Quadrupole-linear Ion Trap Mass Spectrometry Research Articles

Mushroom poisoning of Panaeolus subbalteatus from Ningxia, northwest China, with species identification and tryptamine detection

Mushroom poisoning is a significant contributor to foodborne disease outbreaks in China. This study focuses on two Panaeolus subbalteatus poisoning incidents accompanied by epidemiological investigations, species identification, and toxin detection in Ningxia, northwest China. In these two poisoning incidents, some patients exhibited gastrointestinal or neurological symptoms approximately 0.5 h after ingestion of a large amount of wild mushroom. Specifically, in Case 1, one of the three patients experienced nausea, vomiting, and numbness in the throat and limbs; in Case 2, one patient reported dizziness and an abnormal sense of direction. Through morphological and phylogenetic analyses, mushroom specimens were identified as P. subbalteatus. Psilocybin and psilocin were detected in mushroom samples, and only psilocin was detected in biological samples by liquid chromatography-triple quadrupole-linear ion trap mass spectrometry screening. The average psilocybin and psilocin contents in mushroom samples were 1532.2–1760.7 and 114.5–136.0 mg/kg (n = 3), respectively. Moreover, only psilocin was detected in blood and urine samples, with average concentrations 0.5–1.2 ng/mL (n = 3) and 2.5–3.1 ng/mL (n = 3), respectively. These findings provide technical support for managing similar incidents in the future.

Metabolite identification of salvianolic acid A in rat using post collision-induced dissociation energy-resolved mass spectrometry

BackgroundAs one of the most famous natural products, salvianolic acid A (SAA) is undergoing clinical trials for the treatments of angina pectoris and coronary heart disorders. However, the in vivo metabolites of SAA have only been tentatively identified, leading to a barrier for precise therapeutical drug monitoring.MethodsUltra-high performance liquid chromatography coupled with quadrupole time of flight tandem mass spectrometry (UPLC–Qtof-MS/MS) was firstly employed to acquire high-resolution MS1 and MS2 spectra for all metabolites. Through paying special attention onto the features of ester bond dissociation, metabolism sites were restricted at certain regions. To further determine the metabolism site, such as the monomethylated products (M23, M25, and M26), post collision-induced dissociation energy-resolved mass spectrometry (post-CID ER-MS) was proposed through programming progressive exciting energies to the second collision chamber of hybrid triple quadrupole-linear ion trap mass spectrometry (Qtrap-MS) device.ResultsAfter SAA oral administration, 29 metabolites (M1–M29), including five, thirteen, and sixteen ones in rat plasma, urine, and feces, respectively, were detected in rats. The metabolism route was initially determined by applying well-defined mass fragmentation pathways to those HR-m/z values of precursor and fragment ions. Metabolism site was limited to SAF- or DSS-unit based on the fragmentation patterns of ester functional group. Through matching the dissociation trajectories of concerned 1st-generation fragment ions with expected decomposition product anions using post-CID ER-MS strategy, M23 and M25 were unequivocally assigned as 3'-methyl-SAA and 3''-methyl-SAA, and M26 was identified as 2-methyl-SAA or 3-methyl-SAA. Hydrolysis, methylation, glucuronidation, sulfation, and oxidation were the primary metabolism channels being responsible for the metabolites' generation.ConclusionTogether, the metabolism regions and sites of SAA metabolites were sequentially identified based on the ester bond dissociation features and post-CID ER-MS strategy. Importantly, the present study provided a promising way to elevate the structural identification confidence of natural products and metabolites.Graphical abstract

Combined analysis of inorganic elements and flavonoid metabolites reveals the relationship between flower quality and maturity of Sophora japonica L.

Flos Sophorae (FS), or the dried flower buds of Sophora japonica L., is widely used as a food and medicinal material in China. The quality of S. japonica flowers varies with the developmental stages (S1-S5) of the plant. However, the relationship between FS quality and maturity remains unclear. Inductively coupled plasma optical emission spectrometry (ICP-OES) and ultra-high performance liquid chromatography coupled with electrospray ionization-triple quadrupole-linear ion trap mass spectrometry (UPLC-ESI-Q TRAP-MS/MS) were used to analyze inorganic elements and flavonoid metabolites, respectively. A combined analysis of the inorganic elements and flavonoid metabolites in FS was conducted to determine the patterns of FS quality formation. Sixteen inorganic elements and 173 flavonoid metabolites that accumulated at different developmental stages were identified. Notably, 54 flavonoid metabolites associated with the amelioration of major human diseases were identified, and Ca, P, K, Fe, and Cu were postulated to influence flavonoid metabolism and synthesis. This study offers a novel perspective and foundation for the further exploration of the rules governing the quality of plant materials.

Identification strategy of Fructus Gardeniae and its adulterant based on UHPLC/Q-orbitrap-MS and UHPLC-QTRAP-MS/MS combined with PLS regression model

Fructus Gardeniae (FG) is the desiccative and ripe fruits of Gardenia jasminoides Ellis in the Rubiaceae family, which is a commonly used in traditional Chinese medicine (TCM) for clearing away heat, detoxification, relieving restlessness, and eliminating blood stasis. At the same time, it has also been announced as the first batch of TCM with homology of medicine and food. Fructus Gardeniae Grandiflorae (FGG), the fruit of Gardenia jasminoides Ellis var. grandiflora Nakai (Rubiaceae), is a common counterfeit herbal medicine of FG, which still appears in the TCM market, and causes a certain degree of confusion. In order to effectively distinguish FG and its adulterant, the compounds in these two species were thoroughly characterized firstly by ultrahigh-performance liquid chromatography/quadrupole–orbitrap mass spectrometry (UHPLC/Q-Orbitrap MS). Furthermore, a pseudo-targeted metabonomics method with 60 targeted ion pairs was established based on UHPLC-triple quadrupole-linear ion trap mass spectrometry (UHPLC-QTRAP-MS) for discrimination. Multivariate statistical analysis showed that FG and FGG were clustered obviously, and 13 significantly differential markers were screened out by variable importance for projection (VIP) > 1 and p < 0.05 for the construction of the partial least squares (PLS) regression prediction model. The validation of the model proved that its prediction ability was quite satisfactory. Moreover, based on the absolute quantitative analysis of these 13 characteristics, the quality control standards of FG and FFG were established. In summary, an integral method of pseudo-targeted metabonomics combined with chemometrics analysis and a PLS regression model was proposed to provide an effective identification strategy for discrimination FG and FGG.

Eco-friendly simultaneous extraction of pectins and phenolics from passion fruit (Passiflora edulis Sims) peel: Process optimization, physicochemical properties, and antioxidant activity

The objective of this study was to simultaneously extract passion fruit (Passiflora edulis) peel pectins and phenolics using deep eutectic solvents, to evaluate their physicochemical properties and antioxidant activity. By taking L-proline: citric acid (Pro-CA) as the optimal solvent, the effect of extraction parameters on the yields of extracted passion fruit peel pectins (PFPP) and total phenolic content (TPC) was explored by response surfaces methodology (RSM). A maximum pectin yield (22.63%) and the highest TPC (9.68 mg GAE/g DW) were attained under 90 °C, extraction solvent pH = 2, extraction time of 120 min and L/S ratio of 20 mL/g. In addition, Pro-CA-extracted pectins (Pro-CA-PFPP) and HCl-extracted pectins (HCl-PFPP) were subjected to high performance gel permeation chromatography (HPGPC), Fourier transform infrared spectroscopy (FT-IR), thermogram analysis (TG/DTG) and rheological measurements. Results verified that the Mw and thermal stability of Pro-CA-PFPP were higher than those of HCl-PFPP. The PFPP solutions featured a non-Newtonian behavior, and compared with commercially pectin solution, PFPP solution exhibited a stronger antioxidant activity. Additionally, passion fruit peel extract (PFPE) exhibited stronger antioxidant effects than PFPP. The results of ultra-performance liquid chromatography hybrid triple quadrupole-linear ion trap mass spectrometry (UPLC-Qtrap-MS) and high performance liquid chromatography (HPLC) analysis showed that (−)-epigallocatechin, gallic acid, epicatechin, kaempferol-3-O-rutin and myricetin were the main phenolic compounds in PFPE and PFPP. Our results suggest that Pro-CA can be considered as an eco-friendly solvent for high-efficient extraction of high-value compounds from agricultural by-products.

Constituent Analysis and Quality Evaluation of Epimedii Folium from Different Species

Epimedii Folium (EF) is a commonly used traditional Chinese drug that includes many species. In Chinese Pharmacopoeia (2020 edition), EF includes Epimedium brevicornu Maxim, E. Sagittatum (Sieb. et Zucc) Maxim, E. pubescens Maxim, E. koreanum Nakai, and Epimedium Wushanense T.S. Ying. It has been reported that the active constituents in EF are different, resulting in the uneven quality of commercial medicinal materials. To explore the specific differences and make a comprehensive quality evaluation of EF, we established an analytical method to simultaneously detect 45 constituents including 23 flavonoids, 4 phenolic acids, 12 amino acids, 5 nucleosides, and 1 alkaloid in 5 species of EF, based on ultrafast performance liquid chromatography coupled with triple quadrupole-linear ion trap mass spectrometry (UFLC-QTRAP-MS/MS). In addition, orthogonal partial least squares discriminant analysis (OPLS-DA), analysis of variance (ANOVA), and grey correlation analysis (GRA) were used to discriminate and evaluate different species of samples. The results showed that EF could be divided into three categories and EBM was superior to the other four species. This study provides data basis for the comprehensive evaluation and a new perspective on the quality control of EF from different species.

Content determination of ten flavonoids and alkaloids in Gleditsiae Sinensis Fructus, Gleditsiae Fructus Abnormalis, and Gleditsiae Spina

To study the quality control of three traditional Chinese medicines derived from Gleditsia sinensis [Gleditsiae Sinensis Fructus(GSF), Gleditsiae Fructus Abnormalis(GFA), and Gleditsiae Spina(GS)], this paper established a multiple reaction monitoring(MRM) approach based on ultra-high performance liquid chromatography-triple quadrupole-linear ion-trap mass spectrometry(UHPLC-Q-Trap-MS). Using an ACQUITY UPLC BEH C_(18) column(2.1 mm × 100 mm, 1.7 μm), gradient elution was performed at 40 ℃ with water containing 0.1% formic acid-acetonitrile as the mobile phase running at 0.3 mL·min~(-1), and the separation and content determination of ten chemical constituents(e.g., saikachinoside A, locustoside A, orientin, taxifolin, vitexin, isoquercitrin, luteolin, quercitrin, quercetin, and apigenin) in GSF, GFA, and GS were enabled within 31 min. The established method could quickly and efficiently determine the content of ten chemical constituents in GSF, GFA, and GS. All constituents showed good linearity(r&gt;0.995), and the average recovery rate was 94.09%-110.9%. The results showed that, the content of two alkaloids in GSF(2.03-834.75 μg·g~(-1)) was higher than that in GFA(0.03-10.41 μg·g~(-1)) and GS(0.04-13.66 μg·g~(-1)), while the content of eight flavonoids in GS(0.54-2.38 mg·g~(-1)) was higher than that in GSF(0.08-0.29 mg·g~(-1)) and GFA(0.15-0.32 mg·g~(-1)). These results provide references for the quality control of G. sinensis-derived TCMs.

Identification of circular RNAs of Cannabis sativa L. potentially involved in the biosynthesis of cannabinoids.

We identified circRNAs in the Cannabis sativa L. genome and examined their association with 28 cannabinoids in three tissues of C. sativa. Nine circRNAs are potentially involved in the biosynthesis of six cannabinoids. Cannabis sativa L. has been widely used in the production of medicine, textiles, and food for over 2500years. The main bioactive compounds in C. sativa are cannabinoids, which have multiple important pharmacological actions. Circular RNAs (circRNAs) play essential roles in growth and development, stress resistance, and the biosynthesis of secondary metabolites. However, the circRNAs in C. sativa remain unknown. In this study, to explore the role of circRNAs in cannabinoid biosynthesis, we performed RNA-Seq and metabolomics analysis on the leaves, roots, and stems of C. sativa. We identified 741 overlapping circRNAs by three tools, of which 717, 16, and 8 circRNAs were derived from exonic, intronic, and intergenic, respectively. Functional enrichment analysis indicated that the parental genes (PGs) of circRNAs were enriched in many processes related to biological stress responses. We found that most of the circRNAs showed tissue-specific expression and 65 circRNAs were significantly correlated with their PGs (P < 0.05, |r|≥ 0.5). We also determined 28 cannabinoids by High-performance liquid chromatography-ESI-triple quadrupole-linear ion trap mass spectrometry. Ten circRNAs, including ciR0159, ciR0212, ciR0153, ciR0149, ciR0016, ciR0044, ciR0022, ciR0381, ciR0006, and ciR0025 were found to be associated with six cannabinoids by weighted gene co-expression network analysis. Twenty-nine of 53 candidate circRNAs, including 9 cannabinoids related were validated successfully using PCR amplification and Sanger sequencing. Taken together, all these results would help to enhance our acknowledge of the regulation of circRNAs, and lay the foundation for breeding new C. sativa cultivars with high cannabinoids through manipulating circRNAs.

Metabolomic analysis reveals dynamic changes in secondary metabolites of Sophora japonica L. during flower maturation.

Sophora japonica L. is widely consumed in China because of its medicinal and nutritional value. Its quality is greatly affected by the accumulation of metabolites, which varies with the stage of flower development. However, changes in the characteristics of the secondary metabolites during flower maturity remain unclear. Ultra-high-performance liquid chromatography coupled with electrospray ionization-triple quadrupole-linear ion trap mass spectrometry (UPLC–ESI–QTRAP–MS/MS) revealed dynamic changes in the secondary metabolites of S. japonica during the five flower-maturity stages. We monitored 331 metabolites and screened 164. The differential metabolites showed seven trends during flower maturation, with flavonoids and phenolic acids having the most varied expressions. Flower buds (S2–S3) are rich in flavonoids and are thus suitable for use in high-quality medicine or industrial extraction. Our study provides an empirical basis for the informed harvesting of S. japonica based on its mode of utilization.

Quality Evaluation of Tetrastigmae Radix from Two Different Habitats Based on Simultaneous Determination of Multiple Bioactive Constituents Combined with Multivariate Statistical Analysis.

Tetrastigmae Radix, also known as Sanyeqing (SYQ) in Chinese, is an important traditional Chinese medicine with a long history. Tetrastigma hemsleyanum Diels et Gilg mainly grows in the south of the Yangtze River and is widely distributed. The content of bioactive constituents in SYQ varies greatly in different habitats, and there are obvious differences in the content of bioactive constituents between southwestern SYQ (WS) and southeastern SYQ (ES). To distinguish and evaluate the quality of ES and WS, an analytical method based on ultrafast performance liquid chromatography coupled with triple quadrupole-linear ion trap mass spectrometry (UFLC-QTRAP-MS/MS) was established for the simultaneous determination of 60 constituents including 25 flavonoids, 9 phenolic acids, 15 amino acids, and 11 nucleosides in 47 samples from ES and WS. In addition, orthogonal partial least squares discriminant analysis (OPLS-DA), t-test, and gray correlation analysis (GRA) were used to discriminate and evaluate the ES and WS samples based on the contents of 60 constituents. The results showed that there were significant differences in the bioactive constituents between ES and WS, and ES was superior to WS in terms of quality evaluation. This study not only provides basic information for differentiating ES and WS but also provides a new perspective for the comprehensive evaluation and quality control of SYQ from two different habitats.

Systematic Qualitative and Quantitative Analyses of Wenxin Granule via Ultra-High Performance Liquid Chromatography Coupled with Ion Mobility Quadrupole Time-of-Flight Mass Spectrometry and Triple Quadrupole-Linear Ion Trap Mass Spectrometry.

Wenxin granule (WXG) is a popular traditional Chinese medicine (TCM) preparation for the treatment of arrhythmia disease. Potent analytical technologies are needed to elucidate its chemical composition and assess the quality differences among multibatch samples. In this work, both a multicomponent characterization and quantitative assay of WXG were conducted using two liquid chromatography–mass spectrometry (LC-MS) approaches. An ultra-high performance liquid chromatography–ion mobility quadrupole time-of-flight mass spectrometry (UHPLC/IM-QTOF-MS) approach combined with intelligent peak annotation workflows was developed to characterize the multicomponents of WXG. A hybrid scan approach enabling alternative data-independent and data-dependent acquisitions was established. We characterized 205 components, including 92 ginsenosides, 53 steroidal saponins, 14 alkaloids, and 46 others. Moreover, an optimized scheduled multiple reaction monitoring (sMRM) method was elaborated, targeting 24 compounds of WXG via ultra-high performance liquid chromatography–triple quadrupole linear ion trap mass spectrometry (UHPLC/QTrap-MS), which was validated based on its selectivity, precision, stability, repeatability, linearity, sensitivity, recovery, and matrix effect. By applying this method to 27 batches of WXG samples, the content variations of multiple markers from Notoginseng Radix et Rhizoma (21) and Codonopsis Radix (3) were depicted. Conclusively, we achieved the comprehensive multicomponent characterization and holistic quality assessment of WXG by targeting the non-volatile components.

Degradation of Ochratoxin A by a UV-Mutated Aspergillus niger Strain.

Ochratoxin A (OTA) is a mycotoxin that can contaminate a wide range of crops such as grains and grapes. In this study, a novel fungal mutant strain (FS-UV-21) with a high OTA degradation rate (74.5%) was obtained from Aspergillus niger irradiated with ultraviolet light (15 W for 20 min). The effect of pH, temperature, and inoculation concentration on the degradation of OTA by FS-UV-21 was investigated, and the results revealed that the detoxification effect was optimal (89.4%) at a pH of 8 and a temperature of 30 °C. Ultra-performance liquid chromatography-tandem mass spectrometry was used to characterize the degraded products of OTA, and the main degraded product was ochratoxin α. Triple quadrupole-linear ion trap-mass spectrometry combined with LightSight software was used to analyze the biotransformation pathway of OTA in FS-UV-21, to trace the degraded products, and to identify the main metabolite, P1 (C19H18ClNO6, m/z 404). After the FS-UV-21 strain was treated with OTA, the HepG2 cellular toxicity of the degradation products was significantly reduced. For the real sample, FS-UV-21 was used to remove OTA from wheat bran contaminated by mycotoxins through fermentation, resulting in the degradation of 59.8% of OTA in wheat bran. Therefore, FS-UV-21 can be applied to the degradation of OTA in agricultural products and food.

An integrated strategy for the systematic chemical characterization of Salvianolate lyophilized injection using four scan modes based on the ultra-high performance liquid chromatography-triple quadrupole-linear ion trap mass spectrometry

Salvianolate lyophilized injection (SLI), a freeze-dried powder injection derived from aqueous extract of S. miltiorrhiza, is therapeutically used to treat the syndrome of blood stasis and collateral blockage during the recovery period after stroke. To date, it has remained a significant challenge to comprehensively characterize the compounds of SLI, particularly the minor components with potential bioactivities, in one sample injection analysis. Using an integrative four scan modes approach coupled with ultra-high performance liquid chromatography-triple quadrupole-linear ion trap mass spectrometry (UHPLC-QTRAP-MS/MS), we propose a novel, sensitive, and simple strategy for systematic and rapid profiling of the chemical components of SLI. First, an in-house database of constituents from the water-soluble extract of Danshen was created. Second, the fragmentation behaviors of the representative components in SLI were obtained using the untargeted scan mode enhanced MS (EMS)-information dependent acquisition (IDA)-enhanced product ion (EPI). The specific fragments acquired were then utilized to conduct precursor ion (Prec) and neutral loss (NL)-IDA-EPI scans. Following that, a sensitive predictive multiple reaction monitoring (pMRM)-IDA-EPI scan method with 454 transitions was developed based on the prominent fragment ions and plausible predictions. A total of 171 compounds were tentatively identified from SLI. Among them, 27 minor components have not been previously reported. This strategy allows most isomeric compounds at trace levels to be readily distinguished and annotated. Finally, 15 batches of 13 representative components in SLI selected by the qualitative results were accurately quantified. Salvianolic acid A (Sal A), Sal B, Sal D, lithospermic acid (LA), and rosmarinic acid (RA) were proved to be the predominant constituents. Sal B had the highest amount (195.08–350.46 μg·mg‐1), followed by LA, Sal A, Sal D, and RA. Moreover, these 15 batches of samples showed good uniformity, and no abnormal batches existed. These results suggest that this novel strategy can accelerate the identification of undiscovered chemical components and serve as an alternative method for in-depth profiling of compounds in other traditional Chinese medicines (TCMs).

Analysis of low-abundance molecules in complex matrices by quadrupole-linear ion trap mass spectrometry using a simultaneous fragmentation and accumulation strategy.

Fast and sensitive analysis of low-abundance molecules in complex matrices has always been a challenge in chemical and biological applications. Mass spectrometry (MS) has been widely used in the fields of chemical and biological analysis due to its unparalleled specificity and sensitivity. However, the MS signals consistently deteriorate in the presence of matrices. Demands for more sensitive and efficient methods to analyze those low-abundance molecules in chemical and biological systems are in urgent need. Based on a home-made quadrupole-linear ion trap (Q-LIT) mass spectrometer, a simultaneous fragmentation and accumulation strategy was developed to improve the sensitivity of the analysis for the low-abundance molecules in complex matrices. Ions were filtered by the quadrupole into the LIT. The precursor ions were fragmented and the product ions were isolated and accumulated in the LIT simultaneously. The fragmentation, isolation and accumulation processes were conducted at the same time. The accumulation time could be controlled to accumulate sufficient product ions. With this strategy, the signal intensity of targeted molecules could be increased by 2-8 times and by increasing the accumulation time, this could be further enhanced. Those interferences induced by isomers and matrices can be reduced by using our method. We further applied our method to the quantification and analysis of biological samples. Tryptic digested peptides of myoglobin (Mb) were successfully detected by our method. We have established a new method with great advantages in the detection of molecules in complex matrices. The application of this method promises better results in the bioanalytical area, especially for the analysis of substances in complex matrices in the future.

Multiclass Comparative Analysis of Veterinary Drugs, Mycotoxins, and Pesticides in Bovine Milk by Ultrahigh-Performance Liquid Chromatography-Hybrid Quadrupole-Linear Ion Trap Mass Spectrometry.

A multiclass and multiresidue method for simultaneously screening and confirming veterinary drugs, mycotoxins, and pesticides in bovine milk was developed and validated with ultrahigh-performance liquid chromatography–hybrid quadrupole–linear ion trap mass spectrometry (UHPLC-Qtrap-MS). A total of 209 targeted contaminants were effectively extracted using an optimized QuEChERS method. Quantitative and qualitative confirmation were achieved simultaneously by multiple reaction monitoring–information-dependent acquisition–enhanced product ion (MRM-IDA-EPI) scan mode. The validation results exhibited a good sensitivity with the LOQs of 0.05–5 μg/kg, which was satisfactory for their MRLs in China or EU. The recoveries of in-house spiked samples were in the range of 51.20–129.76% with relative standard deviations (RSD) between replicates (n = 3) 0.82% and 19.76%. The test results of 140 milk samples from supermarkets and dairy farms in China showed that cloxacillin, aflatoxin M1, acetamiprid, and fipronil sulfone were found with lower concentrations. Combined with the residue results from the literature, penicillin G and cloxacillin (beta-lactams), enrofloxacin and ciprofloxacin (fluoroquinolones), and sulfamerazine (sulfonamides) were more frequently detected in different countries and need to receive more attention regarding their monitoring and control.

Target profiling of flavonol glycosides in the extract of Ginkgo biloba leaf and their pharmacokinetics in rat plasma by ultra‐high‐performance liquid chromatography with tandem mass spectrometry

The extract of Ginkgo biloba leaf is a popular herbal product or dietary supplement in the world to treat various diseases, and flavonol glycosides are considered as the main bioactive constituents. In this study, 37 flavonol glycosides were rapidly screened out by precursor ion scanning in positive ion mode with production ions at m/z 287.05, 303.05, and 317.06. Subsequently, a reliable and sensitive ultra-high-performance liquid chromatography coupled with triple quadrupole-linear ion trap mass spectrometry approach was established and validated to quantify the 20 prototype flavonol glycosides in rat plasma. Calibration curves showed good linearity (R2 ≥ 0.9894) over the corresponding concentration range. The precision, accuracy, extraction recovery, matrix effect, and stability were also satisfactory. The validated method was successfully applied to a pharmacokinetic study of prototype flavonol glycosides in rat after oral administration of the extract of G. biloba leaf. As a result, the Tmax of flavonol glycosides was short at 0.11-0.60 h. Quercetin-3-O-(2",6″-di-O-rhamnosyl)-glucoside, kaempferol-3-O-(2'',6''-di-O-rhamnosyl)-glucoside, quercetin-3-O-rutinoside, quercetin- 3-O-glucosyl-(1-2)-O-rhamnoside, and kaempferol-3-O-glucoside presented relatively high systemic exposure levels with AUC0-∞ >500 μg h/L and Cmax >100 μg/L. This study would provide the valuable information for further scientific research and clinical application of the extract of G. biloba leaf.

Determination of lipophilic marine biotoxins in shellfish foods by ultra performance liquid chromatography-hybrid triple quadrupole linear ion trap-mass spectrometry

An ultra performance liquid chromatography-hybrid triple quadrupole linear ion trap-mass spectrometry(UPLC-QqLIT-MS) was established for determination of lipophilic marine biotoxins in shellfish. And the 12 lipophilic marine biotoxins in shellfish were surveyed. The lipophilic marine biotoxins in homogenized shellfish were ultrasonically extracted by methanol in super-sonic instrument, and cleaned up by solid phase extraction of Strata-X column, and eluted with methanol(containing 0.3% ammonia water). The elution was diluted with water, and cleaned by 0.22 μm millipore filter. The filtrate was separated on a Waters ACQUITY UPLC BEH C_(18) column(150 mm×2.1 mm, 1.7 μm)by gradient elution in 12 minutes with acetronitrile-water(containing 0.01%(V/V) ammonia and 2 mmol/L ammonium formate) as mobile phase, and detected by ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS), identified by electrospray ionization(ESI) in simultaneous scanning mode of positive and negative ions using multiple reaction monitoring, and quantified with external standards. Information dependent acquisition scan function(IDA) combined with enhanced production scan(EPI) was used to confirm the 12 lipophilic marine biotoxins. The calibration curves of 12 lipophilic marine biotoxins showed good linearity in the range of 0.5-50 μg/L with correlation coefficients were 0.9984-0.9999.The detection limits of the method were 0.15-0.29 μg/kg. The recoveries of three spiking levels ranged from 80.0% to 116.0%, and the relative standard deviation(RSD) were 0.6%-6.4%(n=7). The method for determination of 12 lipophilic marine biotoxins in shellfish by UPLC-QqLIT-MS was of operation convenience, less interference from impurities and good accuracy, which could meet the requirements for the determination of 12 lipophilic marine biotoxins residues in sea foods.

Quick determination of Glyphosate and AMPA at sub µg/L in drinking water by direct injection into LC-MS/MS

A sensitive, simple and quick method for the determination of glyphosate (Gly) and its degradation product, Aminomethyl phosphonic acid (AMPA), in water through ion chromatography coupled to quadrupole-linear ion trap mass spectrometry has been developed. Sample treatment was based on direct injection and acquisition was implemented in both MS2 and MS3 modes. The LoQs of the method were 0.03 µ/L for both Gly-and AMPA. The recoveries were between 91 and 118% and RSD was lower than 15%. The developed methodology was applied on 436 water samples.

Simultaneous Determination of Iridoid Glycosides, Phenylpropanoid Glycosides, Organic Acids, Nucleosides and Amino Acids in Scrophulariae Radix Processed by Different Processing Methods by HPLC-QTRAP-MS/MS.

Scrophulariae Radix is one of the widely used traditional Chinese medicines. In this study, a high-performance liquid chromatography coupled with triple quadrupole-linear ion trap mass spectrometry method was established for the simultaneous determination of multiple bioactive constituents including four iridoid glycosides, two phenylpropanoid glycosides, six organic acids, 11 nucleosides and 16 amino acids in Scrophulariae Radix. The validated method was used to analyze nine Scrophulariae Radix samples processed by different processing methods. In addition, Grey relational analysis and DTOPSIS were used to evaluate the samples according to the content of 39 ayalytes. The results showed that the quality of Scrophulariae Radix processed by cutting into slices, sun drying and "sweating" methods were better. All the results proved that the developed method was available and could be used to evaluate the quality of Scrophulariae Radix.

Development of a QuEChERS-based method for the analysis of pharmaceuticals and personal care products in lettuces grown in field-scale agricultural plots irrigated with reclaimed water

The use of reclaimed water for agricultural irrigation is an increasingly common practice, which recently has found its own European regulatory frame. However, the partial removal of organic contaminants together with other xenobiotic substances in current wastewater treatment plants leads to the occurrence of residues of such pollutants in the treated effluents. Wastewater reclamation techniques are thus required to provide reclaimed water fitting the minimum quality standards set up for irrigation of crops intended for human consumption. This work describes the development and validation of a simple QuEChERS-based extraction and liquid chromatography quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS/MS) method for the simultaneous quantitative analysis of 55 pharmaceuticals and personal care products (PPCPs) in lettuces irrigated with treated wastewater and reclaimed water. The method showed good recovery rates (80–120%) and low detection limits (0.04–0.8 ng/g dw). In comparison with previous analytical methodologies, this method was simpler, faster and, in most cases, more sensitive. Moreover, is the first one analysing selected personal care products in lettuces. The proposed method was applied to assess the potential transfer of contaminants of urban origin in the use of reclaimed water in agriculture. The case study consisted in the evaluation of the lettuce uptake of the selected contaminants at field scale under two irrigation systems, two soil compositions, and two water types. Benzophenone-2, 4-hydroxybenzophenone, 1H-benzotriazole, 2-(2-Benzotriazol-2-yl)-p-cresol, nalidixic acid, diclofenac, carbamazepine 10,11-epoxy, N-des-methylvenlafaxine, and salicylic acid were transferred to all samples. Highest detected values corresponded to 4-hydroxybenzophenone (84.1 ng/g dw), benzophenone-2 (54.4 ng/g dw), and salicylic acid (53.8 ng/g dw). The best combination to minimize the transfer of the target contaminants from the irrigation water to the lettuces was sprinkling irrigation with water reclaimed by soil infiltration through reactive barriers, and clayey soil.