with cyromazine as the dummy template for the target melamine. The prepared MIP coated stir bar presented a uniform and porous surface as well as good chemical stability and selectivity for melamine. Based on it, a method of MIP coated stir bar sorptive extraction (SBSE) combined with high performance liquid chromatography-ultraviolet detection (HPLC-UV) was developed for the quantification of melamine in food samples. Significant factors affecting the extraction efficiency of melamine by MIP-SBSE, such as the extraction solvent and time, stirring rate, desorption solvent and time, were investigated thoroughly. Under the optimal conditions, the analytical performance of this method was evaluated. The detection limit of the developed method was 0.54 µg L(-1) for melamine with an enrichment factor of 42-fold and the relative standard deviation (RSD) of 6.1% (c = 5 µg L(-1), n = 7), and the linear range was 2-200 µg L(-1). The established method was applied for the determination of melamine in a variety of real samples including cat food, dog food, chicken feed A, chicken feed B and milk powder, and the recoveries for melamine in the spiked samples were in the range of 76.2-98.2%, 80.0-85.5%, 89.5-113%, 85.0-95.5% and 65.0-111%, respectively. The proposed method presented a good specific recognition ability and matrix interference resistance, and was demonstrated to be effective and sensitive for the analysis of melamine in animal food and milk samples.

Development of novel sol-gel coatings by chemically bonded ionic liquids for stir bar sorptive extraction--application for the determination of NSAIDS in real samples.

In this work, a novel ionic liquid (IL) chemically bonded sol-gel coating was prepared for stir bar sorptive extraction (SBSE) of nonsteroidal anti-inflammatory drugs (NSAIDs) followed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). By using γ-(methacryloxypropyl)trimethoxysilane (KH-570) as a bridging agent, 1-allylimidazolium tetrafluoroborate ([AIM][BF4]) was chemically bonded onto the bare stir bar, and the prepared IL-bonded sol-gel stir bar coating showed higher extraction efficiency and better adsorption/desorption kinetics for target NSAIDs over other polydimethylsiloxane (PDMS)-based or monolithic stir bar coatings. The mechanical strength and durability (chemical/thermal stability) of the prepared IL-bonded sol-gel coating were excellent. The influencing factors of SBSE, such as sample pH, salt effect, stirring rate, extraction time, desorption solvent, and desorption time, were optimized, and the analytical performance of the developed SBSE-HPLC-UV method was evaluated under the optimized conditions. The limits of detection (LODs) of the proposed method for three NSAIDs were in the range of 0.23-0.31 µg L(-1), and the enrichment factors (EFs) were in the range of 51.6-56.3 (theoretical enrichment factor was 100). The reproducibility was also investigated at concentrations of 5, 20, and 100 µg L(-1), and the relative standard deviations (RSDs) were found to be less than 9.5, 7.5, and 7.6 %, respectively. The proposed method was successfully applied for the determination of NSAIDs in environmental water, urine, and milk samples.

Polymer monolithic capillary microextraction combined on-line with inductively coupled plasma MS for the determination of trace rare earth elements in biological samples.

A rapid and sensitive method based on polymer monolithic capillary microextraction combined on-line with microconcentric nebulization inductively coupled plasma MS has been developed for the determination of trace/ultratrace rare earth elements in biological samples. For this purpose, the iminodiacetic acid modified poly(glycidyl methacrylate-trimethylolpropane trimethacrylate) monolithic capillary was prepared and characterized by SEM and FTIR spectroscopy. Factors affecting the extraction efficiency, such as sample pH, sample flow rate, sample/eluent volume, and coexisting ions were investigated in detail. Under the optimal conditions, the LODs for rare earth elements were in the range of 0.08 (Er) to 0.97 ng/L (Nd) with a sampling frequency of 8.5 h(-1), and the RSDs were between 1.5% (Sm) and 7.4% (Nd) (c = 20 ng/L, n = 7). The proposed method was successfully applied to the analysis of trace/ultratrace rare earth elements in human urine and serum samples, and the recoveries for the spiked samples were in the range of 82-105%. The developed method was simple, rapid, sensitive, and favorable for the analysis of trace/ultratrace rare earth elements in biological samples with limited sample volume.

Porous aromatic framework/polydimethylsiloxane coated stir bar sorptive extraction coupled with high performance liquid chromatography-diode array detection of trace polychlorinated biphenyls analysis in environmental waters.

A porous aromatic framework (PAF-47) synthesized through Suzuki coupling reaction was introduced to prepare PAF-47/polydimethylsiloxane (PDMS) coated stir bar by sol-gel technique. PAF-47/PDMS coating provided high extraction recovery (77.6-90.6%, the ratio of actual enrichment factor (EF) to theoretical EF) for five polychlorinated biphenyls (PCBs) in a relatively short time (60 min), exhibiting a faster extraction kinetics over commercial PDMS coating (12/24 h). Based on this, a new method based on PAF-47/PDMS coated stir bar sorptive extraction and high-performance liquid chromatography-diode array detection was proposed for trace analysis of target PCBs in environmental water. Under the optimized conditions, the limits of detection for five PCBs were within 44-70 ng/L, with actual EF of 64.0-71.5-fold (maximal EF of 83.3-fold). This method was successfully used to detect trace PCBs in Yangtze River water and East Lake water, with recoveries of 81.0-113% and 86.1-111%, respectively.

Triazine covalent organic polymer coated stir bar sorptive extraction coupled with high performance liquid chromatography for the analysis of trace phthalate esters in mineral water and liquor samples.

Cyanuric chloride and 4,4'-diamino-p-terphenyl were adopted as monomers to synthesize poly (4,4'-diamino-p-terphenyl-triazine) (PDT) covalent organic polymer. PDT coated stir bar was prepared and evaluated for the extraction of five phthalate esters (PAEs) with relatively lower logP values (2.7-4.9), including diethyl phthalate, diallyl phthalate, dipropyl phthalate, benzylbutyl phthalate and dibutyl phthalate. It exhibited higher extraction recovery (> 65%) and faster extraction kinetics (50 min vs 240 min) for target PAEs over commercial polydimethylsiloxane coated stir bar. Based on the superior performance, PDT coated stir bar sorptive extraction was combined with high-performance liquid chromatography-diode array detection for trace analysis of five PAEs plasticizers. The limits of detection for target PAEs were 0.04-0.27 µg/L, with the enrichment factors of 54-80-fold. The potential of the method was demonstrated by detecting five target PAEs in Chinese liquor and mineral water samples. No target analytes were detected in Chinese liquor sample, and recoveries of 85.4-109% were obtained for target analytes in spiked liquor samples; trace diethyl phthalate (1.19-2.98 µg/L) and dibutyl phthalate (0.77-0.91 µg/L) were detected in two mineral water samples, with recoveries of 85.4-117% and 87.4-117% respectively in spiked mineral water samples.

Stir bar sorptive extraction and its application.

Recent progress of stir bar sorptive extraction (SBSE) in the past six years is reviewed. The preparation methods including electrodeposition, self-assembly, solvent exchange, physical magnetic adsorption and electrostatic spinning, for the coated stir bar are summarized and compared, specifically for a specific material for coatings fabrication, e.g., carbon-based materials and metal organic frameworks. The emerging materials (e.g., graphene, graphene oxide, carbon nanotubes, monolith, metal-organic frameworks and porous organic polymers) applied for coated stir bar fabrication are one of the focus of this review, along with their respective advantages in extraction process and application in trace analysis. The development and application of extraction apparatus of SBSE are also involved. Based on these information, the development status and prospects of SBSE as an efficient sample pretreatment technique in real sample analysis are discussed.

Study of Fe3O4-PPy Core-Shell Nanocomposite in the Diagnosis of Tumor Markers in the Tissues of Early Gastric Cancer Patients.

In order to study Fe3O4-Polypyrrole (Fe3O4-PPy) core-shell nanocomposite in the diagnosis of tumor markers in the diseased gastric tissues of early cancer patients, a total of 160 cases of patients, who were confirmed as early gastric cancer by gastroscopy or postoperative pathology at a designated hospital of the study from December 2014 to December 2018, were selected as research objects and were divided into two groups of observation and control group with 80 cases in each group. For each patient in the two groups, two pieces of diseased gastric tissue were firstly taken through gastroscopy; then the observation group applied Fe3O4-PPy with the particle diameter of 150-350 nm as carrier to detect the contents of carbohydrate antigen 19-9 (CA19-9), alpha-fetoprotein (AFP), carbohydrate antigen 242 (CA242), carcinoembryonic antigen (CEA) and carbohydrate antigen 72-4 (CA72-4) in the diseased gastric tissue, while the control group directly detected the contents of corresponding tumor markers; after the detections, the sensitivity, specificity and diagnostic efficiency of each marker in the two groups of patients were calculated, and receiver operating characteristics (ROC) curves with the areas under the curves (AUC) were drawn to analyze the correlation between the level of Fe3O4-PPy and the detection efficiency of gastric cancer markers. The results show that the detection sensitivity (82.17%, 80.32%, 79.48%, 84.63%, and 85.66%) and specificity (76.75%, 79.66%, 81.07%, 83.47%, and 85.24%) of CA19-9, AFP, CA242, CEA, and CA72-4 in the tumor tissue of patients in observation group for the diagnosis of early gastric cancer are higherthan the sensitivity (78.66%, 79.25%, 76.18%, 82.11%, and 83.45%) and specificity (74.37%, 76.94%, 77.24%, 81.22%, and 81.59%) of that in control group with statistically significant differences (P < 0.05). Therefore, it is believed that the Fe3O4-PPy is of great significance for the detection of early gastric tumor markers in the tissues of patients with early gastric cancer, and has certain value for the auxiliary diagnosis of early gastric cancer and the observation of therapeutic effects. This study results provide a reference for the further researches of Fe3O4-PPy in the diagnosis of tumor markers in patients with early gastric cancer.

Azo-linked porous organic polymers/polydimethylsiloxane coated stir bar for extraction of benzotriazole ultraviolet absorbers from environmental water and soil samples followed by high performance liquid chromatography-diode array detection.

With 4,4'-diaminoterphenyl and phloroglucinol as the monomers, Azo-linked porous organic polymer (PP) was prepared by a green mild azo reaction. Azo-PP is rich in phenolic hydroxyl groups and benzene rings, which can form intermolecular hydrogen bonds with the phenolic hydroxyl groups in interest benzotriazoles (BZTs). The π-π interaction between the benzene ring and the triazole ring would promote the adsorption of target BZTs on Azo-PP. Azo-PP/polydimethylsiloxane (PDMS) coated stir bar was prepared via sol-gel technique for the extraction of target BZTs. Compared with commercial stir bar, Azo-PP coated stir bar showed superior extraction efficiency (75-88% vs 45-65%) under similar conditions and kinetics (50 min vs 120 or 360 min). A method of stir bar sorptive extraction (SBSE) combined with high performance liquid chromatography (HPLC)-diode array detector (DAD) was developed to analyze six target BZT UltraViolet (UV) absorbers. The optimization of SBSE conditions for extraction of interest BZTs was performed by single-factor test. Under the optimized conditions, the limits of detection within 0.12-0.33 µg/L were achieved for six BZT UV absorbers, with the linear range within 0.5-100 µg/L. The method was applied to detect six BZT UV absorbers in the East Lake water, Yangtze River water, and campus soil samples. No BZT was detected in any of the samples. The recoveries of target BZTs in spiked samples were found in the range of 94.9-118%, 96.2-118%, and 88.2-119%.

Hydroxyl-containing porous organic framework coated stir bar sorption extraction combined with high performance liquid chromatography-diode array detector for analysis of triazole fungicides in grape and cabbage samples.

In this work, a hydroxyl-containing porous organic framework (HC-POF) was prepared by a simple solvothermal reaction with 1,4-phthalaldehyde and phloroglucinol as monomers. Sol-gel method was used to coat HC-POF on the glass stir bar. The prepared HC-POF coated stir bar shows better extraction performance for six triazole fungicides (TFs) compared to commercial polydimethylsiloxane and ethylene glycol-silicone coated stir bars. Fourier transform infrared Spectrometry and X-ray photoelectron Spectrometry were used to explore interactions between HC-POF coating and TFs. It is assumed that the coating mainly adsorbs TFs through π-π interactions, hydrogen bonding and hydrophobic interactions. Based on this fact, a new method of HC-POF coated stir bar sorptive extraction combined with high performance liquid chromatography-diode array detector was developed for the determination of six TFs in grape and cabbage samples. A series of extraction and desorption conditions were carefully optimized, including salt concentration, sample solution pH, stirring rate and desorption solvent. Under the optimized experimental conditions, the proposed method displayed limits of detection in the range of 0.022 -0.071 µg L-1, which is the lowest among the reported SBSE methods for target TFs analysis. The linear range for six TFs was 0.1/0.2-500 µg L-1 and the recoveries for the spiked grape and cabbage were 81.0-109% and 80.7-111%, respectively.

Magnetic porous organic polymers for magnetic solid-phase extraction of triazole fungicides in vegetables prior to their determination by gas chromatography-flame ionization detection.

Magnetic porous organic polymers (MOPs) were synthesized by a simple azo reaction, with 1,3,5-tris (4-aminophenoxy) benzene and 1,3,5-trihydroxybenzene as the monomers, and Fe3O4@SiO2 as the core. The preparation process was mild, green and environmental-friendly, avoiding the use of high temperature, metal catalysis and harmful organic reagent. The obtained MOPs were characterized in terms of morphology, pore structure, and magnetism; they exhibited high surface area, good stability/dispersibility, and excellent extraction performance for interest triazole fungicides (TFs). With the prepared MOPs as adsorbent, a method of magnetic solid phase extraction-gas chromatography-flame ionization detection (MSPE-GC-FID) was proposed for the analysis of target TFs in vegetables. After the vegetable samples were chopped and homogenized, acetonitrile was added for ultrasonic extraction, and the extract was diluted for subsequent MSPE process. Different operating conditions affecting the extraction efficiency of TFs, such as extraction time, pH, ionic strength, adsorbent dosage, and volume of sample as well as eluent were carefully optimized. Under the optimized experimental conditions, quantitative extraction could be achieved for target TFs (extraction efficiency of 84.5-90.3%), and the limits of detection were in the rage of 0.12-0.19 µg/L, which is the lowest among the reported GC-FID methods for target TFs presently. The linear range of the method for five TFs was 0.5-200 µg/L with the reproducibility of 2.6-6.8% (n = 7, c = 2 µg/L). The method was assessed by the analysis of target TFs in vegetables, and the recoveries for the spiked cucumber and cabbage were 86.9-117% and 84.7-114% (spiking levels of 80, 400 and 800 µg/kg), respectively, indicating that the matrix effect was negligible in the proposed MSPE procedure. The results show that the developed method of MSPE-GC-FID with MOPs as adsorbent is efficient for the analysis of trace TFs in vegetables.

Magnetic solid-phase extraction using sulfur-containing functional magnetic polymer for high-performance liquid chromatography-inductively coupled plasma-mass spectrometric speciation of mercury in environmental samples.

1,2-Ethanedithiol was firstly involved in preparing sulfur-containing functional magnetic polymer material of Fe3O4@SiO2@ glycidyl methacrylate (GMA)-S-SH. The prepared Fe3O4@SiO2@GMA-S-SH magnetic nanoparticles (MNPs) show better adsorption capacity and adsorption/desorption dynamics for mercury species than other -SH functional materials due to the high affinity of both thioether and thiol group towards mercury. A new method of magnetic solid phase extraction (MSPE) using Fe3O4@SiO2@GMA-S-SH as sorbents combined with high performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) was developed for the analysis of trace Hg2+, methylmercury (MeHg+) and phenylmercury (PhHg+). Variables affecting the simultaneous extraction of three target mercury species were investigated. It was found that Hg2+, MeHg+ and PhHg+ in 200 mL of water sample could be quantitatively adsorbed within 5 min and eluted by 0.5 mL 0.1 mol L-1 nitric acid and 4% thiocarbamide in 2 min. The developed method has high actual enrichment factors of 367, 380, 329-fold for Hg2+, MeHg+ and PhHg+, respectively. The detection limits were 0.40, 0.49 and 1.4 ng L-1 with the relative standard deviations (n = 5, inter-day) of 7.4, 8.1 and 8.3% for Hg2+, MeHg+ and PhHg+, respectively. The accuracy of the method was validated by the analysis of the Certified Reference Materials of GSS-11 soil, GSS-13 soil, GSB21 rice and DORM-2 fish. The established method was successfully used for the mercury speciation in farmland water, soil and rice samples collected from Wanshan, China, and satisfactory recoveries (84.3-116%) were obtained for the spiked samples.

Simultaneous speciation of inorganic selenium and antimony in water samples by electrothermal vaporization inductively coupled plasma mass spectrometry following selective cloud point extraction.

A new method was developed for the simultaneous speciation of inorganic selenium and antimony in water by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) following selective cloud point extraction (CPE). The method is based on the fact that Se(IV) and Sb(III) could form complexes with diethyldithiocarbamate (DDTC) at pH 6.00, and the complexes were quantitatively extracted into the non-ionic surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-114), whereas the Se(VI) and Sb(V) remained as free species in aqueous solutions. Sb(III) and Se(IV) in concentrate were determined by ETV-ICP-MS after proper disposal. The total Se and total Sb were determined by the same protocol after Se(VI) and Sb(V) were reduced by l-cysteine, and Se(VI) and Sb(V) concentrations were obtained by respectively subtracting Se(IV) and Sb(III) from the total Se and the total Sb. Under the optimized conditions, the limits of detection (LODs) were 0.05 microg L(-1) for Se(IV) and 0.03 microg L(-1) for Sb(III), the relative standard deviations (RSDs) were 3.5% for Se(IV) and 4.2% for Sb(III) (C=1.00 microg L(-1), n=5). The proposed method was applied to the speciation of inorganic selenium and antimony in different water samples with satisfactory results.

Melamine-based porous organic polymers inline solid phase extraction coupled with high performance liquid chromatography for the analysis of phytohormones in juice samples.

A melamine-based porous organic polymer (mPMF) was synthesized as solid phase extraction (SPE) adsorbent for inline SPE-high performance liquid chromatography (HPLC)-ultraviolet detector (UV) analysis of five phytohormones. Melamine contributed to the rich π-electron and N-containing triazine structure for mPMF, which could form π-π interaction and intermolecular hydrogen bond with COOH containing phytohormones. The synthesized mPMF adsorbent shows extremely high extraction efficiency for five target analytes (>80%) including salicylic acid, indole-3-acetic acid, abscisic acid, 2,4-dichlorophenoxyacetic acid and 1-naphthalene acetic acid. The factors affecting extraction of the target phytohormones were investigated and the optimized experimental conditions were established. The linear range was 0.2-100 µg/L with the limits of detection in the range of 0.06-0.11 µg/L for five target phytohormones. The developed method of mPMF-inline-SPE-HPLC-UV was applied for the analysis of trace target phytohormones in tomato and grape juice samples, and the recovery in the range of 83.1-116% and 87.2-121% was obtained for the spiked tomato and grape juice, respectively. This method has the advantages of high sensitivity and good reproducibility, and it has good application potential for the analysis of phytohormones in fruit samples. Moreover, inline analysis avoided the problems of sample pollution and sample loss, and provided a sample throughput of 5/h.