Liquid Chromatography-tandem Quadrupole Mass Research Articles

Magnetic surface-imprinted polymer microspheres coupled with HPLC-MS/MS for sensitive detection of amphetamine-type drugs in water

Magnetic surface imprinted polymer microspheres (Fe3O4@MIPs) were successfully synthesized via Pickering emulsion polymerization, utilizing N-Methylphenethylamine as a surrogate template for amphetamine-type drugs. Fe3O4@MIPs not only possessed excellent dispersibility and enough magnetic properties in aqueous solutions, but also displayed good selectivity towards six amphetamines, with an imprinting factor ranging from 1.8 to 2.6. The adsorption kinetics closely aligned with the pseudo-second-order model, and the adsorption efficiency exceeds 80 % for each amphetamine at equilibrium. Fe3O4@MIPs were then employed as the efficient adsorbents for the extraction of amphetamine drugs. Extraction parameters, including sample pH, the mass of adsorbent, and the type and volume of eluting solvent, were carefully optimized. In combination with the high performance liquid chromatography tandem triple quadrupole mass spectrometry (HPLC-MS/MS), a selective magnetic solid-phase extraction (MISPE) method utilizing Fe3O4@MIPs was developed for the detection of six amphetamines in water samples. The limits of detection and limits of quantitation were determined to be 5.2∼23 ng L−1 and 17∼77 ng L−1, respectively. Recoveries for the six target drugs from lake water and sewage samples fell within the range of 87.2∼110 %. Additionally, the MISPE-HPLC-MS/MS method exhibited excellent repeatability, with a precision below 8.5 % at two spiking levels. The prepared Fe3O4@MIPs possessed the advantages of high selectivity, straightforward preparation, facile separation and good reusability, and was highly suitable for the efficient extraction of amphetamine-type substances in complex environmental water.

A multi-technique based analytical platform for characterization and identification of a newly emerged steroid 6β-chlorotestosterone and its in-vivo epimeric metabolites

Doping athletes tend to use new and non-approved drugs in an attempt to circumvent the dope test. Recently, a package of unknown drug was obtained from black market claiming to contain steroid-like compound, which could not be readily identified due to the lack of commercially available reference standards. In order to characterize and identify the chemical structure of the unknown compound, ultra performance liquid chromatography high resolution mass spectrometry (UPLC-HRMS), high performance liquid chromatography tandem quadrupole mass spectrometry (HPLC-MS/MS), gas chromatography tandem quadrupole mass spectrometry (GC–MS/MS) and nuclear magnetic resonance (NMR) instruments were applied in this work. Based on the combined data, the unknown compound was identified as 6β-chlorotestosterone. The aim of this study was to find urinary metabolic biomarkers of 6β-chlorotestosterone for clinical research and doping control analysis. Ten in-vivo metabolites including four phase I metabolites and six phase II metabolites were characterized and potentially identified. The detailed structure of the phase I metabolite was successfully obtained by GC–MS/MS analysis of trimethylsilylation (TMS) released upon dissolution, overcoming the absence of useful fragment ions to demonstrate the structure of sulfate metabolites. Two strategies including metabolic mechanisms and retention time variation of steroids were introduced to determine and distinguish 3α/β- and 5α/β- epimeric metabolites. A comprehensive evaluation was conducted on time of appearance and detection of each metabolite. The sulfate metabolite 6β-chloro-5β-androstan-17-one-3β-O-sulfate (S1) could be detected up to 12 days after oral administration, which was considered to be the long term biomarker for 6β-chlorotestosterone abuse in clinical research and doping control analysis.

A randomized control trial to test the effect of pegbovigrastim treatment at dry-off on plasma and milk oxylipid profiles during early mammary gland involution and the postparturient period

The early period of mammary gland involution is a critical juncture in the lactation cycle that can have significant effects on milk production and mammary gland health. Pegbovigrastim (PEG) administered 1 wk prior and on the day of parturition can enhance immune function and reduce the incidence of mastitis in the early postpartum period. Oxylipids are potent metabolites of polyunsaturated fatty acids (PUFA) and are important mediators of inflammation. The objective of this study was to evaluate effects of PEG given 1 wk before and at the day of dry-off (D0) on concentrations of oxylipids in plasma and milk from 7 d before D0 to 14 d after, as well as the effects during the first 14 d of the subsequent lactation. We hypothesized that both pro- and anti-inflammatory oxylipids would vary based on initiation of mammary gland involution and that pegbovigrastim would affect oxylipid concentrations, particularly those related to leukocytes. A complete randomized blocked design was used to enroll cows into either a PEG treatment group (n = 10) or control group (n = 10; CON). Blood samples were collected -7, -2, -1, 0, 1, 2, 4, 7, and 14 d relative to dry-off and 5, 10, and 14 d postcalving. Samples were analyzed for PUFA and oxylipids in milk and plasma by ultra-performance mass spectrometry and liquid chromatography tandem quadrupole mass spectrometry, respectively. Overall, 30 lipid mediators were measured in both milk and plasma. Repeated measures analyses revealed a significant interaction of treatment by time for milk 8-iso-keto-15-prostaglandin E2, prostaglandin F2α, plasma 8,12-iso-prostaglandin Fα-VI, 11-hydroxyeicosatetraenoic acid, and 12-hydroxyheptadecatienoic acid. The majority of milk PUFA and oxylipids differed significantly during early mammary gland involution and into the early postpartum period. This study demonstrated changes in oxylipids in milk secretions and plasma during early involution, and further investigation may illuminate multiple complex processes and reveal targets for optimization of mammary gland involution.

Detection of Multiple Antibiotic Residues in Turkish Pine and Blossom Honeys Using LC-MS/MS Method.

Due to the high demand for honey, beekeepers often feed the bees with antibiotics to protect honeybees against illnesses; the determination of veterinary drugs and their residues in bee products especially in honey is gaining importance. In this study, commercially available 15 different brands, a total of 22 honey (14 blossoms and 8 pines) samples obtained from 5 chain supermarkets in the city of Bingöl and Diyarbakır, Turkey were analysed for 29 antibiotic residues. These antibiotics belong to 10 different categories, including tetracyclines, aminoglycosides, macrolides, sulfonamides, fluoroquinolones, benzimidazoles, anthelmintic, amphenicols, quinolines, and oxazolidines. For the qualitative and quantitative determination of the antibiotics, a triple quadrupole liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used. A total of 10 out of 22 honey (8 blossom, 57.14 % and 2 pine, 25 %) samples were found to be positive for antibiotics. Among the tested antibiotics, tetracycline, dihydrostreptomycin, streptomycin, erythromycin, and sulfadimidine were detected in the honey samples. Dihydrostreptomycin and sulfadimidine were detected in 6 samples, erythromycin was determined in 4 samples, streptomycin was found in 2 samples, and lastly, tetracycline was detected only in one sample. The highest and the lowest concentrations of antibiotics detected in the samples were dihydrostreptomycin and erythromycin found at the amount of 992.58 μg/kg and 0.77 μg/kg respectively. The proposed method was validated with a limit of quantification (LOQ) and limit of detection (LOD) ranging between 0.42 and 3.22 μg /kg and 0.13-0.97 μg /kg respectively. Good linearities were also achieved ranging between R2 =0.987 and 0.999.

A Negative Association between Plasma Phylloquinone and All-Cause Mortality in Chinese Adults with Hypertension: A Nested Case-Control Study

BackgroundPrevious studies have revealed that vitamin K is essential for preventing various chronic diseases. Phylloquinone is the primary dietary and circulating form of vitamin K. However, data concerning the association between plasma phylloquinone and all-cause mortality are limited. ObjectivesThis study aimed to evaluate the association between plasma phylloquinone and risk of all-cause mortality and examine some potential confounders. MethodsThis study is a post hoc analysis of the RCT and a nested, case-control design was used. Enrolled participants had to have hypertension at baseline. Study initiation was 19 May, 2008, and the median follow-up was 4.5 y. A total of 604 mortality cases and 604 controls matched for age, sex, treatment group, and study site were included in this study. Odds ratios (OR) and 95% confidence intervals (CIs) of all-cause mortality were calculated using conditional or unconditional logistic regression, without or with adjusting for pertinent covariates, respectively. The concentration of phylloquinone was measured by liquid chromatography–tandem quadrupole mass spectrometry (LC-MS/MS). ResultsThe mean and median phylloquinone levels were 1.62 nmol/L and 0.89 nmol/L, respectively. There was a significant negative association between log-transformed plasma phylloquinone and all-cause mortality after controlling for potential confounders (per 1 unit increase-OR: 0.79; 95% CI: 0.66, 0.95). Furthermore, the association of plasma phylloquinone with risk of all-cause mortality differed by body mass index (BMI) (<25 kg/m2 compared with ≥25 kg/m2, P-interaction = 0.004). A significant trend of decreasing risk with increasing concentration of phylloquinone was observed in participants with higher BMI (per 1 unit increase-OR: 0.71; 95% CI: 0.56, 0.90; P = 0.004). No significant correlation was found between phylloquinone and risk of all-cause mortality in those with BMI <25 kg/m2. ConclusionsIn Chinese patients with hypertension, there was a significant negative association between baseline plasma phylloquinone and all-cause mortality, especially among those with higher BMI.

Analytical Techniques in Exploring the Persistent Global PFAS Problem

Per- and polyfluoroalkyl substances (PFAS) are synthetic chemicals with unique properties. They are used in a wide range of different industries because they repel water and oil, and they are heat-resistant. However, PFAS contamination has become a widespread global concern because of their ubiquitous occurrence, persistence in the environment and living organisms, and potential health risks. Governments around the world are continuously introducing and updating regulatory limits for PFAS in drinking water, other types of water, biota, and, most recently, food. Analyzing such a wide range of sample types for PFAS requires high sensitivity and selectivity, typically provided by methods based on advanced liquid chromatography–tandem quadrupole mass spectrometry (LC–MS/MS) instrumentation. However, one critical aspect to sampling and analyzing PFAS accurately is to avoid PFAS contamination during these processes. This paper emphasizes the significance of robust and reliable PFAS analysis to support efforts to mitigate the global PFAS crisis. Collaboration, research, and advanced analytical solutions are essential to safeguard food, water, and the environment, thusly reducing the impact of PFAS on public health and the environment.

A comprehensive analytical strategy based on characteristic fragments to detect synthetic cannabinoid analogs in seized products and hair samples

Synthetic cannabinoids, one of the most widely abused new psychoactive substances (NPS), are now placed under national control generally in China. Due to continuous modification of synthetic cannabinoid structure, an ongoing dilemma in the forensic laboratory is that newly emerging substances cannot be detected by established methods. Thus, the screening methods for simultaneous detection of known or unknown substances have become research hotspots. In this study, the ultra high performance liquid chromatography tandem triple quadrupole mass spectrometry (UPLC-QqQ-MS) with precursor ion scan (PIS) as acquisition mode was used for prescreening purposes of all possible synthetic cannabinoids-related substances. In detail, four common characteristic fragments, m/z of 144.0, 145.0, 135.1, and 109.0 corresponding to acylium-indole, acylium-indazole, adamantyl, and fluorobenzyl cation respectively, were selected for PIS mode, and their collision energies were optimized by 97 available synthetic cannabinoids standards with relevant structures. Those suspicious signals observed in the screening experiment were confirmed by ultra high performance liquid chromatography tandem quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) via high-resolution MS and MS2 data obtained by full scan (TOF MS) and product ion scan mode. After methodological validation, the integrated strategy established above was applied to the screening and identification of the seized e-liquids, herbal blends and hair samples, confirming the presence of multiple synthetic cannabinoids in these samples. In particular, a novel synthetic cannabinoid was identified as 4 F-ABUTINACA, for which no relevant high-resolution mass spectrometry (HRMS) data has been retrieved until now, making this study the first to report the cleavage pattern of this compound in electrospray ionization (ESI) mass spectrometry. In addition, four other suspected by-products of the synthetic cannabinoids were found in the herbal blends and e-liquids, and their possible structures were also deduced via the information from high-resolution mass spectra.

Screening, characterization, and determination of suspected additives bimatoprost and latanoprost in cosmetics using NMR and LC-MS methods.

Recently, many new types of cosmetic illegal additives have been screened in the market. Most of the new additives were new drugs or analogues with very similar structures to other prohibited additives, which were difficult to be identified by liquid chromatography-mass spectrometry (LC-MS) only. Therefore, a new strategy is proposed, which is chromatographic separation combined with nuclear magnetic resonance spectroscopy (NMR) structural identification. The suspected samples were screened by ultra-high-performance liquid chromatography tandem high-resolution mass spectrometry (UPLC-Q-TOF-MS), followed by purification and extraction through silica-gel column chromatography and preparative high-performance liquid chromatography (HPLC). Finally, the extracts were identified unambiguously by NMR as bimatoprost and latanoprost, which were identified to be new cosmetic illegal additives in eyelash serums in China. Meanwhile, bimatoprost and latanoprost were quantified by high-performance liquid chromatography tandem triple quadrupole mass spectrum (HPLC-QQQ-MS/MS). The quantitative method demonstrated good linearity in the range of approximately 0.25-50ng/mL (R2 > 0.9992), with limit of detection (LOD) and limit of quantification (LOQ) values of 0.01 and 0.03mg/kg, respectively. The accuracy, precision, and reproducibility were confirmed to be acceptable.

The Study of Yak Colostrum Nutritional Content Based on Foodomics.

The utilization of yak milk is still in a primary stage, and the nutrition composition of yak colostrum is not systematically characterized at present. In this study, the lipids, fatty acids, amino acids and their derivatives, metabolites in yak colostrum, and mature milk were detected by the non-targeted lipidomics based on (ultra high performance liquid chromatography tandem quadrupole mass spectrometer) UHPLC-MS, the targeted metabolome based on gas chromatography-mass spectrometer (GC-MS), the targeted metabolome analysis based on UHPLC-MS, and the non-targeted metabolome based on ultra high performance liquid chromatography tandem quadrupole time of flight mass spectrometer (UHPLC-TOF-MS), respectively. Meanwhile, the nutrition composition of yak colostrum was compared with the data of cow mature milk in the literatures. The results showed that the nutritive value of yak colostrum was higher by contrast with yak and cow mature milk from the perspective of the fatty acid composition and the content of Σpolyunsaturated fatty acids (PUFAs), Σn-3PUFAs; the content of essential amino acid (EAA) and the ratio of EAA/total amino acid (TAA) in yak colostrum were higher than the value in yak mature milk; and the content of functional active lipids including phosphatidylcholines (PC), phosphatidylglycerol (PG), phosphatidylserine (PS), lyso-phosphatidylcholine (LPC), lyso-phosphatidylglycerol (LPG), lyso-phosphatidylinositol (LPI), sphingomyelin (SM), ganglioside M3 (GM3), ganglioside T3 (GT3), and hexaglycosylceramide (Hex1Cer) in yak colostrum, was higher than the value of yak mature milk. Moreover, the differences of nutritive value between yak colostrum and mature milk were generated by the fat, amino acids and carbohydrate metabolism that were regulated by the ovarian hormone and referencesrenin-angiotensin-aldosterone system in yaks. These research results can provide a theoretical basis for the commercial product development of yak colostrum.

Polygoni Multiflori Radix interferes with bile acid metabolism homeostasis by inhibiting Fxr transcription, leading to cholestasis.

Objective: To explore the possible mechanisms of cholestasis induced by Polygoni Multiflori Radix (PM). Methods: Low and high doses of water extract of PM were given to mice by gavage for 8weeks. The serum biochemical indexes of aspartate aminotransferase (AST), alanine aminotransferase (ALT), glutamyltransferase (GGT) alkaline phosphatase (ALP) and so on were detected in the second, fourth, sixth, and eighth weeks after administration. At the end of the eighth week of administration, the bile acid metabolic profiles of liver and bile were screened by high-performance liquid chromatography tandem triple quadrupole mass spectrometry (HPLC-QQQ-MS/MS). Liver pathological changes were observed by hematoxylin and eosin staining. Real-time quantitative polymerase chain reaction (RT-qPCR) was used to detect the mRNA transcription of the target genes and Western blotting (WB) was used to the detect target protein expression. Results: Biochemical tests results showed the values of ALP and GGT were two and three times greater than the normal values respectively, and the value of R was less than 2. Histopathology also showed that PM caused lymphocyte infiltration, a small amount of hepatocyte necrosis and nuclear fragmentation in mouse liver. The proliferation of bile duct epithelial cells was observed in the high group. These results indicated that PM may lead to cholestatic liver injury. HPLC-QQQ-MS/MS analysis with the multivariate statistical analysis revealed significant alterations of individual bile acids in liver and gallbladder as compared to those of the control group. RT-qPCR showed that the transcription of Fxr, Shp, Bsep, Bacs, Mdr2, and Ugt1a1 were downregulated and that of Cyp7a1, Mrp3, and Cyp3a11 was significantly upregulated in the treatment group. WB demonstrated that PM also markedly downregulated the protein expression of FXR, BSEP, and MDR2, and upregulated CYP7A1. Conclusion: PM inhibited the expression of FXR, which reduced the expression of MDR2 and BSEP, leading to the obstruction of bile acids outflow, and increased the expression of CYP7A1, resulting in an increase of intrahepatic bile acid synthesis, which can lead to cholestasis.

A sensitive LC-MS/MS method-based pharmacokinetic study of fifteen active ingredients of Yindan Xinnaotong soft capsule in rats and its potential mechanism in the treatment of cardiovascular diseases

Yindan Xinnaotong soft capsule (YDXNT) is a commonly used Chinese herbal preparation for the clinical treatment of coronary disease. However, there is a lack of pharmacokinetic studies on YDXNT, and its active ingredients and their mechanism in the treatment of cardiovascular diseases (CVD) are still unclear. In this study, 15 absorbed ingredients in rat plasma after oral administration of YDXNT were quickly identified based on liquid chromatography tandem quadrupole time-of-flight mass spectrometry (LC-QTOF MS), and then a sensitive and accurate quantitative method based on ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometry (UHPLC-QQQ MS) was established and validated for simultaneous determination of the 15 ingredients of YDXNT in rat plasma, which was then applied to the pharmacokinetic study. Different types of compounds showed various pharmacokinetic characteristics, for instance, ginkgolides with higher maximum plasma concentration (Cmax), flavonoids presenting concentration–time curve with double peaks, phenolic acids with shorter time to reach maximum plasma concentration (Tmax), saponins with long elimination half-life (t1/2) and tanshinones showing fluctuant plasma concentration. Then the measured analytes were regarded as effective compounds and their potential targets and mechanism of action were predicted by constructing and analyzing the compound-target network of YDXNT and CVD. Those potential active compounds of YDXNT interacted with targets such as MAPK1 and MAPK8, and molecular docking showed that the binding free energies of 12 ingredients with MAPK1 were less than −5.0 kcal/mol, indicating that YDXNT intervened in the MAPK signaling pathway to display its therapeutic effect on CVD.

A Rapid Determination of 30 Prohibited Pesticide Residues in Lycii Fructus by UPLC-MS/MS

Prohibited pesticide residues have become one of the main factors affecting the quality and safety of Lycii Fructus, However, rarely studies focus on the rapid determination of these residues. Here, a total of 30 kinds of prohibited pesticide residues were determined by ultra-performance liquid chromatography tandem triple quadrupole mass spectrometry (UPLC-MS/MS) in five different process ways. Pretreatment methods, chromatographic separation and detection conditions in mass spectrometry were all optimized accordingly. Among the five different pretreatment methods, the first and third solid phase extraction failed to provide high recoveries of sulfosulfuron compounds (both lower than 60%). Recovery of chlorphenamidine by the Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) was lower than 60%, which did not meet the requirements of trace determination. The concentrations of 30 prohibited pesticides residues treated by straightforward and solid phase extraction showed good linearity in their corresponding ranges, with correlation coefficients over 0.99. The average recoveries of straightforward ranged from 78.13% to 110.9%, while RSD ranged from 1.3% to 16.9%, albeit poor purification was observed. The recovery yield from solid phase extraction was between 67.75% and 103.08% with RSD value from 0.8% to 14.0%, which met the requirements of trace determination, this method has good precision and stability. These results could be employed to other Traditional Chinese Medicines (TCMs) in detecting prohibited pesticide residues.

Plasma pharmacokinetics and pharmacodynamic effects of the 2-benzylbenzimidazole synthetic opioid, isotonitazene, in male rats

Isotonitazene is an illicit synthetic opioid associated with many intoxications and fatalities. Recent studies show that isotonitazene is a potent µ-opioid receptor (MOR) agonist in vitro, but little information is available about its in vivo effects. The aims of the present study were to investigate the pharmacokinetics of isotonitazene in rats, and relate pharmacokinetic parameters to pharmacodynamic effects. Isotonitazene and its metabolites were identified and quantified by liquid chromatography tandem quadrupole mass spectrometry (LC-QQQ-MS). Male Sprague-Dawley rats with jugular catheters and subcutaneous (s.c.) temperature transponders received isotonitazene (3, 10, 30µg/kg, s.c.) or its vehicle. Blood samples were drawn at 15, 30, 60, 120, and 240min post-injection, and plasma was assayed using LC-QQQ-MS. At each blood draw, body temperature, catalepsy scores, and hot plate latencies were recorded. Maximum plasma concentrations of isotonitazene rose in parallel with increasing dose (range 0.2-9.8ng/mL) and half-life ranged from 23.4 to 63.3min. The metabolites 4'-hydroxy nitazene and N-desethyl isotonitazene were detected, and plasma concentrations were below the limit of quantitation (0.5ng/mL) but above the limit of detection (0.1ng/mL). Isotonitazene produced antinociception (ED50 = 4.22µg/kg), catalepsy-like symptoms (ED50 = 8.68µg/kg), and hypothermia (only at 30µg/kg) that were significantly correlated with concentrations of isotonitazene. Radioligand binding in rat brain tissue revealed that isotonitazene displays nM affinity for MOR (Ki = 15.8nM), while the N-desethyl metabolite shows even greater affinity (Ki = 2.2nM). In summary, isotonitazene is a potent MOR agonist whose pharmacodynamic effects are related to circulating concentrations of the parent drug. The high potency of isotonitazene portends substantial risk to users who are exposed to the drug.

Metabolic profiling and pharmacokinetic studies of Baihu-Guizhi decoction in rats by UFLC-Q-TOF–MS/MS and UHPLC-Q-TRAP-MS/MS

BackgroundBaihu-Guizhi decoction (BHGZD) is a well-documented traditional Chinese Medicine (TCM) prescription that has been extensively applied to treating rheumatoid arthritis. Despite of its beneficial outcomes, the chemical constituents of BHGZD have not been fully portrayed and the in vivo absorption, distribution, metabolism, and excretion (ADME) patterns of absorbed components have never been described.MethodsCharacterization of absorbed components and in vivo biotransformation profiling of these feature compounds were based on the ultra-fast liquid chromatography-quadrupole-time-of-flight tandem mass spectrometry (UFLC-Q-TOF-MS/MS). Furthermore, the ultra-high-performance liquid chromatography tandem ion trap quadrupole mass spectrometry (UHPLC-Q-TRAP-MS/MS) system were performed to investigate the pharmacokinetics of active ingredients from BHGZD.ResultsIn this study, we have identified and tentatively characterized 18 feature absorbed prototype and 15 metabolites of BHGZD in rat serum and the in vivo transformation pathways of these absorbed constituents were proposed. Besides, we have established novel quantitative methodology of five crucial components of BHGZD and have monitored the pharmacokinetic behaviors of these constituents spontaneously in rat serum after BHGZD gavage. After rats received two ways of BHGZD gavage, the pharmacokinetic behaviors of each compound exhibited relatively similar behaviors, as evidenced by similar curve track as well as relatively close time to reach maximum concentration (Tmax) and half washout time (T1/2). Whereas the maximum plasma concentration (Cmax) and area under the plasma concentration–time curve (AUC) values of five analytes with multiple dosage were a bit higher than single dosage.ConclusionThis study added knowledge into the material basis and bio-transformation patterns of BHGZD in vivo, which would be of great value for exploring pharmacological effects and mechanism of BHGZD.

Visual authentication of steroidal saponins in Allium macrostemon Bge. and Allium chinense G. Don using MALDI-TOF imaging mass spectrometry and their structure activity relationship

Allium macrostemon Bge. (AMB) and Allium chinense G. Don (ACGD), both named Allii Macrostemonis Bulbus or Xiebai in Chinese, belong to the same genus. They are both used as edible vegetables and medicinal herbs for the treatment of atherosclerosis. So far, comparative analysis of the spatial metabolomes and platelet aggregation function of steroidal saponins has rarely been performed. In this study, high mass resolution matrix-assisted laser desorption/ionization time-of-flight imaging mass spectrometry (MALDI-TOF MSI) were performed on the fresh bulbs of these two herbs for the spatial distribution of steroidal saponins, and ultra-high-performance liquid chromatography tandem triple quadrupole mass spectrometry (UHPLC/TQD-MS) was used to quantify their content levels. Platelet inhibitory activity induced by arachidonic acid, adenosine diphosphate and collagen were fully investigated. A total of 53 differential variables with compounds were identified or tentatively characterized between AMB and ACGD samples by UHPLC/TQD-MS. Furthermore, these steroidal saponins were almost distributed in tunic and outer scale regions of AMB, while they were rich in tunic and whole leaf scale, and rarely in developing flower bud of ACGD bulbs. Quantitative results demonstrated several saponins were the unique components for AMB (macrostemonoside I, timosaponin B-II, macrostemonoside F, etc.) and ACGD (chinenoside I, chinenoside II, chinenoside IV, etc.). Moreover, spirostanol saponins exhibited stronger inhibitory platelet activity than furostanol saponins, and the structure activity relationship was further summarized. In conclusion, high-mass resolution MALDI full-scan MSI provides abundant spatial distribution information of steroidal saponins in AMB and ACGD. And we finished the discussion of their activity characteristics. These findings would benefit the understanding of safety and effectiveness for their edible and medicinal use.

Comprehensive Evaluation of the Quality of Tripterygium Glycosides Tablets Based on Multi-Component Quantification Combined with an In Vitro Biological Assay.

Tripterygium glycosides tablets (TGTs) are widely used in clinical practice to treat rheumatoid arthritis and other autoimmune diseases, with significant beneficial effects but also high toxicity, necessitating rigorous quality evaluation and control. In current study, a rapid resolution liquid chromatography tandem electrospray ionization triple quadrupole mass spectrometry (RRLC–ESI–MS/MS) method was developed and validated for the quantitative analysis of 14 components of ten batches of TGTs produced by different manufacturers, including four diterpenoids, three triterpenoids, and seven sesquiterpene alkaloids. Meanwhile, the NO inhibition effects of these TGTs were evaluated in LPS-induced RAW264.7 cells for their downstream anti-inflammatory activities, as well as their cytotoxicity. The results indicate that the TGTs from different manufacturers showed poor quality consistency, as evidenced by large variations in chemical profiles and biological effects, which may increase the risks associated with clinical use. To improve the quality status of TGTs, it is crucial to identify indicator components whose characterization can accurately reflect the efficacy and toxicity of TGTs from which they were derived. Our study reveals that triptolide, triptoquinone B, celastrol, and demethylzelaysteral considerably contributed to the anti-inflammatory activity and/or cytotoxicity of TGTs, implying that they should be further investigated as candidate indicator components for TGT quality control.

Sample pretreatment and analytical methodology for the determination of antibiotics in swine wastewater and activated sludge.

An analytical method for the simultaneous extraction and determination of eight veterinary antibiotics in swine wastewater and activated sludge was developed and validated based on the instrumental determination by liquid chromatography tandem quadrupole mass spectrometry. Ultrasound-assisted extraction and solid-phase extraction were introduced into the pretreatment procedure of the two complex environmental matrices. The critical steps involved in the sample pretreatment procedure and the instrumental analysis conditions were optimized progressively. Recoveries of the optimized method were good with 75.3-118.2% in wastewater and 82.8-130.1% in sludge. The absolute deviations of methods were lower than 11.7%, presenting a high reproducibility and precision. The limits of quantification for the eight pharmaceuticals in wastewater and sludge were 5-15 ng·L-1 and 2-6 ng·g-1, showing high sensitivity of the methods. The developed method has been successfully applied to evaluate the actual concentration levels of tetracyclines, quinolones, and sulfonamides in actual swine wastewater (maximum detected concentration of 87.377 μg·L-1) and activated sludge (maximum detected concentration of 51242.3 ng·g-1).

Conduction of a chemical structure-guided metabolic phenotype analysis method targeting phenylpropane pathway via LC-MS: Ginkgo biloba and soybean as examples

The phenylpropane pathway (PPP) is one of the most extensively investigated metabolic routes. This pathway biosynthesizes many important active ingredients such as phenylpropanoids and flavonoids that affect the flavor, taste and nutrients of food. How to elucidate the metabolic phenotype of PPP is fundamental in food research and development. In this study, we designed a structural periodical table filled with 103 metabolites produced from PPP. All of them especially the 62 structural isomers were qualified and quantified with high resolution and sensitivity via multiple reaction mode in liquid chromatography tandem triple quadrupole mass spectrometry. Ginkgo biloba and soybean were used as samples for the practical application of this method: The delicate spatial-temporal metabolic balance of PPP from ginkgo biloba has been first elucidated; It is first confirmed that the salt and draught stresses could redirect the biosynthesis trend of PPP to produce more isoflavones in soybean leaves.

Synthesis of superparamagnetic MnFe2O4/mSiO2 nanomaterial for degradation of perfluorooctanoic acid by activated persulfate.

In this paper, magnetic MnFe2O4/mSiO2 nanocomposites were successfully synthesized, and the activation performance of the materials for persulfate was evaluated by the degradation efficiency of perfluorooctanoic acid. The structure of the catalyst was proved to be a core-shell structure by several characterization methods. The mesoporous silicon coating can effectively avoid the agglomeration of MnFe2O4 and at the same time increase the contact area with the reactants. A comparison of different catalyst addition conditions demonstrates that MnFe2O4/mSiO2 can effectively activate the persulfate. The optimal reaction conditions were investigated by several key influencing factors. It was experimentally demonstrated that about 90% of PFOA (10mg·L-1) could be decomposed under the conditions of 0.4g·L-1 MnFe2O4/mSiO2 and PS, pH 5.68, and 25°C within 4h; the defluorination rate reached 58.33%. In addition, the cyclability and stability tests demonstrated that MnFe2O4/mSiO2 is a stable material that can be recycled. Furthermore, XPS characterization and radical scavenging experiments demonstrated that sulfate radicals (SO4·-) and hydroxyl radicals (OH) play a major role in the reaction of MnFe2O4/mSiO2 activated PS. Subsequently, the degradation products were detected by high-performance liquid chromatography tandem triple quadrupole mass spectrometry, indicating that the degradation of PFOA is a gradual process of defluorination and decarbonization in the presence of free radicals. Finally, the metal leaching rate is tested to prove that the material meets environmental requirements while reacting efficiently. In conclusion, this study shows that MnFe2O4/mSiO2 is an easily recoverable and highly efficient and stable material that has great potential for PS activation to treat organic pollutants in water.

Quantification of major milk proteins using ultra-performance liquid chromatography tandem triple quadrupole mass spectrometry and its application in milk authenticity analysis

An authenticity-based method was developed to detect economically motivated adulteration (EMA) in milk. To achieve this goal, 46 peptides released from trypsin digested milk proteins were identified and marker peptides were further selected based on their digestibility and stability characteristics to allow further quantifications of the milk proteins in the original samples using an isotope-dilution ultra-performance liquid chromatography tandem triple quadrupole mass spectrometry (UPLC-TQMS). Furthermore, to detect EMA in milk samples, 22 authentic milk powder samples were analyzed using the isotope-dilution UPLC-TQMS, and an authenticity threshold value --70.26 g/100 g as the content of all five major milk proteins to total protein—was established to evaluate milk samples with high adulteration risks. Finally, the threshold value was validated using soy protein adulterated milk samples. Results showed that the reported authenticity-based method was sensitive enough to detect the tampering of milk samples with as little as 10 % soy protein added. It is clear that this newly developed authenticity-based detection method is a powerful tool to detect unknown adulteration risks in milk samples. • Selected 5 marker peptides from 46 identified peptides based on their digestibility and stability characteristics. • Established and validated an isotope-dilution UPLC-TQMS method to quantitatively analyze major milk proteins. • Developed a milk authenticity threshold value to detect milk adulterations. • Validated the threshold value using artificially adulterated milk samples.