Journal of separation science最新文献

Lenvatinib has been demonstrated effective in advanced hepatocellular carcinoma (HCC), but the pharmacokinetic–pharmacodynamics behavior of lenvatinib and its metabolites remains unclear. To investigate the pharmacokinetic–pharmacodynamics behavior of lenvatinib and its active metabolites in advanced HCC patients, it is important to develop a simple and rapid method to analyze the exposures of lenvatinib and its metabolites in human samples. Here, we established and validated a simple and rapid method for determining lenvatinib and its three major metabolites, descyclopropyl lenvatinib (M1), O-demethyl lenvatinib hydrochloride (M2), and lenvatinib N-Oxide (M3) by liquid chromatography-tandem mass spectrometry method. Lenvatinib and its main metabolites were separated on an X-Terra RP18 column (50 × 2.1 mm, 3.5 µm) at 35°C within 3 min, and the analytes were isocratically eluted with the mobile phase of methanol–water (10:90, v/v) containing 0.1% of formic acid at a flow rate of 0.15 mL/min. The calibration range was 1–1000 ng/mL for lenvatinib, while 0.1–100 ng/mL for M1–M3 under positive electrospray ionization mode. The inter- and intra-batch precisions and accuracy were acceptable for lenvatinib and its metabolites. This method was successfully applied to measure lenvatinib and its metabolites in plasma samples from HCC patients, which provides a robust tool for pharmacokinetic–pharmacodynamics studies of lenvatinib.

Taking Citri Reticulatae Pericarpium (CRP) as an example, it is proved that there are differences between the powder decoction and pieces decoction of traditional Chinese medicine (TCM). In this study, an ultra-high performance liquid chromatography quadrupole exactive orbitrap MS/MS (UHPLC-Q-Exactive Orbitrap MS/MS) method was established to characterize 80 chemical components of CRP. The content of components was compared based on extraction rate, alcohol solubility rate, and mass spectrum peak area. The result showed that the content in CRP powder decoction was generally higher than that in CRP pieces decoction. The principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) were used to distinguish between the two decoctions. In addition, cardiovascular diseases (CVDs) were used as a model to investigate whether the increased content of components has practical significance. Network pharmacology screened five core targets of CRP in CVDs. The results of molecular docking indicated that the binding energies were all ≤ −5.0 kcal/mol between effective compounds (M34, M57, M80, etc.) and key targets (Akt1, SRC, ESR1, EGFR, and PTGS2) with good affinity. These results provide an important reference for further development and use of CRP powder decoction.

Jabuticaba (Plinia cauliflora) is a typical subtropical Brazilian fruit with unique organoleptic properties and a high nutritional value. This study shows a qualitative analysis of jabuticaba peels with volatile and semi-volatile components harvested from Minas Gerais, Brazil. A new device, the hydrophilic microporous cartridge, was developed to extract jabuticaba peels' volatile/semi-volatile components using a solid-phase microextraction method by direct immersion. This cartridge protected the polymer phase fiber, preventing its breakage and impregnation of the material. The developed method is simple, using a few steps to prepare jabuticaba peel samples. The fiber selected for analysis was a divinylbenzene/carboxene/polydimethylsiloxane of 30/50 µm. A comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry system was used to analyze natural products in jabuticaba peels. The method was optimized by a factorial design and could detect 213 organic compounds. Of particular note is the detection of terpenes (33.27%), fatty acids (29.60%), and ethyl esters (9.23%), which are mainly responsible for the nutritional properties and odor of the fruit. This study presents an improved method for extracting volatile compounds, offering enhanced insights into the phytochemical composition, aroma, flavor, and bioactivity of jabuticaba.

In this work, different injection modes (single injection, overlapping injection, and continuous injection) of countercurrent chromatography were used and compared for the isolation and purification of glabridin from the crude extract of Glycyrrhiza glabra. The two-phase solvent system consisting of n-hexane/ethyl acetate/methanol/water (5:4:5:4, v/v) was employed as stationary and mobile phases. Compared with single injection mode, both overlapping injection and continuous injection modes exhibited higher separation efficiency at the same sample loading capacity. Their total separation times were 89.68% and 53.97% of the single injection mode, and the total solvent consumption were 74.88% and 52.49% of the single injection mode, respectively. Meanwhile, the yield, purity, and recovery rate of these three injection modes were almost the same. It was demonstrated that high-speed countercurrent chromatography in continuous injection mode was the most effective way for separating glabridin in three methods and it can be further applied to the separation of other economically valuable natural products.

Lenvatinib has been demonstrated effective in advanced hepatocellular carcinoma (HCC), but the pharmacokinetic–pharmacodynamics behavior of lenvatinib and its metabolites remains unclear. To investigate the pharmacokinetic–pharmacodynamics behavior of lenvatinib and its active metabolites in advanced HCC patients, it is important to develop a simple and rapid method to analyze the exposures of lenvatinib and its metabolites in human samples. Here, we established and validated a simple and rapid method for determining lenvatinib and its three major metabolites, descyclopropyl lenvatinib (M1), O-demethyl lenvatinib hydrochloride (M2), and lenvatinib N-Oxide (M3) by liquid chromatography-tandem mass spectrometry method. Lenvatinib and its main metabolites were separated on an X-Terra RP18 column (50 × 2.1 mm, 3.5 µm) at 35°C within 3 min, and the analytes were isocratically eluted with the mobile phase of methanol–water (10:90, v/v) containing 0.1% of formic acid at a flow rate of 0.15 mL/min. The calibration range was 1–1000 ng/mL for lenvatinib, while 0.1–100 ng/mL for M1–M3 under positive electrospray ionization mode. The inter- and intra-batch precisions and accuracy were acceptable for lenvatinib and its metabolites. This method was successfully applied to measure lenvatinib and its metabolites in plasma samples from HCC patients, which provides a robust tool for pharmacokinetic–pharmacodynamics studies of lenvatinib.

Fagopyri Dibotryis Rhizoma, a traditional Chinese medicine, is widely used to treat various ailments such as pulmonary abscesses, measles pneumonia, and swelling. Its notable therapeutic effects are closely related to the chemical constituents, making it crucial to conduct in-depth research on the chemical components. In this study, a total of 209 compounds were preliminarily identified using ultra-high-performance liquid chromatography-quadrupole time-of-flight tandem mass spectrometry in Fagopyri Dibotryis Rhizoma. Subsequently, a method was established using ultra-high-performance liquid chromatography-triple quadrupole/linear ion trap tandem mass spectrometry for the simultaneous determination of 24 main ingredients (flavonoids and phenolic acids) in Fagopyri Dibotryis Rhizoma from different habitats and growing periods. Quantitative results showed that different compounds displayed varying contents across different habitats, with catechin, epicatechin, procyanidin B2, and procyanidin C1 being relatively abundant. Principal component analysis and partial least squares discriminant analysis showed there were significant differences among Fagopyri Dibotryis Rhizoma from different habitats, and the quality from Yunnan was superior. Entropy weight TOPSIS analysis showed that Fagopyri Dibotryis Rhizoma grown until late October has better comprehensive quality, which is basically consistent with the traditional harvesting time. In summary, this study can provide reference methods for the comprehensive evaluation of the quality of Fagopyri Dibotryis Rhizoma.

Dopamine and serotonin are neurotransmitters that are crucial for numerous physiological processes, including mood regulation, reward, and motor function. Dysregulation of these neurotransmitters is associated with various neuropsychiatric disorders. Albumin in plasma modulates the bioavailability of drugs and free concentrations of bioactive constituents. This study aimed to characterize the interactions of dopamine and serotonin with bovine serum albumin. Capillary electrophoresis in the frontal analysis mode was utilized as an effective method to assess dopamine–bovine serum albumin and serotonin–bovine serum albumin affinity. The free neurotransmitter plateaus were distinctly separated from the bovine serum albumin–neurotransmitter complex plateaus. Free dopamine and serotonin concentrations were determined by monitoring the heights of their respective plateaus. In contrast, the bound concentrations were calculated from the difference between the total and free plateau heights. Dopamine and serotonin were found to bind to bovine serum albumin at independent sites with binding constant values of 1.90 × 10³ and 2.90 × 10³ L/mol, respectively. Additionally, an in silico molecular docking approach revealed the binding sites for dopamine and serotonin near the glutamic acid-291 and serine-428 residues of bovine serum albumin, respectively.

In this work, the covalent organic frameworks–incorporated electrospun nanofiber membranes were used as a highly efficient adsorbent to enrich quinolone antibiotics in food samples. Covalent organic frameworks composed of 1,3,5-tris(4-aminophenyl) benzene and 2,5-dihydroxyterephthalaldehyde were rapid prepared only 20 min at room temperature, then were further synthesized into electrospun polyacrylonitrile nanofiber membranes by electrospinning the binary precursors solution directly. Coupled with high-performance liquid chromatography with ultraviolet detector, the method exhibited good linearity in the range of 1–100 ng·mL⁻¹ for four quinolone antibiotics, with low limits of detection 0.19–0.34 ng·mL⁻¹ (signal-to-noise ratio = 3). The recoveries of four quinolone antibiotics were 86%–116%, and relative standard deviations of the intra- and interday for four quinolone antibiotics were 0.7%–9.0%, respectively. The practical application of the thin film microextraction method using nanofiber membranes as adsorbent for detecting four quinolone antibiotics in animal-derived food samples was demonstrated.

Shenhua Tablet (SHT), a Chinese herbal medicine comprising seven crude drugs, is utilized in the treatment of immunoglobulin A nephropathy (IgAN). However, due to its complex composition, the chemical constituents of SHT in vitro are still incompletely known, which has restricted the comprehensive development and utilization of SHT in clinical practice. In the present study based on ultra-high performance liquid chromatography-quadrupole-orbitrap-linear ion trap mass spectrometry (UHPLC-Q-Orbitrap-LTQ-MS) in data dependent acquisition mode, combining the accurate mass and structural information, the profiling and characterization of chemical constituents in SHT were carried out. The automated spectral matching (of experimental MS² spectra against library spectra of mzCloud) method with a high mass accuracy (within 5 ppm) was used for the rapid identification of compounds. A total of 183 compounds, consisting of 64 flavonoids, 52 terpenoids, 37 organic acids, 6 phenylpropanoids, 5 phenols, and 19 other phytochemicals, were successfully characterized. In addition, the fragmentation pathways and characteristic fragments of some representative compounds were elucidated. The results offered clear insights into its chemical profile, thereby facilitating quality control and advancing pharmacological research.

Shenhua Tablet (SHT), a Chinese herbal medicine comprising seven crude drugs, is utilized in the treatment of immunoglobulin A nephropathy (IgAN). However, due to its complex composition, the chemical constituents of SHT in vitro are still incompletely known, which has restricted the comprehensive development and utilization of SHT in clinical practice. In the present study based on ultra-high performance liquid chromatography-quadrupole-orbitrap-linear ion trap mass spectrometry (UHPLC-Q-Orbitrap-LTQ-MS) in data dependent acquisition mode, combining the accurate mass and structural information, the profiling and characterization of chemical constituents in SHT were carried out. The automated spectral matching (of experimental MS² spectra against library spectra of mzCloud) method with a high mass accuracy (within 5 ppm) was used for the rapid identification of compounds. A total of 183 compounds, consisting of 64 flavonoids, 52 terpenoids, 37 organic acids, 6 phenylpropanoids, 5 phenols, and 19 other phytochemicals, were successfully characterized. In addition, the fragmentation pathways and characteristic fragments of some representative compounds were elucidated. The results offered clear insights into its chemical profile, thereby facilitating quality control and advancing pharmacological research.