A novel ratiometric electrochemical sensing platform combined with molecularly imprinted polymer and Fe-MOF-NH2/CNTs-NH2/MXene composite for efficient detection of ofloxacin.

BACKGROUND: Ofloxacin (OFL) is often abused in medicine and animal husbandry, which poses a great threat to human health and ecological environment. Therefore, it is necessary to establish efficient method to detect OFL. Electrochemical sensor has attracted widespread attention due to the advantages of low cost and fast response. However, most electrochemical sensors usually use one response signal to detect the target, which makes it sensitive to the variable background noise in the complex environment, resulting in low robustness and selectivity. The ratio detection mode and employing molecularly imprinted polymer (MIP) are two strategies to solve these problems. RESULTS: A novel molecular imprinting polymer-ratiometric electrochemical sensor (MIP-RECS) based on Fe-MOF-NH2/CNTs-NH2/MXene composite was prepared for the rapid and sensitive detection of OFL. The positively charged Fe-MOF-NH2 and CNTs-NH2 as interlayer spacers were introduced into the negatively charged MXene through a simple electrostatic self-assembly technique, which effectively prevented the agglomeration of MXene and increased the electrocatalytic activity. A glass carbon electrode was modified by the composite and a MIP film was electropolymerized on it using o-phenylenediamine and ß-cyclodextrin as bifunctional monomers and OFL as template. Then a MIP-RECS was designed by adding dopamine (DA) into the electrolyte solution as internal reference, and OFL was quantified by the response current ratio of OFL to DA. The current ratio and the concentration of OFL displayed a satisfying linear relationship in the range of 0.1 µM-100 µM, with a limit of detection (LOD) of 13.2 nM. SIGNIFICANCE: Combining molecular imprinting strategy and ratio strategy, the MIP-RECS has impressive selectivity compared with the non-imprinted polymer-RECS, and has better repeatability and reproducibility than non-ratiometric sensor. The MIP-RECS has high sensitivity and accuracy, which was applied for the detection of OFL in four different brands of milk and was verified by HPLC method with satisfactory results.

A hydrophobic deep eutectic solvent-based vortex-assisted liquid-liquid microextraction applied for doping control of aromatase inhibitors from equine urine.

Aromatase inhibitors (AIs) can indirectly cause increased testosterone in animals, which leads to the improvement of the athletic ability of horses. For the protection of horses and the consideration of fair competition, AIs were listed as prohibited drugs by the Federation Equestre Internationale (FEI). There were several disadvantages using traditional pretreatment methods before analyzing these drugs from biological samples. A rapid and green pretreatment method has been developed by utilizing the hydrophobic deep eutectic solvent (DES)-based vortex-assisted liquid-liquid microextraction (DES-VALLME) followed by ultra-high performance liquid chromatography tandem triple-quadrupole mass spectrometry (UHPLC-MS/MS) technique for the efficient extraction and sensitive detection of AIs in equine urine samples. The combination of menthol and 4-fluorophenol in a molar ratio 1:4 was chosen as the optimum composition of DES for extracting AIs. Under the optimum conditions, only 80 µL of DES, 1 mL equine urine and 2 min were expended. An external standard calibration method was utilized for determination, and a linear relationship was achieved with a concentration range of 0.02-4000 ng mL-1 (r2 ≥ 0.9983). The limits of detection of the method based on a signal-to-noise ratio of 3 were 0.01-4 ng mL-1. The accuracy recoveries ranged from 94.9% to 113.4% within the intra-day and inter-day relative standard deviations of less than 9.1%. Compared with traditional extraction methods, the DES-VALLME method had the advantages of rapidity, simplicity, efficiency, low toxicity, and low cost. This method has potential and possessed brilliant prospects for doping control.

A molecularly imprinted polymer monolithic column with dual template and bifunctional monomers for selective extraction and simultaneous determination of eight phenolics from polycarbonate cups.

A molecularly imprinted polymer (MIP) monolithic column was prepared in situ in a pipette tip using phenol and bisphenol A as dual templates, 4-vinyl pyridine and ß-cyclodextrin as bifunctional monomers. It was used for the selective and simultaneous solid phase extraction of eight phenolics, including phenol, m-cresol, p-tert-butylphenol, bisphenol A, bisphenol B, bisphenol E, bisphenol Z, and bisphenol AP. The MIP monolithic column was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and nitrogen adsorption experiment. The results of selective adsorption experiments showed that the MIP monolithic column can selective recognize the phenolics and have excellent adsorption property. The imprinting factor for bisphenol A can be as high as 4.31, and the maximum adsorption capacity for bisphenol Z can reach 201.66 mg g-1. Under the optimal extraction conditions, a selective and simultaneous extraction and determination method for eight phenolics was established based on the MIP monolithic column and high-performance liquid chromatography with ultraviolet detection. The linear ranges (LRs) of the eight phenolics were 0.5-200 µg L-1, the limits of quantification (LOQs) and detection (LODs) were 0.5-2.0 µg L-1 and 0.15-0.67 µg L-1. The method was applied to detect the migration quantity of the eight phenolics from polycarbonate cups and had satisfactory recovery. The method has the advantages of simple synthesis, short extraction time, as well as good repeatability and reproducibility, which provides a sensitive and reliable strategy for extracting and detecting phenolics from food contact material.

A Zn-based metal coordination cluster Zn5 used for solid phase microextraction of ten phenolic compounds from water and soil.

Exploring coating materials with superior extraction efficiency has always been the pursuit in the field of solid phase microextraction (SPME). Metal coordination clusters with high thermal and chemical stability, abundant functional groups as active adsorption site are the promising coatings. In the study, a Zn5(H2Ln)6(NO3)4 (Zn5, H3Ln =(1,2-bis-(benzo[d]imidazol-2-yl)-ethenol) cluster coating was prepared and applied for SPME of ten phenols. Zn5 based SPME fiber exhibited high extraction efficiencies for phenols in headspace (HS) mode, which circumvented the pollution of SPME fiber. The adsorption isotherm and theoretical calculation indicated the adsorption mechanism of phenols on Zn5 was hydrophobic interaction, H-bond interaction and π-π stacking. Under the optimized extraction conditions, an HS-SPME-GC-MS/MS method was developed for the determination of ten phenols in water and soil samples. For ten phenolic compounds in water and soil samples, the linear ranges were 0.5-5000 ng/L and 0.5-250 ng/g, respectively. The limits of detection (LODs, S/N = 3) were 0.010-1.20 ng/L and 0.0048-0.16 ng/g, respectively. The precisions of single fiber and fiber-to-fiber were lower than 9.0% and 14.1%, respectively. The proposed method was applied for the detection of ten phenolic compounds in various water and soil samples, showing satisfactory recovery (72.1-118.8%). This study delivered a novel and efficient SPME coating material for the extraction of phenols.

Fabrication and application of Zn5 functionalized copolymer monolithic column for pipette tip micro-solid phase extraction of 4 polycyclic aromatic hydrocarbons in edible oil.

The contamination of polycyclic aromatic hydrocarbons (PAHs) in edible oil is a health threat. Thus, trace analysis of PAHs is of high necessity. Based on the efficient adsorption of PAHs on Zn5 metal cluster, a Zn5 functionalized copolymer monolithic column was rationally designed for pipette tip micro-solid phase extraction (µ-SPE). The modified Zn5 improved the adsorption selectivity and capacity of the monolith for naphthalene, phenanthrene, fluoranthene and pyrene. Chemical doping and copolymerization stabilized the monolith with a long life. Under optimal extraction conditions, a µ-SPE-high performance liquid chromatography with ultraviolet detector method was established for the detection of 4 PAHs in edible oils. The method yielded detection ranges of 0.15-250 µg L-1 (R2 > 0.997), detection limits of 0.050-1.5 µg L-1, satisfactory recoveries (86.3-101.5 %), and high precisions (RSDs < 7.9 %). The results indicated that the Zn5 functionalized copolymer monolithic column was an ideal separation medium for the detection of PAHs residues in edible oils.

Preparation and application of a nanocomposite of dopamine modified zirconium metal organic framework and polythiophene for solid-phase microextraction/gas chromatography of phenols released from polycarbonate materials.

The zirconium metal-organic framework (MOF) UiO-66 was modified by dopamine (DA) and electrodeposited with Poly (3,4-ethylenedioxothiophene) (PEDOT) on an etched stainless steel wire to prepare a UiO-66-DA/PEDOT nanocomposite coating. The coating was characterized by scanning electron microscopy, energy dispersive spectrometer, Fourier transform infrared and thermogravimetric analysis, respectively. The coating has high specific surface area and more porous structure, which can be used to extract eight phenols, including 2-chlorophenol, o-cresol, m-cresol, 2, 4-dichlorophenol, 4-tert-butylphenol, 4-chlorophenol, 4-tert-octylphenol and α-naphthol. The adsorption behavior of the phenols on the UiO-66-DA/PEDOT coating had significant correlation with Langmuir isothermal model. A determination method for the eight phenols was established by combining with direct immersion solid-phase micro extraction and gas chromatography. Under the optimal experimental conditions, the detection linear range (LRs) was 0.05-50 µg mL-1 and the detection limit (LODs) was 0.01-0.08 µg mL-1 (S/N = 3). The method was applied for the migration detection of eight phenols in polycarbonate cups, which showed satisfactory recovery.

Simultaneous detection of eight phenols in food contact materials after electrochemical assistance solid-phase microextraction based on amino functionalized carbon nanotube/polypyrrole composite.

An electrochemical assistance solid-phase microextraction (EA-SPME) was developed based on amino functionalized multi-walled carbon nanotube/polypyrrole (MWCNTs-NH2/PPy) composite coating. It was applied for the extraction of eight phenols in food contact material, including 2-chlorophenol, o-cresol, m-cresol, 2,4-dichlorophenol, 4-tert-butylphenol, 4-chlorophenol, 4-tertoctylphenol and alpha-naphthol. MWCNTs-NH2/PPy coating was characterized by scanning electron microscopy, transmission electron microscope, X-ray energy spectrometer, X-ray diffraction, Fourier transform infrared and thermogravimetric analysis. The adsorption mechanism of phenols on the composite coatings was investigated. The coating modified steel-wire as an extraction fiber has good electroconductibility, reproducibility and long service life. A determination method for the eight phenols was established by EA-SPME coupled with gas chromatography-flame ionization detection. Under the optimal experimental conditions (extraction temperature: 40 °C; extraction time: 30 min; stirring rate: 600 rpm; NaCl concentration: 0.15 g mL-1; desorption temperature: 250 °C and desorption time: 4 min), the detection linear range was 0.005-50 µg L-1 (R2>0.99), and the detection limit was 0.001-0.1 µg L-1 (S/N = 3). For the quintuple analysis of 50 µg L-1 phenols, the single fiber RSDs were 2.2-12.4%, and the fiber-to-fiber RSDs were 1.9-10.5%. The method was used to detect the migration quantity of the eight phenols from five canned packaging materials, which showed satisfactory recovery 87.3-118.9%.

Magnetic Fe3O4@SiO2@ß-cyclodextrin for solid phase extraction of methyl parathion and fenthion in lettuce samples.

In this study, magnetic Fe3O4@SiO2@ß-cyclodextrin copolymerized microparticles were synthesized and applied for the extraction of methyl parathion and fenthion in lettuce samples followed by HPLC-UV detection. The magnetic ß-cyclodextrin copolymerized microparticles were prepared by dispersion polymerization with acryloyl ß-cyclodextrin as the functional monomer and ethylene glycol dimethyacrylate as the crosslinker. The composite magnetic microparticles were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, magnetic measurement, and thermogravimetric analysis, and used as the adsorbent of magnetic solid-phase extraction (MSPE) for methyl parathion and fenthion. The extraction conditions including sample pH and ionic strength, desorption solvent type and volume, and adsorption and desorption times were optimized. Under the optimal extraction conditions, an MSPE-HPLC-UV method was developed for the detection of methyl parathion and fenthion in lettuce. Wide linear ranges of 1.0-200 µg kg-1 (R2 = 0.9998) for methyl parathion and 1.5-200 µg kg-1 (R2 = 0.9978) for fenthion were obtained and the limits of detection were 0.3 µg kg-1 for methyl parathion and 0.5 µg kg-1 for fenthion in lettuce, respectively. The proposed method was applied for the determination of methyl parathion and fenthion in lettuce with satisfactory recoveries between 89.2-101.2%, and relative standard deviations were less than 9.1%. Thus, the MSPE-HPLC-UV method has high accuracy and sensitivity for the analysis of methyl parathion and fenthion in lettuce samples.

Moisture-sensitive metal-organic framework constructed from cobalt and 4-(4-pyridyl) benzoic acid for dispersive solid-phase extraction of polycyclic aromatic hydrocarbons in apple.

A moisture-sensitive metal-organic framework CoII (pybz)2 ·2DMF was synthesized and applied as the adsorbent of dispersive solid-phase extraction. The structure changed after water treatment due to the fact that two chelate carboxylate groups on the skeleton were transformed to monodentate because of the coordination of water molecules. The material showed good adsorption for fluorene, phenanthrene, fluoranthene, and pyrene in water because of the π-π conjugation and π-complexation effects. Coupled with high-performance liquid chromatography, a dispersive solid-phase extraction method of determining the content of fluorene, phenanthrene, fluoranthene, and pyrene in apple samples was established after optimizing the extraction conditions. Methanol containing 4% acetic acid was used as the effective eluent. The linearities were 0.5-1000 µg/kg for fluorene, phenanthrene and 5-1000 µg/kg for fluoranthene, pyrene. The limits of detection were 0.06-0.6 µg/kg, and the recoveries were 94.4-116.4%. The method has a high sensitivity for the determination of four polycyclic aromatic hydrocarbons in apple samples.

A polythiophene/UiO-66 composite coating for extraction of volatile organic compounds migrated from ion-exchange resins prior to their determination by gas chromatography.

A Poly (3,4-ethylenedioxothiophene) (PEDOT)/UiO-66 composite was electrodeposited on an etched stainless-steel wire as head-space solid-phase microextraction (HS-SPME) coating. A robust, well controlled thickness, and uniform coating of metal organic framework composites can be realized by the electrodeposited strategy. The incorporated UiO-66 not only enhanced the uniformity and stability of the composite coating, but also effectively decreased the stacking phenomenon of PEDOT and improved its extraction efficiency, which was over 100 times higher than that of the PEDOT coating without UiO-66. The composite coating was used to enrich seven types of volatile organic compounds (VOCs) in ion-exchange resins, including methyl cyclohexane, benzene, toluene, ortho-xylene, styrene, para-xylene and divinyl-benzene. The results of adsorption isotherm analysis showed that π stacking effect played dominant role between the composite coating and VOCs in the extraction process. The composite coating was characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared and thermogravimetric analysis, respectively. A determination method for seven kinds of VOCs was established by HS-SPME coupled with gas chromatography-flame ionization detection (GC-FID). Under the optimal experimental conditions, the detection linear range (LRs) was 0.09-100 ng mL-1, and the detection limit (LODs) was 0.03-0.06 ng mL-1 (S/N = 3). The method was applied for the migration detection of VOCs in four types of ion-exchange resin, which showed satisfactory recovery (84.5-117.2%).

Fe3 O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and ß-cyclodextrin for magnetic solid-phase extraction of carbaryl and carbofuran.

In this study, porous sandwich structure Fe3 O4 nanoparticles coated by polyhedral oligomeric silsesquioxanes and ß-cyclodextrin were prepared by surface polymerization and were used as the magnetic solid phase extraction adsorbent for the extraction and determination of carbaryl and carbofuran. The Fe3 O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and ß-cyclodextrin were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, and scanning electron microscopy. After optimizing the extraction conditions, a method that combined magnetic solid phase extraction with high-performance liquid chromatography was developed for the determination of carbaryl and carbofuran in apple. The method exhibited a good linearity in the range of 2-400 µg/kg for carbaryl and carbofuran (R2  = 0.9995), respectively. The limits of detection were 0.5 µg/kg of carbaryl and 0.7 µg/kg for carbofuran in apple, respectively. Extraction recoveries ranged from 94.2 to 103.1% with the preconcentration factor of 300 and the relative standard deviations were less than 5.9%. These results indicated that the method combined magnetic solid phase extraction with high-performance liquid chromatography and was promising for the determination of carbaryl and carbofuran at trace amounts.

A nanocomposite consisting of etched multiwalled carbon nanotubes, amino-modified metal-organic framework UiO-66 and polyaniline for preconcentration of polycyclic aromatic hydrocarbons prior to their determination by HPLC.

A polyaniline composite doped with etched multi-walled carbon nanotubes and UiO-66-NH2 was prepared by electropolymerization. It was used as a sorbent to extract the polycyclic aromatic hydrocarbons (PAHs) phenanthrene, fluoranthene and pyrene. Its surface morphology, crystal structure and capability of adsorbing PAHs were characterized by scanning electron microscopy, X-ray photoelectron spectrometry, Fourier transform infrared spectrometry and zeta potentiometry. The π stacking and anion-π interactions are shown to play dominant roles in the sorption mechanism. Coupled with high performance liquid chromatography, the composite-modified fiber was applied to detect PAHs in lake water samples by direct immersion extraction. The method excels by (a) wide linear range (0.05-20 ng mL-1), (b) low limits of detection (10 pg mL-1), (c) satisfactory recovery from spiked samples (84.7-113.8%), and (d) good reproducibility (relative standard deviations of <6.5%). The method is superior in terms of costs and reproducibility compared to some pretreatment methods with mass spectrometric detection. Graphical abstractSchematic representation for interaction between PANI-etched MWCNT/UiO-66-NH2 and polycyclic aromatic hydrocarbons (phenanthrene, fluoranthene, pyrene).

Adsorption Behavior of Polycyclic Aromatic Hydrocarbons on Zn-Based Coordination Cluster Zn5: Competition, Synergy, and Mechanism.

In this work, adsorption behaviors of pyrene (PYR), fluoranthene (FLT), phenanthrene (PHE), and fluorene (FLU) on the coordination cluster [Zn5(H2Ln)6](NO3)4]·8H2O·2CH3OH (Zn5) were studied. The adsorption mechanism and spectrum analyses revealed that the synergistic effect of hydrophobic interaction, π-π stacking, and N-H···π interaction played a crucial role during the adsorption process. The maximum adsorption capacities of PYR, FLT, PHE, and FLU were 406.4, 399.7, 153.7, and 114.3 mg g-1, respectively, resulting from the Langmuir isotherm model. Quick removal of PYR and FLT was found in kinetic experiments with the adsorption equilibrium being reached within 1 min. Competitive adsorption indicated that the adsorption sites for PYR, FLT, PHE, and FLU on Zn5 were identical, and synergistic effects also existed in the adsorption process. Therefore, Zn5 has the potential to be used as an adsorbent in the field of wastewater treatment.

One-pot preparation of an acryloyled ß-cyclodextrin-silica hybrid monolithic column and its application for determination of carbendazim and carbaryl.

This work describes, for the first time, an acryloyled ß-cyclodextrin hybrid monolith column was synthesized, under aqueous-phase conditions, and used for solid-phase microextraction of carbendazim and carbaryl. The monolithic column was characterized using scanning electron microscopy, nitrogen adsorption-desorption, thermogravimetric analysis and Fourier transform infrared spectroscopy, and used as the adsorbent for solid phase microextraction (SPME) of carbendazim and carbaryl. After optimization of the SPME conditions, a simple and sensitive SPME-HPLC method was developed for the determination of carbendazim and carbaryl in leafy vegetables. The method exhibited a good liner response in the range 5-400 µg/kg (R2 = 0.9994) for carbendazim and 10-400 µg/kg (R2 = 0.9996) for carbaryl, respectively. The limits of detection were 1.0 and 1.5 µg/kg for carbendazim and carbaryl, respectively, in leafy vegetables. Recoveries ranged from 92.6% to 110.1%, and the relative standard deviations were less than 6.1%.

A Selective Joint Determination of Salicylic Acid in Actinidia chinensis Combining a Molecularly Imprinted Monolithic Column and a Graphene Oxide Modified Electrode.

A new combination between selective polymer monolith microextraction (PMME) and sensitive differential pulse voltammetry (DPV) was developed for the determination of the phytohormone salicylic acid (SA) in Actinidia chinensis. A molecularly imprinted monolithic column (MIMC) thermally in-situ polymerized in a micropipette tip by using SA as a template, 4-vinyl pyridine (4-VP) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross-linker in the mixed porogen of toluene and dodecanol, was employed for the microextraction of SA. The prepared MIMC was characterized by a Fourier transform infrared spectrometer (FI-TR), scanning electron microscope (SEM) and thermo gravimetric analysis (TGA). The results confirmed the binary continuous structure of the porous network. The extracted SA was determined by DPV on a graphene oxide (GO) modified electrode. The joint conditions between MIMC and DPV were investigated practically. Under the optimum conditions, SA could be determined selectively and sensitively in a linear range from 0.1 to 60.0 µg g-1. The limit of detection was 0.03 µg g-1 and the recoveries were between 86.2 and 105.2%. The proposed joint method was successfully used to determine SA in Actinidia chinensis.

Preparation of an acryloyl ß-cyclodextrin-silica hybrid monolithic column and its application in pipette tip solid-phase extraction and HPLC analysis of methyl parathion and fenthion.

An acryloyl ß-cyclodextrin-silica hybrid monolithic column for pipette tip solid-phase extraction and high-performance liquid chromatography determination of methyl parathion and fenthion has been prepared through a sol-gel polymerization method. The synthesis conditions, including the volume of cross-linker and the ratio of inorganic solution to organic solution, were optimized. The prepared monolithic column was characterized by thermogravimetric analysis, scanning electron microscopy, and Fourier transform infrared spectroscopy. The eluent type, volume and flow rate, sample volume, flow rate, acidity, and ionic strength were optimized in detail. Under the optimized conditions, a simple and sensitive pipette tip solid-phase extraction with high-performance liquid chromatography method was developed for the determination of methyl parathion and fenthion in lettuce. The method yielded a linear calibration curve in the concentration ranges of 15-400 µg/kg for methyl parathion and 20-400 µg/kg for fenthion with correlation coefficients of above 0.9957. The limits of detection were 4.5 µg/kg for methyl parathion and 6.0 µg/kg for fenthion, respectively. The recoveries of methyl parathion and fenthion spiked in lettuce ranged from 96.0 to 104.2% with relative standard deviations less than 8.4%.

Magnetic Solid-Phase Extraction of N,N-Diethyl-m-Toluamide From Baby Toilet Water Prior to its HPLC-UV Detection.

Fe3O4@MIL-100 (MIL, Material Institut Lavoisier) core-shell magnetic microspheres were prepared and applied as the sorbent for the magnetic solid phase extraction (MSPE) of N,N-diethyl-m-toluamide (DEET) in baby toilet water for the first time. The synthesized magnetic metal-organic frameworks were characterized by transmission electron microscope, infrared spectroscopy and thermogravimetric analysis. The functionalized magnetic microparticles showed excellent dispersibility in aqueous solution. The MSPE conditions were investigated in detail. Under the optimized conditions, an MSPE-high performance liquid chromatography method for the determination of DEET was developed. The method was linear in the concentration range from 5 to 500 µg L-1 for DEET in baby toilet water and good linearity (r2 > 0.9998) was obtained for the calibration curve. The limit of detection was 1.5 µg L-1. Both the intra-day and inter-day precisions (relative standard deviations) were <3%.

A novel dispersive solid-phase extraction method using metal-organic framework MIL-101 as the adsorbent for the analysis of benzophenones in toner.

Metal-organic frameworks (MOFs) have been paid widespread attention in the field of adsorption and separation materials due to its porosity, large specific surface area, unsaturated metal-ligand sites and structural diversity. In this study, the green powder MIL-101 was synthesized and used for the extraction of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples for the first time. The synthesized MIL-101 was characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry and nitrogen adsorption porosimetry. The MIL-101 was applied as the dispersive solid phase extraction (DSPE) adsorbent for the extraction and preconcentration of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone from toner samples. The extraction conditions were investigated. Under the optimized conditions, a DSPE-HPLC method for the determination of benzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxy-benzophenone was developed. The method yielded a linear calibration curve in the concentration ranges from 4.0 to 3500 µg L(-1) for the three analytes in toner samples with regression coefficients (r(2)) of 0.9992, 0.9999 and 0.9990, respectively. Limits of detection were 1.2, 1.2 and 0.9 µg L(-1), respectively. Both the intra-day and inter-day precisions (RSDs) were <10%.

Preparation and application of a novel electrochemical sensing material based on surface chemistry of polyhydroquinone.

A new analogue of polydopamine (PDA), i.e., polyhydroquinone (PH2Q), was polymerized and its surface chemistry was studied by different ways of characterization. PH2Q was produced by the self-polymerization of H2Q mediated by dissolved oxygen, and the self-polymerization process was strongly dependent on the type and the pH value of the buffer solutions. PH2Q can not only achieve surface hydrophilization of different substrates like polyethylene terephthalate (PET) film, graphite strip, C12SH/Au and wax slice, but also possess several unique properties like reversible adsorption, good solubility and low cost. These properties made PH2Q an ideal polymeric modifier for the noncovalent functionalization of some nanomaterials. By simply grinding with PH2Q, pristine multi-walled carbon nanotubes (MWNTs) can be readily dispersed in water with high solubility and good stability. The resulting MWNT-PH2Q composite exhibited excellent electrochemical performance, which was employed for the simultaneous determination of dopamine (DA) and uric acid (UA).

Preparation of 2,4-dichlorophenoxyacetic acid imprinted organic-inorganic hybrid monolithic column and application to selective solid-phase microextraction.

An organic-inorganic hybrid molecular imprinting monolith (HMIM) has been prepared, characterized and applied for the determination of 2,4-dichlorophenoxyacetic acid (2,4-D) in rice with high-performance liquid chromatography-photodiodes array detector (HPLC-PAD). By optimizing the polymerization conditions, such as the volume ratio of the inorganic alcoholysate and organic part, the 2,4-D-HMIM was synthesized in a micro pipette tip using acrylamide as the functional monomer, ethylene dimethacrylate as the cross-linker and methanol as the porogenic solvent. The morphology of the monolith was studied by scanning electronmicroscopy and Fourier transform infrared spectra. The imprinted factor of the monolith for 2,4-D reached 3.29. A simple, rapid and sensitive method for the determination of 2,4-D in rice using the HMIM microextraction combined with high-performance liquid chromatography-photodiodes array detector was developed. Some parameters affecting the sample pretreatment were investigated, including the type and volume of eluent, the flow rate and volume of sample solution. The assay exhibited a linear dynamic range of 167-4167µg/kg with the correlation coefficient above 0.9972. The detection limit (at S/N=3) was 50µg/kg. The proposed method was successfully applied for the selective determination of 2,4-D in rice.