Search

γ-Glutamyl-β-cyanoalanylglycine (gEcnAG) is a glutathione analog in which the cysteine moiety in glutathione is replaced with β-cyanoalanine, a known plant cyanide metabolite. Previously, gEcnAG was detected in the liver of rats and chicks exposed to β-cyanoalanine. We reported the detection of gEcnAG in naïve mammalian cells using liquid chromatography coupled with tandem quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). LC-QTOF-MS analysis enabled high-resolution confirmation (exact mass determination and MS/MS fragmentation) of the gEcnAG structure. The detection of gEcnAG in rat pheochromocytoma (PC12) cells that were not exposed to β-cyanoalanine suggests its endogenous production. Furthermore, the inhibition of myeloperoxidase, an enzyme potentially required for endogenous cyanide generation, decreased gEcnAG levels in PC12 cells. This supports the notion that PC12 cells intrinsically produce cyanide, unlike HepG2 cells, which exhibited lower intracellular gEcnAG levels. Notably, β-cyanoalanine was undetectable in PC12 cells. Moreover, depleting glutathione with buthionine sulfoximine reduced intracellular gEcnAG levels, whereas supplementation with glutathione reduced ethyl ester increased them. These observations suggest that endogenous gEcnAG may be generated from glutathione, potentially through its reaction with endogenous cyanide. Our findings implicate gEcnAG as a possible metabolite of endogenous cyanide. [ABSTRACT FROM AUTHOR]

Lonicera japonica Thunb. and Lonicera hypoglauca are famous Chinese medicines used for hyperglycemia; however, the specific compounds that contributed to the hypoglycemic activity and mechanism are still unknown. In this study, the antidiabetic activity of L. japonica buds and L. hypoglauca buds, roots, stems, and leaves extracts was primarily evaluated, and the L. japonica buds and L. hypoglauca buds, roots, and stems extracts displayed significant hypoglycemic activity, especially for the buds of L. hypoglauca. A total of 72 high-level compounds, including 9 iridoid glycosides, 12 flavonoids, 34 organic acids, and 17 saponins, were identified by ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) combined with the fragmentation pathways of standards from different parts of L. japonica and L. hypoglauca extracts. Among them, 19 metabolites, including 13 saponins, were reported for the first time from both medicines. Seven high-content compounds identified from L. hypoglauca buds extract were further evaluated for hypoglycemic activity. The result indicated that neochlorogenic acid, chlorogenic acid, isochlorogenic acid A, isochlorogenic acid B, and isochlorogenic acid C displayed significant antidiabetic activity, especially for isochlorogenic acid A and isochlorogenic acid C, which demonstrated that the five chlorogenic-acid-type compounds were the active ingredients of hypoglycemic activity for L. japonica and L. hypoglauca. The potential mechanism of hypoglycemic activity for isochlorogenic acid A and isochlorogenic acid C was inhibiting the intestinal α-glucosidase activity to block the supply of glucose. This study was the first to clarify the hypoglycemic active ingredients and potential mechanism of L. japonica and L. hypoglauca, providing new insights for the comprehensive utilization of both resources and the development of hypoglycemic drugs. [ABSTRACT FROM AUTHOR]

Broccoli microgreens represent a novel type of vegetable characterized by high levels of bioactive compounds. Here, we investigated the effects of light-emitting diode (LED) light quality on the development and nutritional uptake of broccoli microgreens. The plants were exposed to five distinct light treatments: white, single red, and red: blue at 5:1, 5:3, and 5:5 ratios. The soluble sugars, nutrients, and secondary metabolites of broccoli sprout extracts were examined using high-performance liquid chromatography and ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry under various light-quality conditions. In addition, the expression levels of genes encoding important enzymes in the glucosinolates (GLs) biosynthesis pathway were examined using quantitative real-time polymerase chain reaction. Overall, the findings demonstrated that mixed red-blue light, especially the 5:1 red: blue ratio, was beneficial for broccoli microgreens in terms of their hypocotyl length, fresh weight, edible rate, soluble proteins, vitamin C, total phenolics, total flavonoids, and GLs. Our findings provide a foundation and reference point for selecting the most appropriate LED light ratio in microgreens production. [ABSTRACT FROM AUTHOR]

Rational: Aconiti Lateralis Radix Praeparata (AC) is a traditional Chinese medicine with a long history of use. However, the current research on the material basis of AC and its processed products is still not comprehensive, especially the changes in lipo‐diterpenoid alkaloids (LDAs) that can be hydrolyzed into diester‐diterpenoid alkaloids in AC before and after processing. This study aimed to provide material basis guidance for the clinical use of AC and its processed products by comprehensively analyzing the changes in substances between AC and its processed products. Methods: An ultra‐high‐performance liquid chromatography with quadrupole time‐of‐flight mass spectrometry (UHPLC/Q‐TOF‐MS/MS) approach was optimized to chemical profiling. The MS data were processed using molecular networking combined with the in‐house library database to fast characterize the compounds. Multivariate statistical methods were adopted to determine the dissimilarities of components in AC and its processed products. Results: A total of 310 compounds were tentatively identified from AC, including 109 potential new alkaloids, of which 98 were potential novel LPAs. A metabolomics approach was applied to find the characteristic marker components. As a result, 52 potential chemical markers were selected to distinguish the AC samples of different extraction methods and 42 potential chemical markers for differentiating between AC and its processed products were selected. Conclusion: The results indicate that UHPLC/Q‐TOF‐MS/MS and Global Natural Products Social Molecular Networking coupled with multivariate analysis strategies was a powerful tool to rapidly identify and screen the chemical markers of alkaloids between the AC samples and its processed products. These results also indicate that the toxicity of water extracts of AC and its processed products were decreased. This research not only guides the clinical safe use of AC and its processed products, but also extends the application of the molecular networking strategy in traditional herbal medicine. [ABSTRACT FROM AUTHOR]

Purpose: To investigate the anti-inflammatory and antiprotozoal effects as well as chemical profile of ethanol extracts of Hedyotis diffusa (Rubiaceae) (HDE) and Scutellaria barbata (Lamiaceae) (SBE). Methods: Dried whole plants collected in Vietnam were extracted with ethanol (30 and 96 %) by maceration for 4 weeks. The resulting extracts obtained after evaporating the solvent were stored in a refrigerator at 4 oC. Mouse carrageenan-induced inflammation and mouse macrophage cell line RAW264.7 were used to assess the in vivo and in vitro anti-inflammatory activities, respectively, while ciliate, Tetrahymena pyriformis was used to determine antiprotozoal effects. Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS) was employed to analyze the chemical profiles of the extracts. Results: All the extracts manifested anti-inflammatory effects in vitro and in vivo. The HDE exhibited significantly higher in vitro anti-inflammatory activity than SBE (p < 0.05). Furthermore, in vivo antiinflammatory activity was higher in SBE compared to HDE. Both extracts exhibited antiprotozoal effects. The 96 % ethanol extract of both plants were more active than the 30 % ethanol extracts. Analysis by UHPLC-Q-TOF-MS revealed the presence of chrysin, apigenin and apigenin derivatives, naringenin, wogonin, quercetin and quercetin derivatives, as well as scutellarin. Conclusion: The HDE and SBE extracts from Vietnam exhibit significant in vivo and in vitro antiinflammatory activities and in addition, antiprotozoal activity against Tetrahymena pyriformis. These plants, therefore, are potential sources of antiprotozoal agents. [ABSTRACT FROM AUTHOR]

Many naturally occurring chemical metabolites with significant cytotoxic activities have been isolated from medicinal plants and have become the leading hotspot of anti-cancer research in recent years. Hyptis rhomboidea Mart. et Gal is used as a folk medicine in South China to treat or assist in the treatment of liver disease, ulcers, and edema. But its chemical constituents have not been fully investigated yet. This study aimed to assess the cytotoxicity of H. rhomboidea, which was chemically characterized by chromatography–mass spectrometry methods. The results showed that the 95% ethanol extract of H. rhomboidea has marked inhibitory effects on five human cancer cell lines (HL-60, A549, SMMC-7721, MDA-MB-231, and SW480), with IC50 values ranging from 15.8 to 40.0 μg/mL. A total of 64 compounds were identified by ultra-high-performance liquid chromatography with quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) and gas chromatograph–mass spectroscopy (GC-MS) analysis of H. rhomboidea crude extract. Among them, kaempferol, quercetin, rosmarinic acid, squalene, and campesterol were found to be abundant and might be the major metabolites involved to its bioactivity. The cytotoxic characterization and metabolite profiling of H. rhomboidea displayed in this research provides scientific evidence to support its use as medicinal properties. [ABSTRACT FROM AUTHOR]

Rationale: Cloxacillin and flucloxacillin are prone to degradation and polymerization in humid and hot environments, and their polymers have long been recognized to trigger allergic manifestations. A series of the degradation and polymerized impurities in cloxacillin and flucloxacillin were separated and characterized to ensure safe use of these drugs by the public. Methods: By studying the chromatographic behavior of the degradation impurities and polymerized impurities in reversed‐phase high‐performance liquid chromatography (RP‐HPLC) gradient elution, the impurities in cloxacillin and flucloxacillin were effectively separated and eluted. RP‐HPLC tandem ion trap/time‐of‐flight mass spectrometry (MS) was applied to characterize the structures of unknown impurities eluted from the RP‐HPLC methods for cloxacillin and flucloxacillin. The mechanisms of formation of the impurities in cloxacillin and flucloxacillin were also investigated. Results: The structures of 10 unknown impurities in cloxacillin and 8 unknown impurities in flucloxacillin were elucidated based on the high‐resolution MSn data at positive and negative modes, respectively. Six polymerized impurities were found and characterized, of which three were from the polymerization of cloxacillin and three were from the polymerization of flucloxacillin. Conclusions: The study on the impurity profiles of cloxacillin and flucloxacillin provided a scientific basis for improving their production processes and quality control. [ABSTRACT FROM AUTHOR]

The study aimed to analyze nusinersen metabolites in the cerebrospinal fluid samples using ion-pair reversed-phase ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. Three different sample preparation methods were tested for extraction and purification, but solid phase extraction appeared to be the most suitable, allowing a significant sample enrichment (40-fold). This step was necessary to detect and identify metabolites of nusinersen in the cerebrospinal fluid. The developed and applied analytical procedure enabled the identification of nusinersen metabolites: sequences shorter by several nucleotides from the 3′ end; shorter by several nucleotides from both the 3′ and 5′ ends; and some depurination products. To the best of our knowledge, this is the first report on the analysis and identification of nusinersen metabolites in cerebrospinal fluid samples taken from children with spinal muscular atrophy treated with Spinraza. [ABSTRACT FROM AUTHOR]

Objective: Ephedra, widely used in clinical practice as a medicinal herb, belongs to the genus Ephedra in the family Ephedraceae. However, the presence of numerous Ephedra varieties and variants requires differentiation for accurate identification. Methods: In this study, we employed headspace gas chromatography mass spectrometry (HS-GC-MS), ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOFMS), and global natural products social molecular networking (GNPS) for chemical component identification. Chemometric analysis was used to analyze the differential components. Metabolic analysis and Kyoto encyclopedia of genes and genomes (KEGG) enrichment were utilized to explore the synthesis pathways of different components. Result: A total of 83 volatile and 79 non-volatile components were identified in Ephedra species. Differential analysis revealed that among the eight Ephedra stems, 18 volatile and 19 non-volatile differential compounds were discovered, whereas Ephedra roots exhibited 21 volatile and 17 non-volatilemarkers. Volatile compounds were enriched in four synthetic pathways, while non-volatile components were enriched in five pathways among the differentiated components. Conclusion: This study is the first to conduct a comparative analysis of chemical components in different Ephedra species and parts. It provides a foundational reference for authenticating Ephedra herbs, evaluating medicinal resources, and comparing quality in future studies. [ABSTRACT FROM AUTHOR]

Rationale: As per International Council for Harmonization (ICH) drug stability test guideline Q1A(R2), inherent stability characteristics of a drug should be studied. This work was designed to investigate inherent degradation characteristics of the drug idelalisib under ICH prescribed stress conditions, identify its degradation products, and postulate their corresponding degradation pathways. Methods: Idelalisib was subjected to the ICH prescribed conditions of hydrolytic (neutral, acidic, and alkaline), photolytic, oxidative, and thermal stress according to ICH guideline Q1A(R2). An ultrahigh‐performance liquid chromatography with photodiode array (UHPLC‐PDA) method was developed to adequately resolve the drug from its degradation products, validated as per the ICH guidelines, and subsequently extended to UHPLC with electrospray ionization quadrupole time‐of‐flight mass spectrometry (ESI‐QTOFMS) studies to identify the degradation products. Results: Significant degradation was noted under conditions of acidic/alkaline hydrolysis, acid photolysis, and oxidative stress. The UHPLC/ESI‐QTOFMS studies revealed the generation of four degradation products (I–IV), which were satisfactorily resolved from the drug by UHPLC on a Kinetex® C18 (100 × 4.6 mm; 2.6 μm) column by the developed isocratic elution method. Detection wavelength was selected as 270 nm. All the degradation products (I–IV) could be identified and characterized from their mass spectral data. The degradation pathways for the generation of various products from the drug were postulated. Conclusions: A UHPLC‐PDA method was developed and validated for idelalisib. Four degradation products of idelalisib were revealed through UHPLC/ESI‐QTOFMS studies, and corresponding degradation pathways were postulated for the same. [ABSTRACT FROM AUTHOR]

A method was developed for the determination of tropane alkaloids (TAs), including atropine, scopolamine, anisodamine and homatropine in buckwheat and related products. This work presents an optimised methodology based on QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction procedure followed by ultra-high performance liquid chromatography combined with time-of-flight mass spectrometry for the determination of TAs (atropine, scopolamine, anisodamine and homatropine) in buckwheat samples. The analytical methodology was successfully validated, demonstrating good linearity, low limit of quantification, repeatability (RSDr < 15%), inter-day precision (RSDR < 19%) and recovery (74–113%). Finally, 13 commercial samples of buckwheat were analysed and the results demonstrated that they were in compliance with the current European regulations regarding TAs. [ABSTRACT FROM AUTHOR]

Biocide resistance poses a significant challenge in industrial processes, with bacteria like Pseudomonas oleovorans exhibiting intrinsic resistance to traditional antimicrobial agents. In this study, the impact of biocide exposure on the metabolome of two P. oleovorans strains, namely, P. oleovorans P4A, isolated from contaminated coating material, and P. oleovorans 1045 reference strain, were investigated. The strains were exposed to 2-Methylisothiazol-3(2H)-one (MI) MIT, 1,2-Benzisothiazol-3(2H)-one (BIT), and 5-chloro-2-methyl-isothiazol-3-one (CMIT) at two different sub-inhibitory concentrations and the lipids and polar and semipolar metabolites were analyzed by ultra-high performance liquid chromatography quadrupole time-of-flight mass spectrometry UPLC–Q–TOF/MS. Exposure to the BIT biocide induced significant metabolic modifications in P. oleovorans. Notable changes were observed in lipid and metabolite profiles, particularly in phospholipids, amino acid metabolism, and pathways related to stress response and adaptation. The 1045 strain showed more pronounced metabolic alterations than the P4A strain, suggesting potential implications for lipid, amino acid metabolism, energy metabolism, and stress adaptation. Improving our understanding of how different substances interact with bacteria is crucial for making antimicrobial chemicals more effective and addressing the challenges of resistance. We observed that different biocides trigged significantly different metabolic responses in these strains. Our study shows that metabolomics can be used as a tool for the investigation of metabolic mechanisms underlying biocide resistance, and thus in the development of targeted biocides. This in turn can have implications in combating biocide resistance in bacteria such as P. oleovorans. [ABSTRACT FROM AUTHOR]

Rationale: Lomefloxacin hydrochloride ear drops are highly unstable to light and prone to produce photodegradation impurities. These impurities might be related to the phototoxicity of lomefloxacin, which could seriously threaten the health of patients. In this article, the photodegradation impurity profile in lomefloxacin hydrochloride ear drops was studied for further improvement of quality control of the drug. Methods: By studying the chromatographic behavior of photodegradation impurities, the photodegradation impurities in lomefloxacin hydrochloride ear drops were separated and detected effectively. Liquid chromatography combined with ion trap/time‐of‐flight mass spectrometry was applied to characterize the structures of the photodegradation impurities in lomefloxacin hydrochloride ear drops. Results: The structures of 17 impurities in lomefloxacin hydrochloride ear drops were elucidated based on high‐resolution MSn data in positive ion mode, 12 of them being unknown impurities. Conclusions: The structural characteristics and fragmentation patterns of the photodegradation impurities were also studied. The study of the photodegradation impurity profile in lomefloxacin hydrochloride ear drops provides a scientific basis for quality control of these ear drops and ensures the safety of drug use by the public. [ABSTRACT FROM AUTHOR]

Rational: Pogejiuxin decoction (PGJXD) is one of the most important formulas for the treatment of heart failure. However, there is a great lack of research on the material basis of this formula, especially research on its compatibility laws, which restricts its clinical use. Studying the complete ingredients and compatibility rules of PGJXD has great significance for guiding clinical medication. Methods: The entire formula, the major single herbs, the drug pairs and the disassembled formula were analyzed by ultrahigh‐performance liquid chromatography with quadrupole time‐of‐flight mass spectrometry (UHPLC/QTOFMS/MS), matching the chemical composition database and global natural product social molecular networking to explain the chemical composition as well as the combination pattern of PGJXD. Results: A total of 1048 chemical constituents were fully analyzed from the major single herbs, the drug pairs and the disassembled formula and 188 chemical constituents, including 13 potential novel compounds, were firstly identified from the whole formula. We found that the chemical compositions were reduced after the single herbs were matched to the other herbs, especially the significant reduction of highly toxic diester alkaloids after compatibility, indicating that the medicines of PGJXD were interdependent and controlled by each other. Conclusion: This study innovatively researches and compares the compositional differences between the entire formula of PGJXD, the single, paired and separated formulas, greatly extending our understanding of the chemical substance basis of these compounds, and preliminarily explores the compatibility laws of PGJXD, providing some theoretical guidance for clinical medication. [ABSTRACT FROM AUTHOR]

Background: Trachelospermi Caulis et Folium, the stems and leaves of Trachelospermumjasminoides (Lindl.) Lem, has been used as a remedy for rheumatism, gonarthritis, backacheand pharyngitis, according to the Chinese Pharmacopoeia. However, the correspondingchemical substances of this ethnic medicinal plant with anti-inflammatory activitykept unclear. This study aimed to explore the active substances attribute to its anti-rheumaticactivity of this medical plant. Methods: Ultra-high performance liquid chromatographycombined with quadrupole time-of-flight mass spectrometry was used to identifythechemical components in the extract of T. jasminoides. Molecular docking was appliedtoanalyze the binding affinity of potential active lignans to inducible nitric oxide synthaseenzyme. The anti-inflammatory effects of the potential active fraction were verifiedbycell experiments in vitro. Results: Forty-one compounds, mainly are lignans and nine of whichwere reported for the first time from the genus of Trachelospermum, were characterizedusingultra-high performance liquid chromatography quadrupole-time-of-flight mass spectrometrymethod. Molecular docking results showed these identified lignans had excellent interactions with the inducible nitric oxide synthase enzyme, and the lignans-enrichedfraction could significantly inhibit the release of nitric oxide and the expression of induciblenitric oxide synthase protein in LPS-induced RAW264.7 cells. Conclusion: Lignans arethemain active substances that responsible for the anti-inflammatory activity of the ethnicherbal medicine T. jasminoides. [ABSTRACT FROM AUTHOR]

Host immunity can influence the composition of the gut microbiota and consequently affect disease progression. Previously, we reported that a Mycobacterium vaccae vaccine could ameliorate allergic inflammation in asthmatic mice by regulating inflammatory immune processes. Here, we investigated the anti‐inflammatory effects of M. vaccae on allergic asthma via gut microbiota modulation. An ovalbumin (OVA)‐induced asthmatic murine model was established and treated with M. vaccae. Gut microbiota profiles were determined in 18 BALB/c mice using 16S rDNA gene sequencing and metabolomic profiling was performed using liquid chromatography quadrupole time‐of‐flight mass spectrometry. Mycobacterium vaccae alleviated airway hyper‐reactivity and inflammatory infiltration in mice with OVA‐induced allergic asthma. The microbiota of asthmatic mice is disrupted and that this can be reversed with M. vaccae. Additionally, a total of 24 differential metabolites were screened, and the abundance of PI(14:1(9Z)/18:0), a glycerophospholipid, was found to be correlated with macrophage numbers (r = 0.52, p = 0.039). These metabolites may affect chemokine (such as macrophage chemoattractant protein‐1) concentrations in the serum, and ultimately affect pulmonary macrophage recruitment. Our data demonstrated that M. vaccae might alleviate airway inflammation and hyper‐responsiveness in asthmatic mice by reversing imbalances in gut microbiota. These novel mechanistic insights are expected to pave the way for novel asthma therapeutic strategies. [ABSTRACT FROM AUTHOR]

Dragon's Blood (DB) serves as a precious Chinese medicine facilitating blood circulation and stasis dispersion. Daemonorops draco (D. draco; Qi-Lin-Jie) and Dracaena cochinchinensis (D. cochinchinenesis; Long-Xue-Jie) are two reputable plant sources for preparing DB. This work was designed to comprehensively characterize and compare the metabolome differences between D. draco and D. cochinchinenesis, by integrating liquid chromatography/mass spectrometry and untargeted metabolomics analysis. Offline two-dimensional liquid chromatography/ion mobility-quadrupole time-of-flight mass spectrometry (2D-LC/IM-QTOF-MS), by utilizing a powerful hybrid scan approach, was elaborated for multicomponent characterization. Configuration of an XBridge Amide column and an HSS T3 column in offline mode exhibited high orthogonality (A0 0.80) in separating the complex components in DB. Particularly, the hybrid high-definition MSE-high definition data-dependent acquisition (HDMSE-HDDDA) in both positive and negative ion modes was applied for data acquisition. Streamlined intelligent data processing facilitated by the UNIFI™ (Waters) bioinformatics platform and searching against an in-house chemical library (recording 223 known compounds) enabled efficient structural elucidation. We could characterize 285 components, including 143 from D. draco and 174 from D. cochinchinensis. Holistic comparison of the metabolomes among 21 batches of DB samples by the untargeted metabolomics workflows unveiled 43 significantly differential components. Separately, four and three components were considered as the marker compounds for identifying D. draco and D. cochinchinenesis, respectively. Conclusively, the chemical composition and metabolomic differences of two DB resources were investigated by a dimension-enhanced analytical approach, with the results being beneficial to quality control and the differentiated clinical application of DB. [ABSTRACT FROM AUTHOR]

Rhizoma Panacis Japonici (RPJ) is an ancient herbal medicine from China that has long been employed for its medicinal benefits in relieving arthritis physical debility and diverse afflictions. The primary bioactive constituents found in RPJ are triterpene saponins, which exhibit numerous pharmacological actions, including anti-inflammatory, antioxidant, and immunomodulating effects. The present study established a straightforward and effective approach for characterizing triterpene saponins in RPJ. An offline HILIC × RP LC/QTOF-MS method was developed, along with a self-constructed in-house database containing 612 saponins reported in the Panax genus and 228 predicted metabolites. The approach achieved good chromatographic performance in isolating triterpene saponins of RPJ, with the HILIC column as the first dimension (1D) and the BEH C18 column as the second dimension (2D). The developed two-dimensional liquid chromatography system exhibited an orthogonality of 0.61 and a peak capacity of 1249. Detection was performed using a QTOF mass spectrometer in a data-independent manner (MSE) in a negative ion mode. Using the in-house database, the collected MS data were processed by an automatic workflow on UNIFI 1.8.2 software, which included data correction, matching of precursor and product ions, and peak annotation. In this study, 307 saponins were characterized from RPJ and 76 saponins were identified for the first time in Panax japonicus. This research not only enhances our understanding of the chemical characteristics of RPJ but also offers a simple and efficient method for analyzing the complex composition of herbal medicine. [ABSTRACT FROM AUTHOR]

Capsaicinoids are the main bioactive compounds in hot chili peppers. In the present work, Ultra-performance liquid chromatography coupled with a photodiode detector-quadrupole and tandem time-of-flight mass spectrometry detector (UPLC-ESI-Q-TOF-MS/PDA) was established to characterize, identify and quantify 7 capsaicinoid derivatives based on their MS spectra, and comparisons with standards when available, as well as with literature data. According to the systematic analysis of the collected MS spectra and the observed fragmentation, the detected compounds were glycosylated and acylated capsaicinoids. Namely, capsaicin-glucoside, dihydrocapsaicin-glucoside, nordihydrocapsaicin-glucoside, homocapsaicin-glucoside and homodihydrocapsaicin-glucoside, beside capsaicin-ferulate and dihydrocapsaicin-ferulate, were isolated for the first time from pepper cultivars. Capsaicinoid-glucoside were detected in Xingshuzaohui and Shuailiang cultivars (cultivated in a greenhouse), while capsaicinoid-ferulate were detected in Hangzhou and Xiaomila cultivars. The capsaicinoid-glucoside content ranged from 6.93 to 9.85 mg/kg of fresh weight, while total capsaicinoid-ferulate content ranged from 1.79 to 3.78 mg/kg. The changes in the content of the detected capsaicinoid derivatives depended on the pepper-cultivated method and maturity stages. The scatterplot demonstrated a strong correlation between pepper extracts' anti-oxidant activity (DPPH and ABTS) and their capsaicinoid content, particularly capsaicin-glucoside. [ABSTRACT FROM AUTHOR]

IntroductionThe use of illicitly manufactured synthetic opioids, specifically fentanyl and its analogs, has escalated exponentially in the United States over the last decade. Due to the targeted nature of drug detection methods in clinical laboratories and the ever-evolving list of synthetic opioids of concern, alternative analytical approaches are needed.MethodsUsing the fentanyl analog screening (FAS) kit produced by the Centers for Disease Control and Prevention (CDC), we developed a liquid chromatography-high resolution mass spectrometry (LC-HRMS) synthetic opioid spectral library and data acquisition method using information dependent acquisition of product ion spectra. Chromatographic retention times, limits of detection and matrix effects, in urine and serum, for the synthetic opioids in the FAS kit (n = 150) were established. All urine and serum specimens sent to a clinical toxicology laboratory for comprehensive drug testing in 2019 (n = 856) and 2021 (n = 878) were analyzed with the FAS LC-HRMS library to determine the prevalence of fentanyl analogs and other synthetic opioids, retrospectively (2019) and prospectively (2021).ResultsThe limit of detection (LOD) of each opioid ranged from 1 to 10 ng/mL (median, 2.5 ng/mL) in urine and 0.25-2.5 ng/mL (median, 0.5 ng/mL) in serum. Matrix effects ranged from -79 % to 86 % (median, -37 %) for urine, following dilution and direct analysis, and -80 % to 400 % (median, 0 %) for serum, following protein precipitation. The prevalence of fentanyl/fentanyl analogs in serum samples increased slightly from 2019 to 2021 while it remained the same in urine. There were only 2 samples identified that contained a fentanyl analog without the co-occurrence of fentanyl or fentanyl metabolites. Analysis of the established MS/MS spectral library revealed characteristic fragmentation patterns in most fentanyl analogs, which can be used for structure elucidation and drug identification of future analogs.ConclusionsThe LC-HRMS method was capable of detecting fentanyl analogs in routine samples sent for comprehensive drug testing. The method can be adapted to accommodate testing needs for the evolving opioid epidemic.

Flavonoid‐C‐glycosides with various pharmacological actions were abundant in corn silk, and fragmentation in mass spectra of flavonoid‐C‐glycosides compounds was particularly important. This paper aimed to supervise the fragmentation patterns of flavonoid‐C‐glycosides in the enriched flavonoids from corn silk by high‐efficiency ultra‐high‐performance liquid chromatography combined with a quadrupole time‐of‐flight mass spectrometry approach. Therefore, the flavonoids were extracted by heating reflux and then purified based on D101 macroporous resin. Thirty‐five flavonoids were triumphantly identified in the purified product. Among them, 14 were flavonoid‐C‐glycosides, seven of them owned luteolin mother nuclei (luteolin‐C‐glycosides) and seven of them owned apigenin mother nuclei (apigenin‐C‐glycosides). Importantly, the diagnostic product ions of luteolin‐C‐glycosides including m/z (431, 413, 395, 369, 367, 313, and 299) and m/z (429, 411, 393, 367, 365, 311, and 297), and the characteristic product ions of apigenin‐C‐glycosides covered m/z (353, 339, and 299) and m/z (339, 327, and 309). In addition, diagnostic H2O neutral loss and glycosyl craking were familiar, and the difference values among product ions mainly contained 40, 60, 70, 80, 90, 100, and 120 Da. Thus, the fragmentations of luteolin‐C‐glycosides and apigenin‐C‐glycosides identified in corn silk were with proper regularity. The obtained fragmentation patterns provided rapid recognition and meaningful guidance for the purification study of flavonoid‐C‐glycosides. [ABSTRACT FROM AUTHOR]

The development of polysaccharide drugs requires a thorough understanding of their quantitative and pharmacokinetic properties. However, the complexity of biological samples presents a challenge for direct analysis using UHPLC-QTOF MS. Therefore, it is essential to establish a method for the selective enrichment of polysaccharides. In this study, we developed an efficient method for the quantitative determination of polysaccharides by integrating magnetic molecularly imprinted polymers (MIPs) for sample pretreatment and UHPLC-QTOF MS for analysis. The MIPs were prepared using molecularly imprinted and boric acid affinity technologies, which combined the advantages of specific recognition and reversible binding to polysaccharides. The MIPs exhibited high dispersibility and uniform particle size, and adsorption experiments demonstrated their specific recognition of BG136, a polysaccharide with immunological activity. The proposed method was used for the purification and enrichment of BG136 in plasma with recoveries between 91.29% and 113.03%. This simple method demonstrated high selectivity, fast separation, and satisfactory recoveries providing an approach for polysaccharide determination with UHPLC-QTOF MS. [ABSTRACT FROM AUTHOR]

Rationale: Pyrrolidone‐based drugs find widespread use in treating conditions such as epilepsy and Alzheimer's disease, and in various other medical applications. Brivaracetam, the latest generation of pyrrolidone drugs, has exhibited significant promise owing to chemical structure modifications. Its affinity to the SV2A receptor is double that of the previous‐generation drug, levetiracetam. Consequently, brivaracetam holds substantial potential for diverse applications. As a novel drug not yet included in the pharmacopeias of developed nations, comprehensive analysis and research are necessary to guarantee its safe utilization in clinical settings. Methods: A liquid chromatography quadrupole time‐of‐flight tandem mass spectrometry (LC/QTOFMS) method has been developed to effectively separate, identify and characterize both the degradation products and process‐related substances of brivaracetam. Stress testing of the sample was carried out following the guidelines outlined in ICH Q1A(R2). The structures of these impurities were identified through positive electrospray ionization QTOF high‐resolution MS and NMR spectroscopy. Additionally, the formation mechanism of each degradation product is thoroughly discussed. Results: Under the analytical conditions outlined in this paper, brivaracetam and its degradation products were effectively separated. Thirteen degradation products were detected and characterized, shedding light on their origins and degradation pathways. Among these, three degradation products align with previously reported impurities, and two unreported degradation products were synthesized and confirmed through NMR spectroscopy. The stress testing results revealed the instability of brivaracetam under acidic, alkaline, oxidative and thermal stress conditions, while it exhibited relative stability under photolytic stress conditions. Conclusion: The study developed an analytical method for brivaracetam that enabled the effective detection and separation of brivaracetam and its 13 degradation products. This method addresses a gap in both current domestic and foreign drug standards. The structures of all the major degradation products were characterized by high‐resolution LC/QTOFMS, which is essential for quality control during the drug production process, stability evaluation and the establishment of proper storage conditions. [ABSTRACT FROM AUTHOR]

Rationale: Tetrandrine, the Q‐marker in Stephaniae Tetrandrae Radix, was proven to present an obvious antitumor effect. Until now, the metabolism and antitumor mechanism of tetrandrine have not been fully elucidated. Methods: The metabolites of tetrandrine in rats were profiled using ultra‐high‐performance liquid chromatography coupled with time‐of‐flight mass spectrometry. The potential antitumor mechanism of tetrandrine in vivo was predicted using network pharmacology. Results: A total of 30 metabolites were characterized in rats after ingestion of tetrandrine (10 mg/kg), including 0 in plasma, 7 in urine, 11 in feces, 9 in liver, 8 in spleen, 4 in lung, 5 in kidney, 5 in heart, and 4 in brain. This study was the first to show the metabolic processes demethylation, hydroxylation, and carbonylation in tetrandrine. The pharmacology network results showed that tetrandrine and its metabolites could regulate AKT1, TNF, MMP9, MMP2, PAK1, and so on by involving in proteoglycan tumor pathway, PI3K‐Akt signaling pathway, tumor pathway, MAPK signaling pathway, and Rap1 signaling pathway. Conclusions: The metabolism features of tetrandrine and its potential antitumor mechanism were summarized, providing data for further pharmacological validation. [ABSTRACT FROM AUTHOR]

Fufang Xiling Jiedu capsule (FXJC), a traditional Chinese medicine that evolved from "Yinqiao Powder", is widely used for the treatment of cold and influenza. However, due to a lack of in vivo metabolism research, the chemical components responsible for the therapeutic effects still remain unclear. Hence, this study aimed to describe the metabolic profiles of the FXJC in rat plasma, urine, and feces. A combined data mining strategy based on ultra‐performance liquid chromatography coupled with quadrupole time‐of‐flight tandem mass spectrometry was employed and 201 xenobiotics, including 117 prototype components and 84 metabolites were detected. Phenolic acids, flavonoids, triterpenes, and lignans were prominent ingredients absorbed in vivo, and the major metabolic pathways of the detected metabolites were glucuronidation, sulfation, methylation, and oxidation. This is the first systematic study on the metabolism of the FXJC in vivo, providing valuable information for future studies on the efficacy, toxicity, and mechanism of the FXJC. [ABSTRACT FROM AUTHOR]

Qiangli Dingxuan (QLDX) tablet is a widely recognized traditional Chinese medicine formula that has been extensively used in China for decades to treat vertigo, tinnitus, and dizziness owing to its outstanding therapeutic outcomes. However, the complexity of the chemical components in this tablet makes it challenging to separate and identify these components. This study presented an effective and sensitive strategy for the rapid separation and simultaneous structural identification of QLDX tablet components using ultra‐performance liquid chromatography with quadrupole time‐of‐flight tandem mass spectrometry and the UNIFI platform. Based on retention times, accurate masses, fragment ions, related literature, and authentic standards, 119 compounds were identified or tentatively characterized; these included 9 iridoids, 12 lignans, 21 phenylpropanoids, 27 flavonoids, 7 phthalides, and 43 others. Among them, 36 were confirmed using reference standards. The representative compounds with various chemical structures were studied by analyzing their fragmentation patterns and characteristic ions. In conclusion, this study established a rapid approach for characterizing the chemical constituents in QLDX tablet. The proposed approach provides a basis for qualitative analysis and quality control in the manufacturing process and is beneficial for advancing investigations into the efficacy and mechanism of action of this tablet. [ABSTRACT FROM AUTHOR]

Recently, we reported the chemical profile and the hypocholesterolemic effects of a decoction of Tessaria absinthioides (Hook. & Arn.) DC. (Asteraceae). In this study, we evaluated a methanolic extract (METa) instead. Metabolite profiling was conducted using ultra-high-resolution liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry (UHPLC-ESI-QTOF-MS), identifying thirty compounds, including flavonoids, phenolic acids, fatty acids, and phorbolesters. Antioxidant properties were assessed through 2,2-diphenyl-1-picrylhydrazyl (DPPH), Trolox equivalent antioxidant activity (TEAC), ferric-reducing antioxidant power (FRAP), and inhibition of lipid peroxidation in erythrocytes (ILP) assays, exhibiting robust antioxidant activity. The in vivo impact of METa on serum lipid parameters and liver X receptors (LXRs) was evaluated in a hypercholesterolemic animal model. After 14 days on a high-fat diet, male rats received either a vehicle (V) or METa100, METa200 or METa500 (100; 200 and 500 mg METa/kg animal, respectively) for an additional two weeks. METa500 reduced total cholesterol levels (17.62%; p < 0.05) and all doses increased high-density lipoprotein cholesterol levels (METa100: 86.27%; METa200: 48.37%, and METa500: 29.42%; p < 0.0001). However, METa did not alter LXRs expression. The observed antioxidant and hypocholesterolemic properties of METa may be linked to the presence of six di-caffeoylquinic acids. These findings underscore T. absinthioides as a potential candidate for the treatment of metabolic disease. [ABSTRACT FROM AUTHOR]

The piperamides profile of Piper nigrum cultivated in Costa Rica was studied using ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight high-resolution mass spectrometry (UPLC-ESI-QTOF-HRMS) on enriched-piperamides extracts. A total of 31 different piperamides were identified, 24 of them with a methylenedioxyphenyl moiety, including piperine and nine other compounds with the characteristic piperidine ring, as well as guineensine, retrofractamide B, and eight other piperamides with an N-isobutyl group. In addition, piperyline and two other compounds with a pyrrolidine ring, as well as piperflaviflorine B, holding a N-2-methylbutyl chain, were characterized. In turn, pellitorine and six other piperamides exhibiting a long olefinic chain instead of the methylenedioxyphenyl group were also tentatively identified. In addition, quantification was performed using UPLC coupled with a diode array detector (UPLC-DAD), with 15 piperamides being quantified, including piperine, piperyline, piperanine, and piperloguminine with values within the range of previous reports, while results obtained for guineensine (276.5–421.0 mg/100 g dry material) and pellitorine (414.4–725.0 mg/100 g dry material) were higher than those reported in the literature. Additionally, preparative and semi-preparative high-performance liquid chromatography (HPLC) separations allowed to isolate, besides piperine, four other piperamides, which were identified through HRMS, 1H and 13C nuclear magnetic resonance (NMR). These included retrofractamide B, guineensine, pellitorine, and (2E,4E,12Z)-N-isobutyl-octadeca-2,4,12-trienamide, with yields of 134.0 mg/100 g dry material, 209.7 mg/100 g dry material, 361.8 mg/100 g dry material and 467.0 mg/100 g dry material, respectively, with all these values higher than those reported in previous studies in the literature. The findings constitute the first report of such a number and diversity of compounds in P. nigrum cultivated in Costa Rica. [ABSTRACT FROM AUTHOR]

Introduction: Twisted-leaf garlic (Allium obliquum L.) is a wild Allium species, which is traditionally used as aroma plant for culinary purposes due to its unique, garlic-like flavor. It represents an interesting candidate for domestication, breeding and cultivation. Objectives: The objective of this work was to explore and comprehensively characterize polar and semi-polar phytochemicals accumulating in leaves and bulbs of A. obliquum. Method: Plant material obtained from a multiyear field trial was analyzed using a metabolite profiling workflow based on ultra-high performance liquid chromatography-coupled electrospray ionization quadrupole time-of-flight mass spectrometry (UHPLC/ESI-QTOFMS) and two chromatographic methods. For annotation of metabolites, tandem mass spectrometry experiments were carried out and the resulting accurate-mass collision-induced dissociation (CID) mass spectra interpreted. Onion and garlic bulb extracts were used as reference samples. Results: Important metabolite classes influencing nutritional, sensory and technological properties were detected and structurally characterized including fructooligosaccharides with a degree of polymerization of 3–5, S-alk(en)ylcysteine sulfoxides and other S-substituted cysteine conjugates, flavonoids including O- and C-glycosylated flavones as well as O-glycosylated flavonols, steroidal saponins, hydroxycinnamic acid conjugates, phenylethanoids and free sphingoid bases. In addition, quantitative data for non-structural carbohydrates, S-alk(en)ylcysteine sulfoxides and flavonoids are provided. Conclusion: The compiled analytical data including CID mass spectra of more than 160 annotated metabolites provide for the first time a phytochemical inventory of A. obliquum and lay the foundation for its further use as aroma plant in food industry. [ABSTRACT FROM AUTHOR]

Huangqi Guizhi Wuwu decoction (HGWWD) is a classic traditional Chinese medicine prescription for the treatment of ischemic stroke, etc. However, the material basis of its efficacy remains unclear, seriously affecting drug development and clinical applications. In the present study, an ultra‐high performance liquid chromatography‐quadrupole time‐of‐flight mass spectrometry method was developed to separate and identify the chemical components of HGWWD. A total of 81 compounds were identified and tentatively characterized. Eight compounds were accurately identified by comparing the retention time and mass spectrometry data with those of reference substances, the remaining compounds were characterized by comparing the mass spectrometry data and reference information. Based on the results of compound attribution, 35 compounds were from Astragali Radix, six compounds were from Cinnamomi Ramulus, 23 compounds were from Paeoniae Radix Alba, eight compounds were from Zingiberis Rhizoma Recens and nine compounds were from Jujubae Fructus. The results showed that monoterpenoids, flavonoids, organic acids, triterpenes, amino acids, gingerols, alkaloids, and glycosides were the main chemical components of HGWWD. This analytical method is suitable for characterizing the chemical constituents of HGWWD, and the results provide important information for elucidating its pharmacodynamic material basis and mechanism of action. [ABSTRACT FROM AUTHOR]

A challenge in the quality control of traditional Chinese medicine is the systematic multicomponent characterization of the compound formulae. Jiawei Fangji Huangqi, a modified form of Fangji Huangqi, is a prescription comprising seven herbal medicines. To address the chemical complexity of the Jiawei Fangji Huangqi decoction, we integrated ion mobility‐quadrupole time‐of‐flight high‐definition MSE coupled to ultra‐high‐performance liquid chromatography and intelligent data processing workflows available in the UNIFI software package. Good chromatographic separation was achieved on CORTECS UPLC T3 column within 52 min, and high‐accuracy MS2 data were acquired using high‐definition MSE in the negative and positive modes. A chemical library of 1250 compounds was created and incorporated into the UNIFI software to enable automatic peak annotation of the high‐definition MSE data. We identified or tentatively characterize 430 compounds in the Jiawei Fangji Huangqi decoction. The potential superiority of high‐definition MSE over conventional MS data acquisition approaches was revealed in its spectral quality (MS2), differentiation of isomers, separation of coeluting compounds, and target mass coverage. The multiple components of the Jiawei Fangji Huangqi decoction were elucidated, offering insight into its improved pharmacological action compared with that of the Fangji Huangqi formula. [ABSTRACT FROM AUTHOR]

Insulin-like growth factor 1 analogues are prohibited in sport for their ability to enhance athletic performance in several sport disciplines. Their detection presents several analytical challenges, mainly due to the minimum required performance limits fixed by the World Anti-Doping Agency. Here, we are presenting analytical workflows to detect IGF-1 and its analogues in different biological matrices. Several off-line immunocapture techniques and protocols were comparatively evaluated. Separation and detection were performed by using standard flow reverse-phase liquid chromatography coupled to a time-of-flight mass spectrometer. The best recoveries were obtained using magnetic beads or pipette tips functionalized with protein A. The analytical workflows were fully validated for qualitative determinations: all the target analytes were clearly distinguishable from the interference of the matrices, with limits of detection and identification in the range of 0.05–0.30 ng/mL in urine and 0.5–2.0 ng/mL in serum/plasma. The extraction efficiency proved to be repeatable (CV% < 10) with recoveries higher than 50%. Intra- and inter-day precision were found to be smaller than 10 and 15%, respectively. The method was successfully applied to the analysis of authentic matrix samples containing the target peptides at the minimum required performance limits, proving that the method developed can be successfully applied to detect and identify IGF-1 analogues for doping control purposes in all the matrices selected. The analytical workflow developed here to detect the target peptides in different matrices can be readily implemented in anti-doping laboratories and has the potential to be adapted for the simultaneous analysis of different similarly sized peptide hormones of doping relevance. [ABSTRACT FROM AUTHOR]

Copyright of Modern Food Science & Technology is the property of Editorial Office of Modern Food Science & Technology and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Lunasin is a cancer-preventive food bioactive peptide. This study reports quantification of lunasin from selected varieties of soybeans, wheat grains and their commercial products. Lunasin was extracted using a simple extraction protocol that combined liquid–liquid extraction with deionized water and n-heptane and solid-phase extraction with C18 stationary phase. The ultra-performance liquid chromatographic (UPLC) separation of lunasin was achieved on an C18 column (50 mm × 2.1 mm, 1.7 µm) using 0.1% aqueous formic acid (A) and 0.1% formic acid in acetonitrile (B) as mobile phase components delivered in a gradient mode for 10 min at a flow rate of 0.4 mL min−1. Electrospray ionisation (ESI) in positive polarity resulted in improved analyte ionisation, and detection was accomplished with a quadrupole time-of-flight mass spectrometer (Q-ToF/MS). Analyte quantification was carried out using ion chromatograms extracted at m/z 838.8. The UPLC-ESI-Q-ToF/MS was validated using matrix-matched standard reference materials. The method was found to be linear (17 to 10,200 ng mL−1), sensitive, accurate (mean recovery values greater than 91.1%), precise (relative standard deviations less than 2.40%). The extraction and quantification process were found to be efficient (88.1%-93.0%) and was used to quantify lunasin (mg/g sample) from soybeans (12.3–10.9), wheat (0.29–0.19), and their commercial products (0.00–5.56). A selective, specific, and reliable liquid chromatography-mass spectrometric method of quantifying lunasin from complex food matrices was developed and validated, allowing for sensitive quantitation as well as a wider concentration range of quantification, making it a viable candidate for regular laboratory assay of lunasin from soybean and wheat-based food products. [ABSTRACT FROM AUTHOR]

Due to the clinical significance of steroidal saponins, multiple stems Paris polyphylla var. yunnanensis (MPPY) has attracted much interest and played a crucial role in drug development. However, developing a simple and efficient method to analyze the chemical composition of MPPY remains a pronounced challenge. Herein, we report for the first time the component analysis of MPPY rhizomes using the chromatographic fingerprint combined with ultra-high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q-TOF-MS) method. Nineteen compositions of MPPY were qualitatively investigated by such strategy and confirmed as steroidal saponins. Among these compositions, 17 steroidal saponins were detected in 10 different batches of MPPY. Thirteen common peaks appeared in chromatographic fingerprint, of which 11 common peaks can be attributed by LC--MS data. The experimental facts demonstrate that the method established is simple, rapid, and reliable to evaluate the quality of MPPY. Besides, the correlation and difference of steroidal saponins in the rhizomes of MPPY from different places were also studied. [ABSTRACT FROM AUTHOR]

Rationale: The flower of Citrus aurantium L. var. amara Engl. (FCAVA), an edible tea and herbal medicine with anti‐obesity effect, has attracted great attention in China. The structural elucidation of chemical components in FCAVA has been realized in our previous work. It is well known that metabolic profiling provided a structural basis to discover potential anti‐obesity ingredients in FCAVA. Nevertheless, there are no reports about in vivo metabolic profiles of FCAVA. Therefore, it is necessary to comprehensively identify in vivo substances of FCAVA. Methods: The identification of in vivo substances of FCAVA remains a challenge due to the strong interference of complex chemical components, biological matrices and metabolite isomers. In this work, ultra‐high‐performance liquid chromatography coupled to quadrupole time‐of‐flight tandem mass spectrometry (UHPLC‐QTOF‐MS/MS) analysis with a data mining strategy was established and applied for the metabolic profiling of FCAVA in rats. The data mining strategy, including diagnostic product ions and neutral loss filtering, improved structural elucidation of xenobiotics in rats after oral administration of FCAVA. Results: A total of 228 xenobiotics, including 80 prototypes (10 unambiguous confirmed with reference standards) and 148 metabolites, were tentatively characterized in rat plasma, urine and fecal samples. Among them, 35 xenobiotics were found in plasma, 124 in urine and 156 in feces. The main biotransformation pathway of FCAVA metabolism was deglycosylation, methylation, glucuronidation and sulfation. The main compounds absorbed into the blood were neohesperidin and naringin, which have been reported to show significant anti‐obesity effect. Conclusions: Collectively, this present study would be conducive to the discovery of active ingredients of FCAVA for the treatment of obesity and the development of quality control of FCAVA. [ABSTRACT FROM AUTHOR]

This work describes a comprehensive achiral × chiral two‐dimensional liquid chromatography separation for enantioselective amino acid analysis coupled to electrospray ionization‐tandem mass spectrometry detection using data‐independent acquisition. Flow splitting after the first and second dimension separation was utilized for volumetric flow reduction and for enabling a multi‐detector approach (with ultraviolet, fluorescence, charged aerosol, and MS detection), respectively. Derivatization with 6‐aminoquinolyl‐N‐hydroxysuccinimidyl carbamate provided a chromophore, a fluorophore, and an efficient mass tag for efficient ionization in positive electrospray ionization‐mass spectrometry. Chiral columns often have limitations in terms of their chemoselectivity, which may be a problem when complex sample mixtures with structurally related compounds need to be separated. It can be alleviated by a reversed‐phase×chiral two‐dimensional‐liquid chromatography setup, in which the first dimension provides the chemoselectivity and a chiral tandem column constituted of quinine‐carbamate derived weak anion‐exchanger and zwitterionic ion‐exchanger in the second dimension separation of D‐ and L‐amino acid enantiomers. The method was used to control the stereointegrity of the therapeutic peptide octreotide. After hydrolysis, all amino acid constituents were detected with the correct configuration and composition. Some options for flow splitting and integration of destructive detectors in the first dimension separation are outlined. [ABSTRACT FROM AUTHOR]

Fuzhuan brick tea, a distinctive dark tea fermented by microorganisms, is a traditional beverage in China throughout history. Recently, it has attracted considerable attention owing to its unique quality characteristics and potential health benefits. The aim of this study was to establish a method for the quality control of Fuzhuan brick tea for stable production. Ultra‐high‐performance liquid chromatography coupled with quadrupole time‐of‐flight tandem mass spectrometry was used to identify Fuzhuan brick tea, and the major components were chosen for further quantitative analysis. Subsequently, a quantification method was developed using ultra‐high‐performance liquid chromatography coupled with triple‐quadrupole mass spectrometry, and its reliability was verified through methodological validation. Finally, a total of 30 compounds were identified, including catechins, flavonoids, alkaloids, and fatty acids. The established method was reliable for methodological validation and was applied to the quantitative analysis of Fuzhuan brick tea. This study provides a fundamental basis for the quality control and further studies on the component analysis of Fuzhuan brick tea. [ABSTRACT FROM AUTHOR]

Monoterpene indole alkaloids exhibit structural diversity in herbal resources and have been developed as promising drugs owing to their significant biological activities. Confidential identification and quantification of monoterpene indole alkaloids is the key to quality control of target plants in industrial production but has rarely been reported. In this study, quantitative performance of three data acquisition modes of ultra‐high‐performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry including full scan, auto‐MS2 and target‐MS2, was evaluated and compared for specificity, sensitivity, linearity, precision, accuracy, and matrix effect using five monoterpene indole alkaloids (scholaricine, 19‐epi‐scholaricine, vallesamine, picrinine, and picralinal). Method validations indicated that target‐MS2 mode showed predominant performance for simultaneous annotation and quantification of analytes, and was then applied to determine monoterpene indole alkaloids in Alstonia scholaris (leaves, barks) after extraction procedures optimization using Box‐Behnken design of response surface methodology. The variations of A. scholaris monoterpene indole alkaloids in different plant parts, harvest periods, and post‐handling processes, were subsequently investigated. The results indicated that target‐MS2 mode could improve the quantitative capability of ultra‐high‐performance liquid chromatography coupled with quadrupole time‐of‐flight mass spectrometry for structure‐complex monoterpene indole alkaloids in herbal matrices. Alstonia scholaris, monoterpene indole alkaloids, quadrupole time of flight mass spectrometry, qualitative and quantitative analysis, ultra‐high‐performance liquid chromatography [ABSTRACT FROM AUTHOR]

Gandouling tablets are used in a clinical agent for the treatment of hepatocellular degeneration; however, their chemical constituents have not been elucidated. Here, we screened and identified the chemical constituents of Gandouling tablets using ultra‐high‐performance liquid chromatography (UHPLC)‐quadrupole time of flight/mass spectrometry. A method for the quality evaluation of Gandouling tablets was developed by combining the UHPLC fingerprints and the simultaneous quantitative analysis of multiple active ingredients. For fingerprint analysis, 20 shared peaks were identified to assess the similarities among the 10 batches of Gandouling tablets and the similarity was >0.9. The levels of nine representative active ingredients were simultaneously determined to ensure consistency in quality. A total of 99 chemical components were identified, including 18 alkaloids, 20 anthraquinones, 13 flavonoids, 11 phenolic acids, 9 polyphenols, 7 phenanthrenes, 5 sesquiterpenes, 3 curcuminoids, 2 lignans, 2 isoflavones, 2 dianthranones, and 7 other components. The retention times, molecular formulae, and secondary fragmentation information of these compounds were analyzed, and the cleavage pathways and characteristic fragments of some of the representative compounds were elucidated. This systematic analysis used to identify the chemical components of Gandouling tablets lays the foundation for its further quality control and research on their pharmacodynamic substances. [ABSTRACT FROM AUTHOR]

Six sartan substances including telmisartan, losartan, valsartan, irbesartan, olmesartan, and candesartan were selected in this work. A simple and sensitive liquid chromatography–tandem mass spectrometry method was developed and validated to simutaniously detect six drugs. Linearity, LOD, and LOQ were satisfied for routine quantitative and qualitative detection. The linearity ranged from 2 to 1000 ng/mL with the determination coefficient more than 0.98. The intra-day and inter-day precisions were all below 27.5%. All the recoveries were above 80%, and matrix effects were between 25 and 120%. Profiling detection of six sartan substances in human urine was also developed after administration. Irbesartan urinary metabolic pathway was firstly investigated by liquid chromatography quadruple time-of-flight mass spectrometry using full scan and targeted tandem mass spectrometry techniques. Fifteen urinary metabolites of irbesartan were identified and characterized, and ten of them were firstly reported. [ABSTRACT FROM AUTHOR]

Pesticides effectively reduce the population of various pests that harm crops and increase productivity, but leave residues that adversely affect health and the environment. Here, a simultaneous multicomponent analysis method based on ultra-high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UHPLC-QTOF-MS) pretreated by the QuEChERS method was developed to control the maximum residual levels. Among the 140 pesticides with high frequency of detection in agricultural products in Gyeongnam region in Korea for 5 years, 12 pesticides with high detection frequency in sweet pepper were selected. The analytical method is validated, linearities are r2 > 0.999, limit of detection (LOD) ranges from 1.4 to 3.2 µg/kg, and limit of quantification (LOQ) ranges from 4.1 to 9.7 µg/kg, and the recovery rate was 81.7–99.7%. In addition, it was confirmed that a meaningful value of these parameters can be achieved by determining the measurement uncertainty. The results proved that parameters such as recovery rate and relative standard deviation of the analysis method were within international standards. Using the developed method, better and safer sweet peppers will be provided to consumers, and effective pesticide residue management will be possible by expanding to other agricultural products. [ABSTRACT FROM AUTHOR]

Cystic fibrosis is a life‐threatening genetic disease that causes damage to the lungs. Ivacaftor, the first drug to target the underlying defect of the disease caused by specific mutations, improves outcomes and reduces hospitalizations. In this study, quantitative determination of ivacaftor was performed by liquid chromatography, while high‐resolution mass spectrometric analyses were performed for qualitative determination. The validation studies of the developed methods were performed according to International Conference on Harmonisation Q2(R1) guideline. Ivacaftor was separated from its degradation product by using Phenomenex Kinetex C18 (150 × 3 mm, 2.6 µm) column. The isocratic mobile phase for binary pump configuration was 0.1% (v/v) formic acid in water and 0.1% (v/v) formic acid in acetonitrile (27:63) (v/v), pH = 2.5; the flow rate of 0.25 mL/min was used in all methods. In the degradation studies, five degradation products were identified using high‐performance liquid chromatography ion trap time‐of‐flight mass spectrometric analyses: three of them have never been reported up to date; whereas the other two were existing in the literature and they were having Chemical Abstracts Services registry numbers since they were synthesized before for various other purposes. Also, analysis of an in‐lab prepared chemical equivalent of Kalydeco® and interlaboratory comparison were performed. [ABSTRACT FROM AUTHOR]

Oligomers are a particular category of non-intentionally added substances (NIAS) that may be present in food contact materials (FCMs), such as polyethylene terephthalate (PET), and consequently migrate into foods. Here, an ultra-high-pressure liquid chromatography quadruple time-of-flight mass spectrometry (UHPLC-qTOF-MS) method was developed for the analysis of 1st series cyclic PET oligomers in virgin olive oil (VOO) following a QuEChERS clean-up protocol. Oligomer migration was evaluated with two different migration experiments using bottles from virgin and recycled PET: one with VOO samples stored in household conditions for a year and one using the food simulant D2 (95% v/v ethanol in water) at 60 °C for 10 days. Calibration curves were constructed with fortified VOO samples, with the LOQs ranging from 10 to 50 µg L−1 and the recoveries ranging from 86.6 to 113.0%. Results showed no migration of PET oligomers in VOO. However, in the simulated study, significant amounts of all oligomers were detected, with the migration of cyclic PET trimers from recycled bottles being the most abundant. Additional substances were tentatively identified as linear derivatives of PET oligomers. Again, open trimer structures in recycled bottles gave the most significant signals. [ABSTRACT FROM AUTHOR]

A method was established for the determination of 18 flavonoids in tea by ultra-performance liquid chromatography coupled with quadrupole/time-of-flight mass spectrometry (UPLC-Q-TOF/MS). The tea samples were extracted by 70% (V/V) methanol aqueous solution, and separation was achieved on a Kinetex F5 column (2.1 mm × 100 mm, 2.6 μm) with methanol and 0.1% formic acid in water as the mobile phase with a gradient elution. The samples were detected in TOF/MS and information-dependent acquisition (IDA)-MS/MS modes. The results showed that the relative standard deviations of 18 flavonoids were less than 5.0 ppm. The correlation coefficients (R2) of the linear equation were greater than 0.998 in the range of 0.10–200 ng/mL. The limits of detection were 0.0010–0.040 ppm, and the limits of quantification were 0.0020–0.10 ppm. The recoveries ranged from 73.8% to 107% at spiked levels of 0.0020–1.0 ppm, with relative standard deviations (RSDs) being less than 10%. The method was simple, specific, and reliable. It could be used for the rapid screening and quantitative analysis of flavonoids in tea. [ABSTRACT FROM AUTHOR]

Commelina africana L. is widespread in southern Africa, including DR Congo, where it traditionally used for skin disorders. Although an ethnobotanical survey was carried out before, no relevant phytochemical information is available. The aim of this study was to perform the phytochemical characterisation of C. africana and to discuss the potential bioactivity of the identified phytochemical constituents. Ultra-performance liquid chromatography with electrospray ionization quadrupole time-of-flight mass spectrometry (UPLC-ESI-QTOF-MS) was used for profiling and identification of the main phytochemical constituents from leaf extracts (MeOH 90%, DCM, EtOAc, n -BuOH, n -hexane and residue) of C. africana. Twenty-two constituents, comprising flavonoids, phenolic acids, hydroxycinnamic acid amides and lignanamides were identified. Most of the identified compounds are known to have antioxidant and anti-inflammatory properties, which could at least in part explain the traditional use of C. africana against skin disorders. [Display omitted] • Phytochemical characterisation of commelina africana by means of UPLC-ESI-QTOF-MS. • Identification of twenty-two flavonoids, phenolic acids, amides and lignanamides. • The identified constituents may explain the traditional use of commelina africana. [ABSTRACT FROM AUTHOR]

The effects of the flow rate, the injection volume, and the mobile phase ratio on the retention time and the resolution of separation of silybin were examined using Box–Behnken design on a symmetry prep C18 column. The optimum values of the operating parameters were 8 ml/min for the flow rate, 3 ml for the injection volume, and 40:60 for the mobile phase ratio. Under the optimal conditions, the retention time of silybin B was 59.552 min and the resolution of silybin A and silybin B was 1.0696, where the purities of the obtained silybin A and silybin B were both over 99% by ultra‐performance liquid chromatography. The preparative‐liquid chromatography simulation was applied with COMSOL. The optimization results of the response surface are consistent with the experiment and the simulation results. The structures of the compounds were identified by ultra‐performance liquid chromatography‐tandem mass spectrometry and ultra‐performance liquid chromatography‐ time of flight mass spectrometry. [ABSTRACT FROM AUTHOR]

Migrants found in migration solutions obtained from commercially available polyethylene products that may contain food were studied and analysed via liquid chromatography coupled with quadrupole time-of-flight mass spectrometry （LC-QTOF） for non-target screening and LC-MS/MS for quantifying 14 substances in migration solutions. Furthermore, an analytical approach based on the retention gap was developed for accurate separation techniques using LC-MS/MS. Irganox 1076 was detected at a maximum of 1.5 mg/kg, which was 1/4 of the Specific Migration Limit in the EU, in nine commercially available plastic bags tested. This is in accordance with European Regulation No 10/2011/EU. Furthermore, migration of Erucamide and Irgafos 168-oxide was confirmed. [ABSTRACT FROM AUTHOR]

Dendrobium nobile and Dendrobium officinale as the main varieties of traditional Chinese medicine Dendrobium are widely used in clinic. The study aimed to systematically explore chemical constituents and their antitumor effect of D. nobile and D. officinale by ultra-performance liquid chromatography coupled with ion trap time-of-flight mass spectrometry (UPLC-IT-TOF), network pharmacology and cancer cell experiments. D. nobile extract and D. officinale extract could significantly inhibit the proliferation of human lung cancer A549 cells, human liver cancer HepG2 cells and human breast cancer MCF-7 cells in the dose-dependent manner (P < 0.05), the antitumor effect of D. officinale extract was stronger than that of D. nobile extract at the same drug concentration. A total of 40 chemical constituents of D. nobile and D. officinale including phenanthrenes, bibenzyls and other types of compounds had been identified by UPLC-IT-TOF, LCMSsolution and MetID software according to retention times, accurate mass, MSn fragmentation, reference compounds and natural product databases. Phenanthrenes with good antitumor activity were mainly present in D. nobile, bibenzyls were the main compounds of D. officinale. Integrated networks of Herb-Compounds-Targets-Cancer revealed that gigantol, moscatilin, tristin, moscatin and densiflorol B were regarded as key antitumor compounds of D. nobile and D. officinale, D. nobile and D. officinale shared 7 targets accounting for 70% of the antitumor core targets, more than half of their antitumor KEGG pathways were similar. The results of molecular docking and western blotting experiments indicated that the antitumor mechanisms of D. nobile and D. officinale may be through inhibiting PI3K-Akt and HIF-1α signaling pathways. [ABSTRACT FROM AUTHOR]

With the rapid development of social economy and the continuous improvement of people’s living standards, the demand for foods of animal origin is also increasing. The problem of veterinary drug residues in foods of animal origin has attracted more and more attention. Meanwhile, higher requirements have been raised for the supervision and inspection of veterinary drug residues. High-resolution mass spectrometry (HRMS) is a powerful tool to retrieve compounds, which can enable the non-targeted screening and confirmation of a variety of veterinary drugs without the use of standards. HRMS is an important technical means for risk monitoring and high-throughput screening of veterinary drug residues, making up for the weaknesses of triple quadrupole mass spectrometry such as poor universality and no ability to screen unknown compounds. This review summarizes the application of liquid chromatography-high resolution mass spectrometry (LC-HRMS) in the field of veterinary drug residue detection from the year 2018 to 2021, and systematically demonstrates the advantages and characteristics of HRMS. With the popularization of HRMS and the development of detection technologies, HRMS will be widely used in the field of veterinary drug residue detection as a routine method.