Simultaneous separation and determination of several chiral antidepressants and their enantiomers in wastewater by online heart-cutting two-dimensional liquid chromatography.

A novel method for simultaneous separation and detection of the racemates and the enantiomers of common chiral antidepressants in wastewater matrix was developed by online heart-cutting two-dimensional liquid chromatography (2D-LC) coupled to solid-phase extraction (SPE). Screening of chiral stationary phases (CSPs) and chromatographic conditions was investigated for complete enantioseparation to be compatible with RP-HPLC in 1st D-LC. Using methanol-0.1 % (v/v) ammonia solution as mobile phase, a 2D-LC system was configured by reversed mode with a combination of C18 column and the serially CPS columns as 2D-LC stationary phases respectively. The target analytes could achieve satisfactory transformation between 2D-LCs with transfer rate of 90.57-98.58 %. By means of freeze-drying and SPE, three antidepressants in wastewater were greatly preconcentrated under the optimized conditions, improving the method performance. The racemates and the enantiomers of mirtazapine, bupropion and fluoxetine exhibited good linearity in the range of 0.10-30.00 ng/mL (R2≥0.9986), and LODs and LOQs ranged in 0.0183-0.0549 ng/mL and 0.0661-0.1831 ng/mL, respectively. By this way, the method was successfully applied to simultaneous determination of the racemates and the enantiomers of mirtazapine, bupropion and fluoxetine in wastewater samples. Among them, three samples contained bupropion at level of 0.401-0.822 ng/mL, and mirtazapine at level of 0.328 and fluoxetine at level of 0.381 ng/mL were detected respectively in the other two samples. The enantiomers were at level of 0.140-0.189 ng/mL for mirtazapine, 0.182-0.419 ng/mL for bupropion and 0.179-0.204 ng/mL for fluoxetine, respectively. The proposed method providing an efficient approach to monitoring chiral drugs and their enantiomers in wastewater, facilitating to pollution assessment of chiral drugs in the environment and regional survey of illicit abuse in drug control.

Sheathed in-situ room-temperature growth covalent organic framework solid-phase microextraction fiber for detecting ultratrace polybrominated diphenyl ethers from environmental samples.

The extraction performance of solid-phase microextraction (SPME) fiber is significantly influenced by coating materials and fabricating process. It is urgently needed for fabricating robust SPME fiber with facile preparation methods. Herein, a novel polyimide (PI) @ covalent organic framework (COF) synthesized by 1,3,5-Tris (4-aminophenyl) benzene (TPB) and 2,5-dimethoxyterephthalaldehyde (DMTP) fiber, named PI@TPB-DMTP fiber, was successfully fabricated with facile method at room temperature. Firstly, a COF crystals TPB-DMTP was in situ grown on stainless steel fiber, where the COF crystals was synthesized by the Schiff-base reaction between TPB and DMTP. Subsequently, the COF coating was covered with an ultrathin layer of PI through a simple dip-coating method to improve the fiber stability. By coupled PI@TPB-DMTP SPME fiber with gas chromatography-negative chemical ion-mass spectrometry (GC-NCI-MS), a sensitive analytical method was established for the determination of ultratrace polybrominated diphenyl ethers (PBDEs) in water sample. To achieve the best efficiency and sensitivity for the analysis of PBDEs, six potential influencing factors in extraction step and desorption step were optimized. Under optimized conditions, the established method showed high enhancement factors of 1470-3555, wide linear range of 0.05-100 ng L-1, low detection limits of 0.0083-0.0190 ng L-1, good repeatability for intra-day in the range of 3.71%-7.62% and inter-day in the range of 5.12%-8.81%, good reproducibility in the range of 6.83%-9.21%. The satisfactory recovery was ranged from 79.2% to 117.3% in determining real water samples. The excellent experimental performance was mainly attributed to the large specific surface area of TPB-DMTP, as well as the high permeability of porous PI film. The results demonstrated that the COF-based fiber showed great potential for analysis of PBDEs in complex environmental samples.

Dual-fiber solid-phase microextraction coupled with gas chromatography-mass spectrometry for the analysis of volatile compounds in traditional Chinese dry-cured ham.

For the purpose of obtaining a more comprehensive flavor profile, volatile compounds in traditional Chinese dry-cured hams were studied by dual-fiber solid-phase microextraction (SPME) using two fibers simultaneously. By using the selected pair of fibers and under the optimal extraction time, there were total seventy-two volatile compounds identified, which was higher than the mono-fiber SPME method using a single fiber. Out of the seventy-two compounds, twenty-six compounds were not detected by using mono-fiber SPME and five among them are classified as the major aromatic compounds in the literatures. Due to the higher coverage and less tendency for the occurrence of competition among the volatiles, the total amount of volatiles extracted by dual-fiber SPME (510.02 ng/kg) was higher than mono-fiber SPME. Three grades of dry-cured hams were successfully distinguished based on dual-fiber SPME. The volatile compounds belonged to nine chemical families and differed in different grades of dry-cured hams. These results show that dual-fiber SPME is capable of analyzing flavor profiles more comprehensively and distinguishing traditional Chinese dry-cured hams.