Rapid screening and characterization of triterpene saponins in Acanthopanax senticosus leaves via untargeted MSAll and SWATH techniques on a quadrupole time of flight mass spectrometry.

This paper focused on untargeted MSAll, also called MSE, and sequential window acquisition of all theoretical fragment-ion spectra (SWATH) fragmentations for comprehensive structural characterization of triterpene saponins (TSs) in leaves of Acanthopanax senticosus through ultra-high performance liquid chromatography electrospray quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF). [M+H]+, [M + NH4]+ and [M + Na]+ precursor ions and the corresponding fragment ions were collected simultaneously in energy-resolved MSAll. SWATH fragmentation was applied as a comparable and complementary method for resolving co-eluting species. A workflow based on MSAll and SWATH fragmentations was constructed for comprehensive structural characterization and rapid discovery of TSs in leaves of A. senticosus. As a result, 89 TSs, along with 14 sapogenins, were unambiguously characterized or tentatively identified. Of these, 33 compounds were characterized as potentially new compounds, including the first report of malonyl-saponin in genus Acanthopanax. This study aimed to systematically analyze TSs in leaves of A. senticosus, and the results are significant for the utilization of A. senticosus leaves.

A generic strategy based on gas phase decomposition of protonated and ammoninted precursors producing predictable MRM-MS ion pairs and collision energies for direct analysis of plant triterpene glycosides.

Optimization of multiple reaction monitoring mass spectrometry (MRM-MS) parameters of triterpene glycosides (TGs) using traditional infusion methods remains to be labor-intensive. However, it was found that mild gas phase decompositions of protonated and ammoninted precursors (DPAP) of TGs could produce a series of abundant dehydrated product ions of aglycones ([A+H-nH2O]+ (n = 0, 1, 2, 3…)) with high efficiency and stability. Based on these considerations and findings, an innovative ESI+-MRM-DPAP-MS strategy was devised on a QTRAP 4000 instrument allowing for rapid the qualitative and quantitative analysis of plant TGs. A detailed study of 85 model compounds from 20 herbal medicines was implemented for validation and evaluation of the ESI+-MRM-DPAP-MS strategy proposed. The central composition design confirmed that collision energy (CE) played more significant roles than declustering potentials (DP) for the formation of these Q1/Q3 ion pairs based on MRM-DPAP-MS. It is also noted that Q1 and Mw were the most important factors for the prediction of CE values by a partial least square regression model. Here, we demonstrated this generic workflow and its merits in: (1) early prediction and selection of MRM ion pairs, no matter which type of TGs, employing a new-found Q1/Q3 calculation formula (Q1=[M+H/NH4]+ and Q3= [A+H-nH2O]+ (n = 0, 1, 2, 3…)); (2) direct determination of practicable CE values using TGs-specific CE-estimating linear equations; (3) appearances of excellent sensitivity, stability and repeatability through real application in Aralia elata, Panax notoginseng and Caulophyllum robustum; (4) seamless application of optimal CE parameters in other triple quadrupole MS instruments such as Thermo TSQ Quantum Ultra. The ESI+-MRM- DPAP-MS may service as an effective and feasible approach for analytical characterization of biological TGs from herbal medicines.

Simultaneous Separation of Eight Lignans in Forsythia suspensa by ß-Cyclodextrin-Modified Capillary Zone Electrophoresis.

The aim of the study was to develop an alternative capillary zone electrophoresis (CZE) for simultaneous determination of phillyrin (1), phillygenin (2), epipinoresinol-4-O-ß-glucoside (3), pinoresinol-4-O-ß-glucoside (4), lariciresinol (5), pinoresinol (6), isolariciresinol (7) and vladinol D (8) in Forsythia suspensa. The structural types of lignans 1-8 could be attributed to bisepoxylignans (1-4 and 6), monoepoxylignans (5 and 8) and cyclolignan (7). The major difficulties in the CZE separation of 1-8 could be summarization as the simultaneous presence of free lignans (1, 2 and 5-8) and lignan glucosides (3 and 4) and simultaneous occurrence of two pairs of isomers (3 and 4 as well as 5 and 7). Without the addition of ß-CD and methanol, the resolution of these analytes was quite poor. However, in this study, compounds 1-8 were excellently separated from each other within 15 min under optimized conditions with a borax running buffer (40 mM borax, pH 10.30) containing 2 mM ß-CD and 5% methanol (v/v) at the voltage of 20 kV, temperature of 35 °C and detection wavelength of 234 nm. Validation of the method included tests of linearity, precision, repeatability, stability and accuracy. In addition, the method offered inherent advantages such as lower analytical cost, no need of specific columns and use of small amounts of organic solvents and reagents. Finally, this green and economic CZE was successfully applied for the determination of these bioactive components 1-8 in F. suspensa fruits and its commercial extracts.

Early pregnancy following multidrug regimen chemotherapy in a gestational trophoblastic neoplasia patient: A case report.

RATIONALE: Gestational trophoblastic neoplasia is a group of rare tumors that can be cured using chemotherapy. The use of artificial contraception for at least 1 year is recommended not only due to the high recurrence rate in the first year after treatment, but also because of the unclear genetic toxic effects of multidrug regimen chemotherapy on reproductive cells. There is no consensus about the contraception duration, but most patients want to have children. PATIENT CONCERNS: This case involved a 33-year-old female suffering from gestational trophoblastic neoplasia and 5-fluorouracil + actinomycin-D chemotherapy. She became pregnant 1 month after finishing the chemotherapy. DIAGNOSIS: Gestational trophoblastic neoplasia. INTERVENTIONS: No treatment during pregnancy. OUTCOMES: The patient had a full-term normal delivery, and the baby showed normal development and growth after a follow-up of 48 months. LESSONS: Pregnancy soon after chemotherapy can be viable with rigorous prenatal care.