On the use of a 2D-carbon microfiber fractionation system to improve flow-injection QTOF-HRMS analysis in complex matrices: the case of Abelmoschus manihot flower extracts.

A two-dimensional microscale carbon fiber/active carbon fiber system combined with a quadrupole time of flight high-resolution mass spectrometry (2DµCFs-QTOF-HRMS) system is proposed for the rapid putative identification of polar, medium-polar and weakly polar constituents in complex matrices while strongly mitigating ionic suppression effects. The capabilities of 2DµCFs-QTOF-HRMS have been proven by analysing the composition of Abelmoschus manihot flower extracts, allowing, in a single run, the detection of 41 known substances and the presence of 6 compounds never revealed before in these samples. 2DµCFs-QTOF-HRMS has been compared with traditional HPLC-MS, showing higher versatility and a significant reduction of both analysis time (70 min to 5 min) and solvent consumption (35 mL to 1.5 mL). A comparison with the results obtained by direct flow-injection MS analyses demonstrated that 2DµCFs-QTOF-HRMS leads to a more comprehensive analysis and to improved detection sensitivity. The proposed method can be considered suitable for the rapid and comprehensive analysis of food, environmental and pharmaceutical complex samples. 2DµCFs-QTOF-HRMS can thus be considered a rapid, versatile, reliable, high-throughput and economical technique that allows for the collection of information on polar, semipolar, and weakly polar components in complex matrices.

A reciprocating magnetic field assisted on-line solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry determination of trace tetracyclines in water.

A reciprocating magnetic-field-assisted on-line solid-phase extraction (RMF-SPE) method coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for continuous enrichment of trace chemicals in water samples. Under the assist of the reciprocating magnetic field, carboxyl-modified magnetic nanoparticles (CMNPs) were applied to prepare microcolumn with even dispersion by periodical motion, instead of traditional compaction as extraction sorbents. When water sample passed through the extraction region, dynamic sorbents generates an advantage of countless contacts between sorbents and targets without blocking for high efficient extraction. In this study, the on-line RMF-SPE method was established and evaluated by determination of tetracyclines (TCs) from water samples as analysis models, including oxytetracycline, tetracycline, demeclocycline, metacycline, chlortetracycline, and doxycycline. Experimental conditions have been investigated such as flow rate, reciprocating speed, elution time, and so on. The method showed high relative recovery (95.4-111.1%) and good repeatability with RSD from 2.9 to 11.8% for the 200 mL water sample. The linearity range, limits of detection (LODs), and limits of quantification (LOQs) were 0.5-200 µg L-1 (chlortetracycline) and 0.1-200 µg L-1 (other TCs), 12.0-74.1 ng L-1, and 40.1-247 ng L-1, respectively. More importantly, the high enrichment factors in a range of 204 (chlortetracycline) to 276 (demeclocycline) indicate that a small amount of dynamic sorbents (only 10 mg) give full play to extraction attributing to the reciprocating movement, especially for trace analysis and continuous extraction, which is significant for water samples from sea, river and domestic waste.

Ex-situ and in-situ rapid and quantitative determination of benzene derivatives in seawater using nanoconfined liquid phase nanoextraction.

Benzene derivatives (BDs) constitute a class of environmental pollutants whose exposure poses a grave risk to human health. These compounds rapidly diffuse from the atmosphere to the marine ecosystem: for this reason, their monitoring in seawater is every day more compelling. In this work, nanoconfined liquid phase nanoextraction (NLPNE), a versatile extraction technique recently described, has been for the first time applied to the gas chromatographic mass spectrometry (GC/MS) analysis of BDs in seawater. Ex-situ and in-situ NLPNE procedures have been developed and optimized in terms of extraction capabilities, analysis time, precision, and accuracy. Compared to the traditional extraction procedures, based on solid-phase microextraction (SPME) and liquid-liquid extraction (LLE), the proposed NLPNE methods allowed a rapid on-site analysis of benzene compounds with low solvent consumption, higher enrichment factors, and improved automation grade. Determination coefficients ranging from 0.9929 to 0.9997 were obtained for all BDs in the range 0.10-500 ng mL-1 and 5.00-500 ng mL-1, for ex-situ and in-situ NLPNE, respectively. Ex-situ and in-situ limits of detection ranged from 0.2 to 7.6 ng mL-1 and 0.04-1.00 ng mL-1. Our results suggest that NLPNE coupled to GC-MS can be considered a powerful technique for high-throughput analyses of trace compounds in environmental, food and biological samples.

Simultaneous determination of multiple phytohormones in tomato by ionic liquid-functionalized carbon fibers-based solid-phase microextraction coupled with liquid chromatography-mass spectrometry.

Phytohormones are interrelated by synergistic or antagonistic crosstalk and play important roles in the regulation of plant growth and development. In order to understand the interaction between phytohormones in the plant physiological network, it is necessary to determine trace levels of multiple phytohormones simultaneously in a complex matrix. Here, we synthesized ionic liquids containing different functional groups and modified the surface of carbon fibers with them. Based on these carbon fibers-ionic liquid (CFs-IL) materials, a solid phase microextraction method was developed to enable the simultaneous extraction of phytohormones. The adsorption specificity of multiple phytohormones was studied by identifying the hydrophobic, electrostatic, and π-π interactions, as well as hydrogen bonds, which favor simultaneous extraction of the relevant acidic, alkaline and neutral phytohormones by improving compatibility. The proposed method, coupled with liquid chromatography-tandem mass spectrometry, was applied to the simultaneous determination of 13 acidic, alkaline and neutral phytohormones in tomato. The limits of quantification were found to be in the range of 0.32-54.05 ng mL-1 and 4.6-185.8 pg mL-1, respectively, when measured by QQQ and Q-TOF. All of the relative recoveries were in the range of 94.40-113.37% with RSDs ≤15.36% (n = 3) for spiked tomato samples. This method is expected to be widely applied to multiple phytohormones analysis for in-depth researches concerning the physiological networks of plants.