Analysis of Bioactive Saponins in Fructus Gleditsiae abnormalis and Fructus Gleditsiae sinensis by LC-ELSD

Fructus Gleditsiae abnormalis and Fructus Gleditsiae sinensis are widely used in traditional Chinese medicine. As different developmental stages of fruits of the same plant Gleditsia sinensis Lam., whether Fructus Gleditsiae sinensis can be used as the substitute of Fructus Gleditsiae abnormalis has long been debated. To compare the differences of the content of main active saponins between the two fruits, we established a new LC-ELSD method for simultaneous determination of four major saponins present in two fruits. After fully validated, the method was successfully applied to quantitatively analyze the four bioactive saponins of twenty samples, 11 of Fructus Gleditsiae abnormalis and 9 of Fructus Gleditsiae sinensis obtained from different locations. It was shown that there were no significant differences in saponins contents and LC profiles between the two fruits. Moreover, the developed method can be used for quality control of Fructus Gleditsiae abnormalis and Fructus Gleditsiae sinensis.     

HPLC–MS/MS determination of flavonoids in Gleditsiae Spina for its quality assessment

Gleditsiae Spina, the thorn of Gleditsia sinensis Lam., has been used as an anti‐inflammatory, anti‐tumor, and anti‐bacterial traditional medicine for hundreds of years in China. This study used high‐performance liquid chromatography and tandem mass spectrometry combined with chemometric methods to allow the fast and accurate identification and quantification of the flavonoids compounds in Gleditsiae Spina, and created reliable criteria for accurate identification of Gleditsiae Spina and its adulterants. This research provides good evidence for the classification and quality evaluation of Gleditsiae Spina. Firstly, eight flavonoids compounds were detected and identified on the basis of their mass spectra, fragment characteristics, and comparison with published data. Then the mass spectroscopic fragmentation pathways of these compounds were determined and, in addition rutin, isoquercitrin, and quercitrin were detected in Gleditsiae Spina for the first time. The quantification was performed on a triple quadrupole tandem mass spectrometer in multi‐reaction monitoring mode, and the baseline separation of the eight bioactive flavonoids components was achieved within 13 min. Furthermore, the proposed method was successfully applied for simultaneous quantitative determination of the eight Gleditsiae Spina compounds and adulterants obtained from different sources in China. Then, we built a classification model which showed a high level of accuracy predicting 100% of the samples, correctly.     

Studies on the Components of Crude and Processed Fructus Corni by ESI-MS

The components of crude and processed Fructus Corni were investigated by means of electrospray ionization-tandem mass spectrometry（ESI-MSn） technique in the negative ion mode. Compared with those of crude Fructus Corni, the chemical components of the processed Fructus Corni were changed both in quality and in quantity. From the ESI-MS spectra of the crude and processed Fructus Corni, six peaks were selected to establish the characte-ristic ESI-MS peaks. Several factors in the processing procedure were examined. The experimental results demonstrate that the chemical reactions that occurred in the processing procedure can be used for the elucidation of the processed mechanism of Fructus Corni, which is regularly affected by the processing conditions. The present article provides both the chemistry evidence for the understanding of the processing procedure of Fructus Corni and the specific methodology for the research of the processing procedure and quality identification of traditional Chinese medicine.     

Exploring the anti-inflammatory effect of Fructus Gleditsia sinensis Lam., Fructus Gleditsiae abnormalis,and Gymnocladus chinensis Baill. using SPME-GC-MS,network pharmacology,and molecular docking

Fructus Gleditsia sinensis Lam. (FGSL), Fructus Gleditsiae abnormalis (FGA), and Gymnocladus chinensis Baill. (GCB) are fruits of leguminous plants that are used in traditional medicine. Among them, FGSL and FGA are developed to different degrees, and GCB is related to them. The literature records indicate their use in the external treatment of carbuncle. Modern pharmacological studies have shown that the formation of a carbuncle is closely related to the occurrence and development of inflammation, and the volatile components contained in the FGSL/FGA drugs have significant anti-inflammatory effects. The solid phase micro extraction-gas chromatography-mass spectrometry (SPME–GC–MS) method was used to analyze the volatile components contained in FGSL, FGA, and GCB. Moreover, the molecular mechanism underlying the anti-inflammatory effects was explored based on network pharmacology and molecular docking. The SPME-GC-MS demonstrated significant differences in the chemical constituents and percentage contents among FGSL, FGA, and GCB. 13 common volatile components were identified in FGSL, FGA, and GCB. Through network pharmacology and molecular docking, the differences in the anti-inflammatory mechanism of FGSL, FGA, and GCB were initially revealed. This study laid the foundation for further study of FGSL, FGA, and GCB. Simultaneously, it also provided a reference for the correct use of FGSL, FGA, and GCB in the clinic.     

Quality differentiation method of similar phytomedicines with high sugar content based on the sugar-marker: Taking Schisandrae Chinensis Fructus and Schisandrae Sphenantherae Fructus as an example

Quality evaluation of phytomedicines is limited to small molecules as quality markers, even for herbs with high sugar contents. We established a high-resolution method for distinguishing similar medicinal materials using sugar as quality marker, taking Schisandrae Chinensis Fructus (SCF) and Schisandrae Sphenantherae Fructus (SSF) as an example. High performance liquid chromatography with an evaporative light-scattering detector (HPLC-ELSD), high performance size exclusion chromatography coupled with multi-angle laser light scattering detector and refractive index detector (HPSEC-MALLS-RID) and high performance liquid chromatography with photo-diode array (HPLC-PDA) after 1-phenyl-3-methyl-5-pyrazolone (PMP) pre-column derivatization were used respectively to determine monosaccharide contents, molecular weights and monosaccharide compositions of polysaccharides in this study. The differences of SCF and SSF from ten producing areas were compared by principal component analysis (PCA) and hierarchical cluster analysis (HCA). Results showed that contents of fructose and glucose were similar between SCF and SSF. Molecular weight (Mw) of SCF polysaccharides was ranging from 1.561 × 10² to 6.599 × 10² kDa, and that of SSF polysaccharides was ranging from 8.524 × 10² to 1.7416 × 10³ kDa. Schisandra polysaccharides were mainly composed of mannose, galacturonic acid, glucose, galactose and arabinose. Based on PCA and HCA, SCF and SSF from ten different areas were classified into three categories. With great accuracy, sensitivity and stability, the methods established in this study had important reference value for quality evaluation, development and utilization of saccharide components in medicinal materials.     

Profiling of widely targeted metabolomics for the identification of chemical composition in epidermis,xylem and pith of Gleditsiae Spina

Gleditsiae Spina, the thorn of Gleditsia sinensis Lam., has a long history of being used as a traditional medicine in East Asian countries. However, only a few biologically active substances have been identified from it. In this study, the epidermis, xylem and pith of Gleditsiae Spina, respectively Gs-E, Gs-X and Gs-P, were studied. We used a widely targeted metabolomics method to investigate the chemical composition of Gs-E, Gs-X and Gs-P. A total of 728 putative metabolites were identified from Gleditsiae Spina, including 211 primary metabolites and 517 secondary metabolites. These primary and secondary metabolites could be categorized into more than 10 different classes. Flavonoids, phenolic acids, lipids, amino acids and derivatives, and organic acids constituted the main metabolite groups. Multivariate statistical analysis showed that the Gs-E, Gs-X and Gs-P samples could be clearly separated. Differential accumulated metabolite (DAM) analysis revealed that more than half of the DAMs exhibited the highest relative concentrations in Gs-E, and most of the DAMs showed the lowest relative concentrations in Gs-X. Moreover, 11 common differential primary metabolites and 79 common differential secondary metabolites were detected in all comparison groups. These results further our understanding of chemical composition and metabolite accumulation of Gleditsiae Spina.     

Holistic quality evaluation of Saposhnikoviae Radix (Saposhnikovia divaricata) by reversed-phase ultra-high performance liquid chromatography and hydrophilic interaction chromatography coupled with ion mobility quadrupole time-of-flight mass spectrometry-based untargeted metabolomics

Untargeted metabolomics more suits the quality evaluation of TCM because of its holistic property. To assess the holistic quality difference of Saposhnikoviae Radix (the roots of Saposhnikovia divaricata), we integrate ultra-high-performance liquid chromatography coupled with ion mobility/quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS)-based untargeted metabolomics and quantitative assay. A BEH C18 column in the reversed-phase mode and a BEH Amide column in Hydrophilic Interaction Chromatography (HILIC) mode were utilized for metabolites profiling, which enabled high coverage of the non-polar to polar components in Saposhnikoviae Radix. Moreover, the application of major components knockout strategy enlarged the exposure of those minor components. Integrated use of high-definition MS^E (HDMS^E) and data-dependent acquisition (DDA) could enhance the metabolites characterization by providing reliable fragmentation information and collision cross section values. Computational in-house library-driven automated peak annotation of the HDMS^E and DDA data assisted to characterize 104 components from Saposhnikoviae Radix. Chemometric analyses of the commercial Saposhnikoviae Radix samples (64 batches collected from 11 cultivars aging from 1 to 4 years), based on the positive MS^E data, in general could indicate large discrimination between Guan-Fang-Feng (from Heilongjiang) and the others, but negligible difference among Saposhnikoviae Radix from the other ten provinces of China and with different ages. Quantitative assays of prim-O-glucosylcimifugin and 4′-O-β-D-glucosyl-5-O-methylvisamminol, by a rapid and fully validated UHPLC-UV method, could primarily deduce that Guan-Fang-Feng aging 2 and 3 years exhibited better quality. The methods established can holistically assess the quality of TCM with wide spans of plant metabolites covered.     

Screening and identification of multi-component in Qingkailing injection using combination of liquid chromatography/time-of-flight mass spectrometry and liquid chromatography/ion trap mass spectrometry

An approach for screening and identification of multi-component in complex traditional Chinese medicine systems with a combinative LC/MS (MSⁿ) technique was described in this paper. The chemical profile of Qingkailing injection, a well-known traditional Chinese formula in China, was studied using the established method as for an application. Benefit from combining the accurate mass measurement of LC/TOF-MS to generate elemental compositions and the complementary multilevel structural information provided by LC/ion trap MSⁿ, 33 components in Qingkailing injection were identified in all. The three isomers of chlorogenic acid, isochlorogenic acid and neochlorogenic acid which are derived from Flos Lonicerae, one of the medicinal materials in Qingkailing, were differentiated by verifying their MS³ fragmentation data. All the components identified were surveyed and classified according to their medicinal materials derivation. This study is expected to provide an effective and reliable pattern for comprehensive and systematic characterization of the complex traditional Chinese medicine systems.     

A simple liquid chromatography coupled with tandem mass spectrometry approach for the simultaneous quantification of thirteen compounds in rats following oral administration of raw and processed Fructus Xanthii: Application in a comparative pharmacokinetic study

A simple and sensitive analysis using ultra high performance liquid chromatography with a tandem mass spectrometric system operated in selected reaction monitoring mode was developed for the determination of 11 phenolic acids, atractyloside, and carboxyatractyloside in rat plasma. The two classes of analytes were then separated on a Waters ACQUITY? UPLC HSS T3 column (50 mm × 2.1 mm, 1.8 µm) using gradient elution with a mobile phase of 0.2% formic acid in water containing 10 mM ammonium acetate and methanol. Detection was accomplished by selected reaction monitoring scanning via an electrospray source operating in negative ionization mode. The calibration curve was linear (R² = 0.990) over a concentration range of 1.20–3500 ng/mL, while the validated lower limit of quantification was 1.20 ng/mL. The precision varied from 0.84 to 4.62%, and the accuracy varied within ±5%. The method proved robust with sample freezing and thawing and with short‐ and long‐term sample storage. The established method was used for simultaneous quantification and was successfully used for the first time for the pharmacokinetic evaluation of 13 compounds after the intragastric administration of raw and processed Fructus Xanthii in rats. The results indicated that processing affects the absorption and metabolism of Fructus Xanthii extract. Importantly, the results also indicated the importance of processing for the clinical application of traditional Chinese medicine.     

Identification of prototypes from Ligustri Lucidi Fructus in rat plasma based on a data-dependent acquisition and multicomponent pharmacokinetic study

The identification and quantization of traditional Chinese medicine (TCM) are a challenge for researchers and industry. Using untargeted analytical methods, the in vivo detection and identification of TCM compounds are difficult because of the significant interference of endogenous substances. Fortunately, the ongoing development of new analytical technologies, especially Q-Orbitrap–MS, offers some solutions. Our team developed a holistic MS method, combining untargeted data-dependent MS² (dd-MS²) modes to extensively identify TCM prototypes in vivo. The method was successfully applied to the analysis of Ligustri Lucidi Fructus (LLF). LLF is a widely used TCM with a remarkable nourishing effect on the liver and kidney. In the study, we aimed to identify the prototypes in rat plasma after oral administration of LLF extract. Following separation on an HSS T₃ column, LLF extract and rat plasma were performed in untargeted dd-MS² mode. Forty-seven compounds were characterized in rats plasma as prototypes of LLF extract. Furthermore, seven major prototypes were chosen as pharmacokinetic markers to investigate LLF's pharmacokinetic properties. The results provides comprehensive determination of compounds in LLF both in vitro and in vivo, which is important for quality control, pharmacology studies and clinical use of LLF.     

A four-dimensional separation approach by offline 2D-LC/IM-TOF-MS in combination with database-driven computational peak annotation facilitating the in-depth characterization of the multicomponents from Atractylodis Macrocephalae Rhizoma (Atractylodes macrocephala)

Plant metabolites represent complex chemical system, which renders it difficult to clarify the chemical composition by conventional liquid chromatography/mass spectrometry (LC/MS) due to the limited selectivity and peak capacity. The rhizomes of Atractylodes macrocephala have been utilized as a traditional Chinese medicine Atractylodis Macrocephalae Rhizoma (Bai-Zhu), and have been reported containing multiple categories of plant metabolites. Targeting the multicomponents from A. macrocephala, an integral approach by offline two-dimensional liquid chromatography/ion mobility quadrupole time-of-flight mass spectrometry (2D-LC/IM-QTOF-MS) was established and validated. By configuring an XBridge Amide column of Hydrophilic Interaction Chromatography and an Atlantis Premier BEH C18AX column of mixed ion exchange and reversed-phase modes, the established 2D-LC/IM-QTOF-MS system showed high orthogonality up to 0.91. Dimension-enhanced, data-independent high-definition MS^E (HDMS^E) in the positive ESI mode was conducted on a Vion IM-QTOF mass spectrometer, and its hyphenation to offline 2D-LC could enable the four-dimensional separation (each dimension in 2D-LC, IM, and MS). Particularly, HDMS^E facilitated the acquisition of high-definition MS¹ and MS² spectra. In-house library-driven computational peak annotation by the bioinformatics platform UNIFI could efficiently process and annotate the HDMS^E data for the structural elucidation. By integrating reference compounds comparison, we could identify or tentatively characterize 251 components from A. macrocephala (including 115 sesquiterpenoids, 90 polyacetylenes, 11 flavonoids, 9 benzoquinones, 12 coumarins, and 14 others), which indicated large improvement in identifying those minor plant components, compared with the conventional LC/MS approach. Conclusively, offline 2D-LC/IM-QTOF-HDMS^E in combination with computational data interpretation proves to be powerful facilitating the in-depth multicomponent characterization of herbal medicine.     

A vascular smooth muscle/cell membrane chromatography–offline-gas chromatography/mass spectrometry method for recognition,separation and identification of active components from traditional Chinese medicines

We describe an analytical method of vascular smooth muscle cell membrane chromatography (VSM/CMC) combined with gas chromatography/mass spectrometry (GC/MS) for recognition, separation and identification of active components from traditional Chinese medicines (TCMs). VSM cells by means of primary culture with rat thoracic aortas were used for preparation of the stationary phase in the CMC model. Retention components by the VSM–CMC model were collected and then analyzed by GC/MS under the optimized conditions in offline conditions. After investigating the suitability and reliability of the VSM/CMC–offline-GC/MS method using nifedipine and nitrendipine as standard compounds, this method was applied in screening active components from the extracts of TCMs such as Radix Angelicae Dahuricae (RAD), Rhizomza Seu Radix Notopterygii (RSRN), Radix Glehniae (RG) and Fructus Cnidii (FC). Retention components from the extracts in the VSM–CMC model were imperatorin and osthole identified by the GC/MS method. In vitro pharmacological trials indicated that imperatorin and osthole could concentration dependently relax the rat thoracic artery pre-contracted by KCl (P < 0.05). The maximum relaxation effects (R_max) were 63 ± 5% and 40 ± 6% for imperatorin and osthole, respectively. The VSM/CMC–offline-GC/MS method is an effective screening system that can rapidly detect and enrich target components from a complex sample and then accurately identify them.     

Nanoelectrospray with ion-trap mass spectrometry for the determination of beta-casomorphins in derived milk products

beta-Casomorphins (b-CMs) are bioactive peptides derived from casein with opioid agonist effects similar to morphine. The use of electrospray (ESI) with quadrupole ion-trap mass spectrometry (QIT-MS) for these compounds in two matrices, cheese and milk, was examined. It was compared to a liquid chromatography (LC) coupled to mass spectrometry (LC-MS), and a “soft” ionisation technique, NanoMate, with selected ion monitoring (SIM), which are unreliable for the determination of trace casomorphins in derived milk products. b-CM mass fragmentation pathways were done for the four most common b-CMs: β-casomorphin (1-5) bovine (b-CM-5), β-casomorphin (1-7) bovine (b-CM-7), [D-Ala2, D-Pro4,Tyr5]-β-casomorphin (1-5) amide (b-CM-10) and β-casomorphin (1-5) amide [D-Ala2,Hyp4,Tyr5] (b-CM-11). The major product ions obtained in QIT-MS were used to construct fragmentation pathways for b-CMs. The different collision energies using automated nanoelectrospray ion source NanoMate and conventional LC in QIT-MS were studied. Calibration data for b-CMs, using spiked milk or cheese samples (10 g or 10 mL), were: NanoMate/MS (25-1000 μg/L), r² = 0.998; NanoMate/MS² (5-1000 μg/L), r² = 0.9992; NanoMate/MS³ (2.5-1000 μg/L), r² = 0.9998. Reproducibility data (% RSD, N = 5) for NanoMate/MSⁿ mode ranged between 2.0 at 500 μg/L and 7.0 at 10 μg/L.     

Ultra-high performance liquid chromatography/ion mobility time-of-flight mass spectrometry-based untargeted metabolomics combined with quantitative assay unveiled the metabolic difference among the root,leaf, and flower bud of Panax notoginseng

Despite Panax notoginseng (Sanchi: the root and rhizome) is globally popular serving as the source of food additives, health-care products, and traditional Chinese medicines (TCMs), the saponin difference between the root (PNR) and two aerial parts (leaf, PNL; flower bud, PNF) that can be vicariously used, remains unclear. Authentication of Sanchi, particular from the Chinese patent medicines (CPMs), poses great challenges. Ultra-high performance liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS)-based untargeted metabolomics and quantitative assay by UHPLC-UV were utilized to establish the “Identification Markers” for Sanchi. Targeted monitoring of multiple identification markers was performed for authenticating Sanchi simultaneously from 15 different CPMs. Dimension-enhanced profiling by UHPLC/IM-QTOF-MS in the negative high-definition MS^E (HDMS^E) mode and in-house library-driven peak annotation could characterize totally 328 ginsenosides (133 from PNR, 125 from PNL, and 161 from PNF). Multivariate statistical analysis of the PNR/PNL/PNF samples (45 batches) identified 27 potential markers. Five major markers (notoginsenoside R1, ginsenosides Rg1, -Rb1, -Rb2, and -Rb3) thereof were quantitatively assayed by a fully validated UHPLC-UV (detected at 203 nm) approach. The application of selective ion monitoring (SIM) of 12 differential saponins coupled with UHPLC separation could precisely identify Sanchi from 15 different CPMs (45 batches). Holistic difference in ginsenosides among three parts of P. notoginseng was unveiled, and the markers deduced may assist to identify the illicit substitution of leaf or flower as the root in the TCM compound formulae. Conclusively, the integration of untargeted metabolomics and quantitative analysis can provide reliable information enabling the precise authentication of TCM.     

Quality evaluation of raw and processed Crataegi Fructus by color measurement and fingerprint analysis

Crataegi Fructus and its processed products have been used as a traditional medicine for a long time, and numerous active components are responsible for their curative effects. However, a comprehensive and fast method for the quality control of its processed products is still lacking. In this study, two analytical methods based on color measurements and fingerprint analysis are established. In the color measurements, the color values of the peel and flesh of Crataegi Fructus were evaluated spectrophotometrically. Based on the results, a color reference range was established using percentiles, and the standard color difference value was established using the median color values. Then, the color values of Crataegi Fructus and its processed products were analyzed using Bayes linear discriminant analysis and mathematical functions were built in order to predict the degree of processing. Moreover, high‐performance liquid chromatography fingerprint analysis was performed on a Hibar C₁₈ column, and a high‐performance liquid chromatography fingerprint pattern was obtained, from which nine peaks were identified. Chemometric methods were successfully applied to differentiate raw and processed Crataegi Fructus.     

Studies on the aconitine-type alkaloids in the roots of Aconitum Carmichaeli Debx. by HPLC/ESIMS/MS

Studies of aconitine-type alkaloids in the Chinese herb Aconitum Carmichaeli were performed by HPLC/ESIMS/MSⁿ and FTICR/ESIMS in positive ion mode. The characteristic fragmentation pathways in the MSⁿ spectra were summarized based on previously published research literature and further study. According to the fragmentation pathways of mass spectrometry, results from the analysis of standard compounds and reports from literature, 111 compounds were identified or deduced in a total of 117 found compounds in A. Carmichaeli. In the 11 monoester-diterpenoid alkaloids (MDA), 10 diesterditerpenoid alkaloids (DDA) and 81 lipo-alkaloids, the novel alkaloids including 1 MDA, 2 DDA and 48 lipo-alkaloids were detected. In addition, 1 DDA, 7 lipo-alkaloids and 2 alkaloids with small molecular weights that possess C19-norditerpenoid skeleton were reported in A. Carmichaeli for the first time.     

Screening of pesticides in blood with liquid chromatography–linear ion trap mass spectrometry

In clinical or forensic toxicology, general unknown screening procedures are used to identify as many xenobiotics as possible, belonging to numerous chemical classes. We present here a general unknown screening procedure based on liquid chromatography coupled with use of a single linear ion trap mass spectrometer, and focus on the identification of pesticides and/or metabolites in whole blood. After solid-phase extraction (SPE), the compounds of interest were separated using a reversed-phase column and identified by the mass spectrometer operated first in the full-scan mass spectrometry (MS) mode, in the positive and negative polarities, followed by MS² and MS³ scanning of ions selected in data-dependent acquisition. The total scan time was 2.45 s. Two mass spectral libraries (MS² and MS³), each of 450 spectra, were created for the 320 pesticides and metabolites detected after injection of pure solutions. Robustness of the spectra and matrix effects were studied and were satisfactory for the present application. Detection limits for the 320 compounds were studied by extracting 1 mL spiked blood at concentrations between 10 μg/L and 10 mg/L. If necessary, it was possible to decrease the detection limits of some compounds by 10–100-fold by scanning MS² in only one polarity, owing to a shorter total scan time. However, at the same time, the detection specificity decreased as no confirmation could be recorded in the following MS³ scan and no information could be registered in the other polarity. So, in these rare cases, confirmation by another method was required.     

Structural elucidation of molecular species of pacific oyster ether amino phospholipids by normal-phase liquid chromatography/negative-ion electrospray ionization and quadrupole/multiple-stage linear ion-trap mass spectrometry

Although marine oysters contain abundant amounts of ether-linked aminophospholipids, the structural identification of the various molecular species has not been reported. We developed a normal-phase silica liquid chromatography/negative-ion electrospray ionization/quadrupole multiple-stage linear ion-trap mass spectrometric (NPLC-NI-ESI/Q-TRAP-MS³) method for the structural elucidation of ether molecular species of serine and ethanolamine phospholipids from marine oysters. The major advantages of the approach are (i) to avoid incorrect selection of isobaric precursor ions derived from different phospholipid classes in a lipid mixture, and to generate informative and clear MSⁿ product ion mass spectra of the species for the identification of the sn-1 plasmanyl or plasmenyl linkages, and (ii) to increase precursor ion intensities by “concentrating” lipid molecules of each phospholipid class for further structural determination of minor molecular species. Employing a combination of NPLC-NI-ESI/MS³ and NPLC-NI-ESI/MS², we elucidated, for the first time, the chemical structures of docosahexaenoyl and eicosapentaenoyl plasmenyl phosphatidylserine (PS) species and differentiated up to six isobaric species of diacyl/alkylacyl/alkenylacyl phosphatidylethanolamine (PE) in the US pacific oysters. The presence of a high content of both omega-3 plasmenyl PS/plasmenyl PE species and multiple isobaric molecular species isomers is the noteworthy characteristic of the marine oyster. The simple and robust NPLC-NI-ESI/MSⁿ-based methodology should be particularly valuable in the detailed characterization of marine lipid dietary supplements with respect to omega-3 aminophospholipids.     

Global detection and identification of components from crude and processed traditional Chinese medicine by liquid chromatography connected with hybrid ion trap and time‐of‐flight‐mass spectrometry

We herein present a chemical profiling method to efficiently process the information acquired by ultra fast liquid chromatography (UFLC)‐electrospray ionization source in combination with hybrid ion trap and high‐resolution time‐of‐flight mass spectrometry (UFLC‐(ESI)‐IT‐TOF/MS), facilitating the structural determination of serial components contained in crude or processed traditional Chinese medicine (TCM). Under the optimized UFLC and IT‐TOF‐MSⁿ conditions, over 39 compounds were separated and detected in crude or processed Fructus corni within 25 min. The components were identified by comparing the mass spectra and retention time with reference compounds, or tentatively assigned by elucidating low‐energy collision‐induced dissociation (CID) fragment ions and matching empirical molecular formula with that of the published compounds. Several factors in the processing procedure were examined. The experimental results demonstrate that the chemical reactions that occurred in the processing procedure can be used to elucidate the processed mechanism of F. corni, which is regularly affected by the processing conditions. This study provides a novel approach and methodology to identify the complicated components from various complex mixtures such as crude TCM, processed TCM, and biological samples. It can be used as a valid analytical method for further understanding the processing mechanism of TCM, along with the intrinsic quality control of TCM and its processed product.