CuI-p-DPA coordination polymer isomers for "turn-on" fluorescence detection of thiophanate-methyl.

Three copper iodide coordination polymer (CuI-p-DPA) isomers were prepared from the fluorescent organic ligand p-DPA and cuprous iodide (CuI) under different solvothermal conditions, which exhibited quenched fluorescence behaviors after forming coordination polymers (CPs). These CuI-p-DPA isomers showed discrepant fluorescence responses to thiophanate-methyl (TM). Among these CuI-p-DPA isomers, α-CuI-p-DPA exhibited the maximum fluorescence enhancement after its incubation with TM in aqueous solution. The fluorescence enhancement mechanism was that TM competed with the ligand p-DPA to coordinate with CuI clusters, and then α-CuI-p-DPA released p-DPA into the solution and induced fluorescence enhancement. The present detection method possesses the advantages of good selectivity, high sensitivity, short response time, and strong anti-interference ability with a linear range of 0.5-100 µM and a detection limit of 0.01 µM. This study not only reveals that the spatial structures of CPs play an important role in the fluorescence response ability, but also provide a new fluorescence signal-on analysis method to rapidly and sensitively determine the pesticide residue for TM.

Comparison of supercritical fluid chromatography-tandem mass spectrometry and liquid chromatography-tandem mass spectrometry for the stereoselective analysis of chlorfenvinphos and dimethylvinphos in tobacco.

This study used reversed-phase liquid chromatography-tandem mass spectrometry and supercritical fluid chromatography-tandem mass spectrometry for determination of the stereoisomers of chlorfenvinphos and dimethylvinphos in tobacco. Tobacco samples were extracted and purified with a modified quick, easy, cheap, effective, rugged, and safe technique using spherical carbon. The performance of both methodologies was comprehensively compared in terms of methods validation parameters (separation efficiency, linearity, selectivity, recovery, repeatability, sensitivity, matrix effect, etc.). Under optimized conditions, the calibration curves of the stereoisomers of chlorfenvinphos and dimethylvinphos in the range of 10-500 ng/mL showed excellent linearity with R2 ≥ 0.997 in both methods. The adequate recoveries of analytes from three different spiked tobaccos were obtained using reversed-phase liquid chromatography-tandem mass spectrometry (86.1-95.7%) as well as supercritical fluid chromatography-tandem mass spectrometry (86.5-94.0%). The relative standard deviations for spiked samples were all below 7.0%. Compared with supercritical fluid chromatography-tandem mass spectrometry, lower matrix effects and LODs can be obtained in reversed-phase liquid chromatography-tandem mass spectrometry.

Metal-Organic Framework with Near-Infrared Luminescence for "Switch-on" Determination of Kaempferol and Quercetin by the Antenna Effect.

The establishment of a reliable and sensitive method for the detection of flavonoids, such as kaempferol (Kae) and quercetin (Que), is important and challenging in food chemistry and pharmacology because numerous structural analogues may interfere with the detection. Until now, designing an efficient switch-on fluorescence sensing strategy for Kae and Que was still in the unachievable stage. In this work, a switch-on near-infrared (NIR) luminescence sensing assay for Kae and Que was fabricated based on a metal-organic framework (MOF) called IQBA-Yb for the first time. The fluorescence enhancing mechanism was that analytes served as additional "antenna" of Yb3+, leading to the efficient switch-on NIR emission under excitation at 467 nm. Meanwhile, the combination results of experiment and theoretical calculation revealed that there existed hydrogen bonds between Kae, Que, and the MOF skeleton, further promoting the energy transfer between the analyte and Yb3+ and facilitating fluorescence enhancement response. The developed probe possessed excellent sensing capability for Kae and Que, accompanied by a wide linear range (0.04-70, 0.06-90 µM), low detection limit (0.01, 0.06 µM), and short response time (20 min, 6 min), which was used to determine the Kae and Que contents in Green Lake and eatable Que samples with satisfactory results.

Morphology-Dependent Peroxidase Mimicking Enzyme Activity of Copper Metal-Organic Polyhedra Assemblies.

The morphology of nanomaterials (geometric shape and dimension) play a significant role in its various physical and chemical properties. Thus, it is essential to link morphology with performance in specific applications. For this purpose, the morphology of copper metal-organic polyhedra (Cu-MOP) can be modulated through distinct assembly process, which facilitates the exploration of the relationship between morphology and catalytic performance. In this work, the assemblies of Cu-MOP with three different morphologies (nanorods, nanofibers and nanosheets) were facilely prepared by the variation of solvent mixture of N, N-dimethylformamide (DMF) and methanol, revealed the important role of the interaction between the surface group and the solvent on the morphology of these assemblies. Cu-MOP nanofibers exhibited the highest mimetic peroxidase enzyme activity over the Cu-MOP nanosheets and nanorods, which have been utilized in the detection of glucose. Cu-MOPs assemblies with tunable morphology accompanied with adjustable mimic peroxidase activity, had great potential applications in the field of bioanalytical chemistry and biomedicals.

Electrochemical Sensor Based on Rh(III) Ion-Imprinted Polymer as a New Modifying Agent for Rhodium Determination.

A rhodium (III) ion carbon paste electrode (CPE) based on an ion imprinted polymer (IIP) as a new modifying agent has been prepared and studied. Rh(III) ion imprinted polymer was synthesized by copolymerization of acrylamide-Rh(III) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Acrylamide acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. The ion imprinted carbon paste electrode (IIP-CPE) was prepared by mixing rhodium IIP-nanoparticles and graphite powder in n-eicosane as an adhesive and then embedding them in a Teflon tube. Amperometric i-t curve method was applied as the determination technique. Several parameters, including the functional monomer, molar ratio of template, monomer and cross-linking agent, the amounts of IIP, the applied potential, the buffer solution and pH have been studied. According to the results, IIP-CPE showed a considerably higher response in comparison with the electrode embedded with non-imprinted polymer (NIP), indicating the formation of suitable recognition sites in the IIP structure during the polymerization stage. The introduced electrode showed a linear range of 1.00×10-8~3.0×10-5 mol·L-1 and detection limit of 6.0 nmol L-1 (S/N = 3). The IIP-CPE was successfully applied for the trace rhodium determination in catalyst and plant samples with RSD of less than 3.3% (n = 5) and recoveries in the range of 95.5~102.5%.

A Novel Sensitive Electrochemical Sensor for Podophyllotoxin Assay Based on the Molecularly Imprinted Poly-o-Phenylenediamine Film.

An electrochemical sensor for podophyllotoxin (PPT) based on the molecular imprinting polymer (MIP) membranes was constructed. The sensor was prepared by electropolymerizing o-phenylenediamine (o-PD) on a glassy carbon electrode (GCE) in the presence of PPT as template, and then removing the template by immersing the modified GCE in ethanol. Experimental parameters such as the types of monomer, scan cycles, concentration of o-PD and extraction condition were optimized. Under optimal conditions, the sensor exhibits a good selectivity and high sensitivity. A good linearity was obtained in the range of 4 x 10-8 mol · L(-1) to 3.2 x 10(-5) mol · L(-1) with an estimated detection limit of 4.8 x 10(-9) mol · L(-1). The sensor was applied to the determination of PPT in podophyllum hexandrum and human serum samples with satisfactory results.

Qualitative determination of volatile substances in different flavored cigarette paper by using headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) combined with chemometrics.

In order to investigate the difference of volatile substances among flavored cigarette paper, which are supplied by several manufacturers with different batches, the stability of the complex system of scented cigarette paper was analyzed and evaluated. In this study, Headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) was used to detect the aroma compounds of 23 flavored cigarette paper samples. Based on fingerprint analysis, the differences and changes of aroma compounds of different samples were studied in the form of data visualization. Principal component analysis, partial least squares regression analysis, cluster heatmap analysis and artificial neural network analysis were used to evaluate the stability of different cigarette paper. The results show that: A total of 29 volatile substances were identified from different scented cigarette paper. Fingerprint analysis revealed that the volatile substances of different cigarette paper samples were roughly the same, but not the content. The results of chemometrics analysis showed that there were significant differences in the characteristic aroma compounds of cigarette paper from different manufacturers. HS-GC-IMS technology combined with chemometrics method could be applied to determine the difference of volatile substances among different flavored cigarette paper, which theoretically and technically supported the quality stability maintenance and identification of flavored cigarette paper processed in different places.

Analysis of 10 Phthalate Esters in Water-Based Adhesives by Supercritical Fluid Chromatography-Tandem Mass Spectrometry Combined With Spherical Carbons-Based Dispersion Solid-Phase Extraction.

BACKGROUND: Spherical carbons have a porous structure and large surface area for adsorption of macromolecules in water-based adhesives. Supercritical fluid chromatography (SFC) can improve selectivity and obtain better separation for phthalate esters (PAEs). OBJECTIVE: The aim of this study was to develop a simple and green method for the simultaneous determination of 10 PAEs in water-based adhesives using SFC-tandem mass spectrometry with dispersion solid-phase extraction by spherical carbons. METHOD: Separation of PAEs on a Viridis HSS C18 SB column and the parameters affecting the extraction were evaluated. RESULTS: Good accuracy and precision were obtained with the recoveries at 0.5, 2.0, and 10.0 mg/kg ranging from 82.9 to 99.5% and the intra- and inter-day precision less than 7%. The method had excellent sensitivity with limits of detection in the range of 0.015-0.029 mg/kg. In the 10-500 ng/mL concentration range, the linear correlation coefficients of all compounds were between 0.9975 and 0.9995. CONCLUSIONS: The method was applied to the determination of 10 PAEs in actual samples. This method is simple and rapid with low solvent consumption and high extraction efficiency. When applied to the determination of PAEs in actual samples, the method is sensitive and accurate and can meet the batch processing requirements for trace PAEs in water-based adhesives. HIGHLIGHTS: PAEs in water-based adhesives can be determined using inexpensive materials and simple procedures with SFC.

Establishment of a Colloidal Gold Immunochromatographic Method for the Detection of Cypermethrin in Tobacco.

In this study, the establishment of a colloidal gold immunochromatographic method for the detection of cypermethrin in tobacco was achieved by using colloidal gold immunochromatography: strong specificity and high sensitivity of cypermethrin semi-antigens and encapsulants were prepared during the study. The best colloidal gold solution was prepared by spectrophotometer and transmission electron microscope screening; the preparation process of gold-labeled antibodies was optimized, and finally the product of colloidal gold rapid detection test strips for cypermethrin was developed. The results of technical parameters and detection indexes showed that the detection limit of cypermethrin in tobacco was 1 mg/kg, and there was no cross-reaction with bifenthrin, cypermethrin, cyfluthrin and phenothrin, and the detection results of 30 tobacco samples were consistent with those of gas chromatography.

Development of Colloidal Gold Test Strips for the Detection of Oxamyl Residues in Tobacco.

In this study, monoclonal antibodies against oxamyl were prepared, and colloidal gold immunochromatography was used to design a rapid test strip product for the detection of oxamyl in tobacco with high specificity, accuracy and stability without cross-reactivity to commonly used tobacco fungicides based on the optimization of conditions such as pH value of diluent, diluent dosage, concentration of antibody marker, type of confining solution and complex solution. 5 The results of five samples of post-harvest ready-to-bake tobacco and first-harvest tobacco were consistent with the gas chromatographic method, which proved the reliability of the test strips. The limits of detection for the post-harvest and first-harvest tobacco samples were 0.1 mg/kg, and the test strips developed in this study are suitable for mass testing in tobacco laboratories with good application prospects because of their short detection time, simple pre-treatment and detection methods.

Development of Colloidal Gold Test Strips for the Detection of Triadimenol Residues in Tobacco.

The rapid and accurate determination of triadimenol residues is of great significance. In this study, based on the advantages of high efficiency, rapidity, reliability, simplicity and low cost of immunology, a test strip product for the rapid detection of triadimenol residues in tobacco was designed based on the optimization of conditions such as pH and dosage of diluent, concentration of antibody stock solution, type of confining solution and complex solution, with high specificity, accuracy and The results of 20 samples of fresh and first roasted tobacco were all consistent with the method of gas chromatography, which proved the reliability of the test strips. The detection limit for fresh and roasted tobacco was 5 mg/kg, and the test strips developed in this study are suitable for mass testing of tobacco samples in tobacco-related laboratories because of their short detection time, simple pre-treatment and detection methods, and good application prospects.

A portable smartphone-based detection of glyphosate based on inhibiting peroxidase-like activity of heptanoic acid/Prussian blue decorated Fe3O4 nanoparticles.

The rapid and onsite detection of glyphosate in tobacco products is still a great challenge. In this study, a novel smartphone-assisted sensing platform for the detection of glyphosate has been successfully proposed through the peroxidase-like activity of Fe3O4-based nanozyme. Heptanoic acid/Prussian blue (PB) decorated Fe3O4 nanoparticles (Fe3O4@C7/PB) could catalyze and oxidize 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS, colorless) into a steel blue colored product in the presence of hydrogen peroxide. Glyphosate could specifically inhibit the peroxidase-like activity of Fe3O4@C7/PB by occupying the active site, thereby the glyphosate detection could be accomplished within 10 min by monitoring the color change of ABTS. This study has developed a smartphone-based portable detection platform for online analysis of glyphosate with a detection limit of 0.1 µg mL-1. The absorbance response curve of glyphosate showed good linearity in the concentration range of 0.125-15 µg mL-1 at 415, 647, and 730 nm. Moreover, by employing a co-precipitation technology and inhibiting the peroxidase-like activity, the glyphosate analysis would be less affected by the tobacco sample matrix. The nanosensor possesses excellent selectivity and anti-interference ability, which has application value in actual samples for onsite screening.

Star-shaped porous nitrogen-doped metal-organic framework carbon as an electrochemical platform for sensitive determination of Cd(II) in environmental and tobacco samples.

In this study, cetyltrimethylammonium bromide and zeolitic imidazolate framework-8 (ZIF-8) were first assembled via the chemical co-precipitation, and high-quality carbon-based metal-free nanomaterials were synthesized using a heat-treatment process. The internal and morphological characteristics of hexagonal Star ZIF-8 were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The electrochemical sensor with a good response to Cd(II) was prepared via square-wave anodic stripping voltammetry (SWASV) with Star ZIF-8 nanomaterial-modified glassy carbon electrodes. The main parameters were adjusted to obtain the optimal stripping response and a wide linear range. Concurrently, under the calculation of SWASV, the sensitivity of Star ZIF-8-Nafion/GCE to Cd(II) was increased by five orders of magnitude (0.5-230 µg/L), and the determination level was even low to 0.48 µg/L. Based on the high anti-interference ability and stability of the sensor, the application potential of Star ZIF-8 carbon-based metal-free nanomaterials for the detection of trace Cd(II) in was confirmed.

A novel sensitive electrochemical sensor based on in-situ polymerized molecularly imprinted membranes at graphene modified electrode for artemisinin determination.

To develop a rapid and simple method for sensitive determination of artemisinin (ART) in complicated matrices, a novel electrochemical sensor was constructed by in-situ polymerization of ART-imprinted membranes (ART-MIMs) on the surface of graphene (G) modified glassy carbon electrode (GCE) using acrylamide (AM) as functional monomer, ethylene glycol dimethacrylate (EGDMA) as cross-linking agent after the experimental parameters for the preparation of ART-MIMs such as functional monomer, molar ratio of template, monomer and cross-linking agent together with extraction condition were optimized. Under the optimal conditions, the sensor named as ART-MIM/G/GCE exhibited a good selectivity, high sensitivity and considerably better resistance against some analogs of artemisinin such as dihydroartemisinin (DHA), artemether (ARM) and artesunate (ARTS). The calibration graph for the determination of artemisinin by the sensor was linear in the range of 1.0 × 10(-8)mol L(-1) to 4.0 × 10(-5)mol L(-1) with the detection limit of 2.0 × 10(-9)mol L(-1). Meanwhile, this sensor possessed of good regeneration, stability and practicability. It could retain more than 94% of its original response after used at least 80 times or stored in water at room temperature for 60 days. The obtained sensor was successfully applied to determine the contents of artemisinin in the extract of Artemisia annua L. with the relative standard deviation (RSD) of less than 3.5% (n=5).