Cellulose Nanocrystals Induced Loose and Porous Graphite Phase Carbon Nitride/Porous Carbon Composites for Capturing and Determining of Organochlorine Pesticides from Water and Fruit Juice by Solid-Phase Microextraction.

Herein, novel, loose, and porous graphite phase carbon nitride/porous carbon (g-C3N4@PC) composites were prepared by decorating cellulose nanocrystals (CNCs). The characterization results demonstrate that the as-prepared composites presented high specific surface areas, porous structures, and abundant chemical groups, with the modification of CNCs. In view of the unique advantages, g-C3N4@PC was used as the coating material for the solid-phase microextraction (SPME) of organochlorine pesticides (OCPs) in water and juice samples. The g-C3N4@PC-coated fibers showed better extraction efficiencies than commercial fibers (100/7 µm PDMS and PA) toward the OCPs, with the enrichment factors of the g-C3N4@PC-coated fibers 5-30 times higher than the latter. Using a gas chromatography-mass spectrometry (GC-MS) instrument, the g-C3N4@PC-coated fibers exhibited a gratifying analytical performance for determining low concentrations of OCPs, with a wide linear range (0.1-1600 ng L-1 for water; 0.1-1000 ng L-1 for juice), low limits of detection (0.0141-0.0942 ng L-1 for water; 0.0245-0.0777 ng L-1 for juice), and good reproducibility and repeatability in optimal conditions. The established method showed good sensitivity and recovery in the determination of OCPs in the water and fruit juice samples, which displayed broad prospects for analyzing organic pollutants from environmental samples.

High-throughput profiling volatiles in edible oils by cooling assisted solid-phase microextraction technique for sensitive discrimination of edible oils adulteration.

In this study, a cooling assisted solid-phase microextraction technique (CA-SPME) was proposed and used for identifying volatile and semi-volatile compounds in edible oil innovatively coupled to gas chromatography-mass spectrometry. Compared with regular SPME technique, CA-SPME presented significantly higher extraction efficiencies for analytes in edible oil due to its synergistic effect of heating and cooling. After optimization of the extraction conditions including heating temperature, cooling temperature, extraction time, and added amount of edible oil, thirty-eight, thirty-six, twenty-nine, and thirty-three kinds of compounds in peanut oil, olive oil, canola oil, and soybean oil were successfully identified, respectively, using DVB/CAR/PDMS coating with extraction time of 30 min and edible oil amounts of 20 µL. Principal component analysis, partial least squares discriminant analysis, and hierarchical clustering analysis (HCA) were performed to evaluate the potential of proposed method in discriminating edible oils adulteration (peanut oil adulterated with canola oil, peanut oil adulterated with soybean oil, olive oil adulterated with canola oil) subsequently. Results demonstrated that the method was useful in successful discrimination of pure and adulterated edible oils with adulteration percentages ranging from 0.5 to 10%. Furthermore, volatiles contributing to classifications between pure and adulterated edible oils were also illustrated based on variable importance for the projection analysis and distributions of volatiles in HCA heatmaps. The proposed method provided a novel strategy for sensitive detection of edible oil adulteration without any other sample pretreatment.

Lotus-like Ni@NiO nanoparticles embedded porous carbon derived from MOF-74/cellulose nanocrystal hybrids as solid phase microextraction coating for ultrasensitive determination of chlorobenzenes from water.

Lotus-like Ni@NiO embedded porous carbons (Ni@NiO/PCs) were fabricated by pyrolysis of MOF-74/cellulose nanocrystal hybrids, and used as a solid phase microextraction (SPME) coating for ultrasensitive determination of chlorobenzenes (CBs) from water combined with gas chromatography-mass spectrometry. Owing to its abundant chemical groups, high porosity, and excellent thermal stability, the as-prepared Ni@NiO/PCs presented superior extraction performance compared to commercial SPME coatings. Notably, Ni@NiO/PCs derived from MOF-74/CNC hybrids presented higher extraction efficiencies towards CBs than that derived from pristine CNC and MOF-74 due to the formation of micro/mesopores and more abundant oxygen-containing groups. Under the optimum extraction conditions, the proposed analytical method presented wide linearity range (0.5-1500 ng L-1), ultra-low detection of limit (0.005-0.049 ng L-1), and excellent precision with relative standard deviations of 4.7-9.2% for a single fiber and 8.8-10.9% for 5 fibers, and long lifetime (≥160 times). The proposed analytical method was finally applied for determination of CBs from real water samples, and the recoveries were in the range of 93.2-116.8% towards eight CBs. This study delivered a novel and efficient sorbent as SPME coating to extraction and determination of CBs from water.

Core-shell structured Fe2O3/CeO2@MnO2 microspheres with abundant surface oxygen for sensitive solid-phase microextraction of polycyclic aromatic hydrocarbons from water.

Core-shell structured Fe2O3/CeO2@MnO2 microspheres were fabricated and used as solid-phase microextraction coating for determination of polycyclic aromatic hydrocarbons (PAHs) in water samples. XPS spectra demonstrated the generation of abundant surface oxygen on Fe2O3/CeO2@MnO2 microspheres, which provided binding sites for enhancement of analyte extraction. Under optimized conditions, the proposed method presented good linearity in the concentration range 0.04-100 ng mL-1, with low limits of detection varying from 0.38 to 3.57 ng L-1 for eight PAHs. Relative standard deviations for a single fiber and five batches of fibers were in the ranges of 4.1-8.2% and 7.1-11.4%, respectively. The proposed method was successfully used for determination of PAHs in real river water samples with recoveries ranging from 87.1 to 115.9%. The proposed method using as-prepared Fe2O3/CeO2@MnO2 microspheres as SPME coating exhibit significant potential for real sample analysis due to its excellent reproducibility, high sensitivity, and good linearity.

A facile cooling-assisted solid-phase microextraction device for solvent-free sampling of polycyclic aromatic hydrocarbons from soil based on matrix solid-phase dispersion technique.

Solvent-free analysis of organic pollutants from a complex matrix has attracted significant attention. In this work, we designed and fabricated a facile cooling-assisted solid-phase microextraction device (CA-SPME) that could be used for the solvent-free extraction of volatile and semivolatile compounds from a complex matrix using a commercial SPME probe. Determination of polycyclic aromatic hydrocarbons (PAHs) from soil samples was carried out to evaluate the performance of the designed CA-SPME device. The effects of heating temperature, cooling temperature, extraction time, and moisture content in soil on extraction efficiency were investigated. To enhance the extraction efficiency of the targeted analytes, the matrix solid-phase dispersion technique (MSPD) by grinding soil with silica gels was applied. The results showed that grinding with silica gels promoted the release of PAHs from the soil matrix to the headspace by disrupting the matrix structure, which then facilitated the extraction efficiency. Under optimized conditions, for all of the targeted PAHs, the method exhibited good linearity (40-4000 ng g-1) with regression coefficients (R2) ranging from 0.9586 to 0.9964. The limits of detection and limits of quantification ranged from 4.2 to 8.5 ng g-1 and 14.0-28.5 ng g-1, respectively. Relative standard deviations corresponding to the analysis of spiked soil samples (n = 5) were 8.1-13.4%. The solvent-free analysis of the certified soil sample using the proposed method demonstrated satisfactory results.