The study investigated the intrinsic changes in material basis of Angelicae Sinensis Radix during wine processing by headspace-gas chromatography-ion mobility spectrometry(HS-GC-IMS), headspace-solid phase microextraction-gas chromatography-mass spectrometry(HS-SPME-GC-MS), and ultra-high performance liquid chromatography-quadrupole-orbitrap mass spectrometry(UPLC-Q-Orbitrap-MS) combined with chemometrics. HS-GC-IMS fingerprints of Angelicae Sinensis Radix before and after wine processing were established to analyze the variation trends of volatile components and characterize volatile small-molecule substances before and after processing. Principal component analysis(PCA) and orthogonal partial least squares-discriminant analysis(OPLS-DA) were employed for differentiation and difference analysis. A total of 89 volatile components in Angelicae Sinensis Radix were identified by HS-GC-IMS, including 14 unsaturated hydrocarbons, 16 aldehydes, 13 ketones, 9 alcohols, 16 esters, 6 organic acids, and 15 other compounds. HS-SPME-GC-MS detected 118 volatile components, comprising 42 unsaturated hydrocarbons, 11 aromatic compounds, 30 alcohols, 8 alkanes, 6 organic acids, 4 ketones, 7 aldehydes, 5 esters, and 5 other volatile compounds. UPLC-Q-Orbitrap-MS identified 76 non-volatile compounds. PCA revealed distinct clusters of raw and wine-processed Angelicae Sinensis Radix samples across the three detection methods. Both PCA and OPLS-DA effectively discriminated between the two groups, and 145 compounds(VIP>1) were identified as critical markers for evaluating processing quality, including 4-methyl-3-penten-2-one, ethyl 2-methylpentanoate, and 2,4-dimethyl-1,3-dioxolane detected by HS-GC-IMS, angelic acid, β-pinene, and germacrene B detected by HS-SPME-GC-MS, and L-tryptophan, licoricone, and angenomalin detected by UPLC-Q-Orbitrap-MS. In conclusion, the integration of the three detection methods with chemometrics elucidates the differences in the chemical material basis between raw and wine-processed Angelicae Sinensis Radix, providing a scientific foundation for understanding the processing mechanisms and clinical applications of wine-processed Angelicae Sinensis Radix.
Wine/analysis* ; Gas Chromatography-Mass Spectrometry/methods* ; Chromatography, High Pressure Liquid/methods* ; Angelica sinensis/chemistry* ; Solid Phase Microextraction/methods* ; Drugs, Chinese Herbal/isolation & purification* ; Chemometrics ; Volatile Organic Compounds/chemistry* ; Principal Component Analysis ; Ion Mobility Spectrometry/methods*

Objective To establish a method for determination of escitalopram in biological samples by ultrasound-assisted ionic liquid-dispersive liquid-liquid microextraction combined with gas chromatography-tandem mass spectrometry （GC-MS/MS） and provide evidences for forensic determination of cases related to escitalopram. Methods The 1-hexyl-3-methylimidazolium hexafluorophosphate （[C₆MIM][PF₆]） was selected as an extract solvent to process biological samples. Ultrasound-assisted extraction was used on the samples. Then the samples were detected by GC-MS/MS. Results The linear range of escitalopram in blood and liver were 5.56-1 111.10 ng/mL and 0.025-5.00 mg/g, respectively. The correlation coefficient （r） were greater than 0.999, limit of detection （LOD） were 4.00 ng/mL and 2.00 μg/g, limit of quantitation （LOQ） were 14.00 ng/mL and 6.00 μg/g, respectively. The extraction recovery rates were all greater than 50%, the interday and intraday precision were less than 20%. Escitalopram was detected in blood and liver samples from the actual poisoning case by this method with a content of 1.26 μg/mL and 0.44 mg/g, respectively. Conclusion The ultrasound-assisted ionic liquid-dispersive liquid-liquid microextraction combined with GC-MS/MS is environment friendly, rapid, has good enriching effect and consumes less organic solvent and can be used for forensic determination of escitalopram related cases.
Citalopram ; Gas Chromatography-Mass Spectrometry ; Limit of Detection ; Liquid Phase Microextraction ; Tandem Mass Spectrometry

Currently, the main sample pretreatment methods for forensic toxic analysis are liquid-liquid extraction （LLE） and solid-phase extraction （SPE）. As a simple, convenient, and low-cost LLE method, dispersion liquid-liquid microextraction （DLLME） has high enrichment factor and good extraction efficiency, and therefore has attracted the attention of many researchers in the field of toxicology analysis in recent years. As a multi-functional microextraction method, DLLME has been widely used in the analysis of pesticides, sleeping sedatives, drugs and heavy metal poisons in forensic toxic analysis. Meanwhile, it can also be used in combination with such a variety of analytical instruments as gas chromatography-electron capture detectors （GC-ECD）, high performance liquid chromatography-diode array detectors （HPLC-DAD）. As a sample pretreatment method, DLLME has the advantages of simple operation, less use of organic solvent, reliable results and good reproducibility, thus can meet the requirements of modern court toxic analysis.
Forensic Toxicology ; Liquid Phase Microextraction ; Reproducibility of Results ; Solid Phase Extraction ; Solvents

The current methods to prepare and determine pesticide residues in Chinese herbal medicine were summarized in this paper. In addition,the new techniques to prepare and determine pesticide residues used in recent years was reviewed, which included solid-phase micro-extraction (SPME) , supercritical fluid extraction ( SFE) , accelerated solvent extraction (ASE) , immune affinity chromatography (IAC), supercritical fluid chromatography (SFC), column switching high performance liquid chromatography (CSHPLC), high performance liquid chromatography/mass spectrometry (HPLC/MS), capillary electrophoresis (CE) and capillary zone electrophoresis (CZE) , and immune analysis (IA), etc. To sum up, these would bring a great progress in analysis of the pesticide residues in Chinese herbal medicine, and make it more rapidly, accurately and normatively.
Chromatography, High Pressure Liquid ; Chromatography, Supercritical Fluid ; Drugs, Chinese Herbal ; chemistry ; Electrophoresis, Capillary ; Gas Chromatography-Mass Spectrometry ; Pesticide Residues ; analysis ; isolation & purification ; Plants, Medicinal ; chemistry ; Reproducibility of Results ; Solid Phase Microextraction ; Technology, Pharmaceutical ; methods