Quadrupole Time Research Articles

Phytochemical Composition and Antioxidant Properties of Canarium odontophyllum (Sarawak Olive): A Seasonal Fruit from Borneo, East Malaysia.

BackgroundCanarium species are reported rich of polyphenol, alkaloids, flavones, and saponins compounds. Canarium odontophyllum from Borneo's variety, on the other hand is remaining unclear especially on the antioxidant activity towards radicals. PurposeTo investigate phytochemical composition and antioxidant properties of C. odontophyllum. MethodsAntioxidant properties were evaluated using 2,2-diphenyl-1-picrylhydrazyl-hydrate (DPPH) assay, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) assay, and ferric-reducing antioxidant power (FRAP) assay with different polarity of extraction solvents (methanol, acetone and hexane). The phytochemical composition was determined by Liquid Chromatography Mass Spectrometry Quadrupole Time of Flight (LCMS-QTOF). ResultsAcetone showed the highest scavenging activity in the DPPH (0.0307 mg/ml) and FRAP (3.926 mg/ml) assays, while hexane exhibited the highest activity in the ABTS assay (0.119 mg/ml). The LCMS-QTOF chromatogram identified 22 potential compounds. Among these, the major compounds oleamide (10.49%) and emmotin A (7.23%) have previously been reported to exhibit antioxidant activity. Other health-beneficial compounds were also found, such as palmitic amide (2.46%), deoxymiroestrol (6.23%), and N-Cyclohexanecarbonylpentadecylamine (48.92%), which are important in preventing metal corrosion, regulating hormones, and distinguishing between N-palmitoylethanolamine-hydrolyzing acid amidase (NPAA) and fatty acid amide hydrolase (FAAH), respectively. ConclusionThe results indicate that C. odontophyllum shows a promising potential an alternative drug in pharmaceutical developments.

Bioactivity-Based Analysis and Chemical Characterization of Hypoglycemic Components from Helicteres angustifolia L.

Helicteres angustifolia L. (H. angustifolia), a well-known traditional Chinese medicine, has been demonstrated to have hypoglycemic activity. We found that the EtOAc extract of H. angustifolia (HAEF) showed stronger α-glucosidase inhibitory activity than that of positive control. Furthermore, the hypoglycemic activity of HAEF was evaluated in streptozotocin (STZ)-induced type 2 diabetes mellitus (T2DM) rats. The results demonstrated that HAEF reduced the drinking quantity, feeding quantity, and controlled weight loss in diabetic rats. Besides, the fasting blood glucose (FBG), viscera index, and the area under time-blood glucose curve (AUC) were significantly decreased, and the oral glucose tolerance was also improved after 5 weeks. Then, the high-performance liquid chromatography with quadrupole time of flight tandem mass spectrometry (HPLC-Q-TOF-MS/MS) method was performed for qualitative analysis of the chemical constituents in HAEF. Twenty-one compounds were identified from in HAEF. Four compounds were further isolated from HAEF and subjected to α-glucosidase inhibition experiments. At the end, molecular docking was empolyed simulate the interaction of three compounds with α-glucosidase. This is the first report on major hypoglycaemic components has been identified in the roots of H. angustifolia. These findings provide a material basis for the use of H. angustifolia in the treatment of diabetes.

Investigating the chemical space coverage of multiple chromatographic and ionization methods using non-targeted analysis on surface and drinking water collected using passive sampling

Multiple non-targeted analysis tools were used to look for a broad range of possible chemical contaminants present in surface and drinking water using liquid chromatography separation and high-resolution mass spectrometry detection, including both quadrupole time of flight (Q-ToF) and Orbitrap instruments. Two chromatographic techniques were evaluated on an LC-Q-ToF with electrospray ionization in both positive and negative modes: (1) the traditionally used reverse phase C18 and (2) the hydrophilic interaction liquid chromatography (HILIC) aimed to capture more polar contaminants that may be present in water. Multiple ionization modes were evaluated with an LC-Orbitrap, including electrospray (ESI) and atmospheric pressure chemical ionization (APCI), also in both positive and negative modes. A suspect screening library of over 1300 possible environmental contaminants, including pesticides, pharmaceuticals, personal care products, illicit drugs/drugs of abuse, and various anthropogenic markers was made with experimentally collected data with the LC-Q-ToF with both column types, with 227 chemicals being retained by the HILIC column. The non-targeted methods using multiple chromatographic and ionization modes were applied to environmental water samples collected with polar organic chemical integrative samplers (POCIS), including surface water upstream and downstream from wastewater effluent discharge, and the downstream drinking water intake and treated drinking water for three distinct sampling events. For the LC-Q-ToF, 442 chemical features were detected on the C18 column and 91 with the HILIC column in the POCIS extracts, while 556 features were found on the Orbitrap workflow by ESI and 131 features detected by APCI. Over 100 chemicals were tentatively identified by suspect screening and database searching. The comprehensive and systematic evaluation of these methods serve as a step in characterizing the chemical space covered when utilizing different chromatography and ionization methods, or different instrument workflows on complex environmental mixtures.

Evaluating the Root Extract of Reynoutria ciliinervis (Nakai) Moldenke: An Analysis of Active Constituents, Antioxidant Potential, and Investigation of Hepatoprotective Effects in Rats

Reynoutria ciliinervis (Nakai) Moldenke (R. ciliinervis) root, a traditional Chinese medicine, was found to exhibit remarkable pharmacological properties through a series of comprehensive investigations. Our study commenced with a qualitative phytochemical analysis that identified 12 bioactive compounds within the plant. Subsequently, utilizing ultraviolet-visible spectrophotometry, the methanol extract emerged as the optimal solvent extract, which was abundant in diverse classes of compounds such as carbohydrates, phenolics, steroids, alkaloids, phenolic acids, and tannins. In vitro antioxidant assays underscored the exceptional free radical scavenging, metal ion chelation, hydrogen peroxide scavenging, singlet oxygen quenching, and β-carotene bleaching capabilities of the methanol extract, significantly outperforming other solvent extracts. Further ultra high-performance liquid chromatography–electrospray ionization–quadrupole time of flight–mass spectrometry analysis revealed the presence of 45 compounds, predominantly anthraquinones and phenolics, in the methanol extract. The extract demonstrated robust stability under various conditions, including high temperatures, varying pH levels, and simulated gastrointestinal digestion as well as efficacy in inhibiting the oxidation in edible oils. Acute toxicity tests in mice confirmed the safety of the methanol extract and provided a valuable dosage reference for future studies. Importantly, high-dose methanol extract exhibited a significant pre-protective effect against D-galactosamine-induced liver injury in rats, as evidenced by reduced alanine aminotransferase, aspartate aminotransferase, γ-glutamyl transpeptidase, malondialdehyde levels, and elevated catalase and albumin levels. These findings suggest a potential role for the methanol extract of R. ciliinervis root in treating oxidative stress-related disorders, highlighting the plant’s immense medicinal potential. Our research offers a thorough evaluation of the bioactive components, antioxidant properties, stability, and liver-protecting effects of the methanol extract, setting the stage for deeper investigation and potential clinical applications.

Metabolomic insights into idiopathic xerostomia: The central role of caffeine metabolism in salivary biochemistry

ObjectiveThis study aims to delineate the salivary metabolomic profile of patients with idiopathic xerostomia using untargeted metabolomics techniques, with the goal of addressing the lack of clear diagnostic markers and providing insights into the pathophysiological mechanisms of the condition. DesignIn this observational, cross-sectional study, saliva samples from 33 patients with idiopathic xerostomia and 34 healthy controls were analyzed using Ultra Performance Liquid Chromatography Quadrupole Time of Flight Mass Spectrometry (UPLC-QTOF MS). Metabolomic profiling was complemented by multivariate statistical analysis to differentiate between affected individuals and controls. ResultsMetabolomic analysis delineated a pronounced differentiation between patients with idiopathic xerostomia and healthy controls. A total of 195 metabolites displayed significant differential expression, each with a variable importance in projection (VIP) greater than 1 and a P-value less than 0.05. Pathway enrichment analysis, according to the Kyoto Encyclopedia of Genes and Genomes (KEGG), identified 22 metabolites that participated in 18 distinct metabolic pathways. Among these, the caffeine metabolism pathway, characterized by notable alterations in impact values (VIP, P-value, Log2-fold change, Rich factor), emerged as the most significantly disrupted, underscoring its potential role in the pathophysiology of idiopathic xerostomia (P = 0.0000395). ConclusionsThe salivary metabolomic profiling revealed distinct alterations in idiopathic xerostomia, with a significant reduction in caffeine metabolism pathways, underscoring potential neuropathic involvement. This study advances our understanding of the metabolic alterations in xerostomia, suggesting that salivary metabolomics may offer viable biomarkers for diagnosing and understanding the etiology of idiopathic xerostomia. Future research should focus on therapeutic targeting of these metabolic disturbances and evaluating their reversibility with treatment.

Thevetia thevetioides Cardenolide and Related Cardiac Glycoside Profile in Mature and Immature Seeds by High-Resolution Thin-Layer Chromatography (HPTLC) and Quadrupole Time of Flight-Tandem Mass Spectrometry (Q-TOF MS/MS) Reveals Insights of the Cardenolide Biosynthetic Pathway.

Thevetia thevetioides is a species within the Apocynaceae family known for containing cardenolide-glycosides, commonly referred to as cardiac glycosides, which are characteristic of this genus. The seeds of the Thevetia species are frequently used as a model source for studying cardiac steroids, as these glycosides can be more readily extracted from the oil-rich seeds than from the plant's green tissues. In this work, the cardenolide profile of ripe and immature seeds was determined and compared to establish the main differences. Ripe seeds contain six related cardenolides and triosides, with thevetin B being the predominant component. In contrast, immature seeds exhibit a total of thirteen cardiac glycosides, including monoglycosides such as neriifolin and peruvosides A, B, and C, as well as diglycosides like thevebiosides A, B, and C. Some of these compounds have previously been identified as degradation products of more complex cardiac glycosides; however, their presence in immature seeds, as described in this study, suggests that they may serve as biosynthetic precursors to the triosides observed in mature seeds. The glycoside patterns observed via HPTLC are associated with specific chemical structures characteristic of this genus, typically featuring thevetose or acetyl-thevetose at the first position, followed by glucose or gentibiose in di- or trisaccharides, independent of the trioside aglycones identified: digitoxigenin, cannogenin, or yccotligenin. Ripe seeds predominantly contain triosides, including thevetin B, C, and A, the latter of which has not been previously reported.

In-depth phytochemical profiling of Roscoea purpurea (Kakoli): Comparative UHPLC-MS/QToF and GC-MS/MS analysis of supercritical CO2 fluid - and conventional solvent - based extractive processes

The remarkable biodiversity of medicinal plants worldwide highlights their significance in traditional and alternative medicine. Astavarga, a group of eight medicinal herbs from the Himalayan region of India, including Roscoea purpurea (commonly known as Kakoli), is esteemed in Ayurveda for its health-promoting and rejuvenating properties. In this comprehensive study, we aimed to develop and optimise robust UHPLC-MS/QToF (Ultra-high-performance liquid chromatography-mass spectrometry coupled with quadrupole time of flight) and GC-MS/MS (Gas chromatography-tandem mass spectrometry) methods to identify the phytochemicals in R. purpurea root hydromethanolic extract and essential oil. We also conducted a comparative assessment of supercritical fluid extraction and conventional solvent extraction methods for the first time in R. purpurea root, highlighting their relevance to the medicinal field. Using the UHPLC/MS-QToF method, we identified a total of fifty-six phytometabolites, while sixteen volatile constituents were discerned within the essential oil of R. purpurea by GC-MS/MS method. Among the volatile constituents, β-eudesmol (40.84 %), guaiac acetate (10.55 %), and γ-eudesmol (10.31 %) were emerged as the principal components. Our findings were further compared with the volatile constituents extracted via supercritical fluid extraction and conventional solvent extraction methods. Notably, our research unveiled the presence of a carotenoid metabolite, 15-methyl retinol, for the first time. Furthermore, our fatty acid analysis of the supercritical fluid extract revealed elevated levels of unsaturated fatty acids, particularly oleic and linoleic acids. The methods were validated in terms of system specificity also. The discovery of these well-recognised therapeutically active components in R. purpurea significantly enhances its potential, highlighting its unique profile among medicinal plants in the Himalayan region and its suitability for traditional Ayurveda.

Comprehensive phytochemical profiling of Phyllanthus emblica L. flowers on UHPLC/MS quadrupole time of flight, HPTLC, HPLC, and NMR analytical platforms reveals functional metabolites with potent anti-inflammatory effects in human (THP-1) macrophages.

Phyllanthus emblica L., renowned for its pharmacological benefits found in its fruits and leaves, has received considerable attention. However, there is a notable lack of research on its flowers, specifically on metabolite profiling and pharmacological activity. The present study aims to delineate the phytochemical constituents of hydromethanolic extract of P.emblica flowers by ultra-high-performance liquid chromatography coupled with quadrupole time of flight mass spectrometry (UHPLC-QToF-MS), high-performance thin layer chromatography (HPTLC), high-performance liquid chromatography (HPLC), infrared and nuclear magnetic resonance spectroscopic methods and subsequent evaluation of its anti-inflammatory potential. The identification and characterization of phytochemicals in P.emblica flowers was performed by UHPLC/MS-QToF in both positive and negative ionization modes. Additionally, marker compounds present in flower extract were analyzed using HPTLC, HPLC, FT-IR, and NMR methods. The anti-inflammatory potential was evaluated in lipopolysaccharide-stimulated THP-1 macrophages by evaluating inflammatory biomarkers. UHPLC/MS-QToF analysis facilitated the identification of 51 compounds from P.emblica flowers including gallic acid derivatives, flavonoid glycosides, and tannins based on their fragmentation patterns and previous literature reports. Notably, the study also identified spermidine compounds for the first time in this species. Optimization of HPTLC and HPLC methods marked the presence of corilagin as major compound followed by FT-IR and NMR spectral methods. Moreover, treatment with hydromethanolic extract of P.emblica flowers resulted in decreased levels of proinflammatory cytokines, TNF-α, IL-1β, and IL-6, alongside modulation of nuclear factor-κB activity in lipopolysaccharide-induced THP-1 macrophages. Chromatographic techniques in conjunction with spectral methods found robust prevalence in the identification of signature phytometabolites present in P. emblica flowers, which sets the basis for its anti-inflammatory potentials. The studies established a foundation for further exploration of potential applications of P. emblica flowers across various domains.

Enhancement of per- and Polyfluoroalkyl Substances (PFAS) quantification on surface waters from marinas in the douro river, Portugal

PFAS, known as "forever" compounds, are prevalent in various environments, including soils and aquatic systems, due to extensive usage. Surface waters in several European countries, especially marinas and ports with high boat traffic, require further study as potential contamination sources. Reliable methods for the extraction and quantification of these emergent compounds are essential. This study aimed to improve an existent solid phase extraction method to analyse marinas and ports’ surface waters with variable salinities (2, 9 and 17 PSU). The objectives were to: 1) optimise the solid phase extraction method, considering matrix salinity effects and cross-contaminations, 2) validate the extraction and quantification method of 18 EPA 537.1 PFAS in estuarine surface waters, using the Ultra-High Performance Liquid Chromatography – Quadrupole Time – Of – Flight – Tandem Mass spectrometry, and 3) apply the optimised method for PFAS quantification in three Portuguese marinas. All ICH criteria were successfully validated considering 9 PSU. Limits of quantification ranged from 117.80 ng/L to 385 ng/L, except for PFHpA (645.85 ng/L). PFAS levels (PFOA, HFPO-DA, PFBS, PFHxS and PFOS) were relatively low, reaching a maximum of 0.32 ng/L only for the PFOA. In Freixo marina, total average concentrations were slightly higher (∑PFAS = 1.02 ng/L) when compared to the ones found in Cais da Ribeira Port (∑PFAS = 0.94 ng/L) and Afurada marina (∑PFAS = 0.81 ng/L). PFOS concentrations are below the limit values set by the Environmental Quality Standards (36000 ng/L of PFOS for inland surface water, respectively), similar to other Portuguese river studies. This study enabled the development of a precise and reliable extraction and quantification method to quantify PFAS in estuarine surface waters, particularly from marinas. This method can be readily applied to analyse PFAS in other estuarine samples.

Profiling of saponins in four different species of Chlorophytum by liquid chromatography quadrupole time of flight mass spectrometry

The genus Chlorophytum, rich in saponins is used in Ayurveda, an Indian alternative system of medicine. This study illustrates a comprehensive picture of saponins in four different species of Chlorophytum viz., Chlorophytum borivilianum Santapau and Fernandes, Chlorophytum glaucoides Blatt, Chlorophytum glaucum Dalz, Chlorophytum bharuchae Ansari, Sundargarh, Hemadri, from the western ghats of India. Metabolite profiling of leaves and tubers using Liquid Chromatography Quadrupole Time Of Flight Mass Spectrometry (LC-Q-TOF-MS) indicated presence of 13 saponins. C. glaucum was found to be abundant in saponins followed by C. glaucoides. Tokorogenin, diosgenin and sarsasapogenin are most abundant saponins confirmed from the leaves of C. glaucum and tubers of C. glaucoides.

Detection of the benzodiazepine bromazolam by liquid chromatography with quadrupole time of flight mass spectrometry in postmortem toxicology casework and prevalence in Indiana (2023).

For the past 60 years, benzodiazepines such as chlordiazepoxide, diazepam, and alprazolam have been used as pharmaceutical medications for the treatment of myriad conditions including anxiety, seizures, and insomnia. In more recent years, novel benzodiazepine derivatives have emerged as illicit substances in powders and counterfeit tablets on the illicit drug market. In 2016, bromazolam, a brominated derivative of alprazolam, emerged on the illicit drug market in Europe, but the substance was not reported in the USA until 2019-2020. In this study, we report the emergence and subsequent prevalence of bromazolam in postmortem blood in the state of Indiana during 2023. Analysis was completed by a solvent protein precipitation extraction with acetonitrile and detection by liquid chromatography with quadrupole time of flight mass spectrometry. During 2023, bromazolam was detected in 94 cases across 25 counties in Indiana. It was never the sole substance detected and was commonly detected alongside fentanyl (83 cases), norfentanyl (77 cases), 4-anilino-N-phenethylpiperidine (76 cases), acetylfentanyl (49 cases), methamphetamine (32 cases), naloxone (25 cases), 11-nor-9-carboxy-tetrahydrocannabinol (24 cases), and benzoylecgonine (20 cases). After official query with the Indiana Department of Health, it was found that bromazolam was specifically included in the cause of death certification in 31 fatalities (32.9%). Due to the scarcity of information regarding this novel benzodiazepine derivative in postmortem toxicology and its involvement in fatalities, it is important that forensic toxicology laboratories consider adding bromazolam to their comprehensive scope of analysis.

Comparative study of antioxidant activities of Allium sativum (a novel variety, HG17) and Allium ampeloprasum (SMG): Revealing the higher potential of HG17 and analyzing its phytochemicals.

Garlic, belonging to the genus Allium, is renowned for its rich antioxidant potential. Snow Mountain garlic (SMG) (Allium ampeloprasum) has been traditionally used for medicinal purposes because of its higher antioxidant potential. Considering its potential in medical therapies, we compared the antioxidant activity of SMG with a novel variety of Allium sativum, Hisar garlic 17 (HG17). Comparative antioxidant activity data (2,2-diphenyl-1-picrylhydrazyl and 2,2-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) revealed the higher antioxidant activity of HG17 than SMG, which prompted us to conduct a comprehensive phytochemical investigation to elucidate the factors contributing to antioxidant potential of HG17. To get a detailed antioxidant and phytoconstituents profiling, we differentially extracted HG17 by processing it in different forms (fresh, dry, heated, and aged) with two solvents (50% methanol and n-butanol). Our data (antioxidant activities, total phenolics, and flavonoids) showed that dry garlic methanolic extract (DgM) had maximum potential than other HG17 forms/solvents, which concludes that different extraction techniques had direct impact on the phenolics/flavonoids and antioxidant potential of the extracts. Further, phytochemical analysis of HG17 extracts by high resolution liquid chromatograph mass spectrometer quadrupole time of flight validated the maximum potential of DgM. LCMS revealed the presence of garcimangosone C, osmanthuside A, and protoaphin aglucone polyphenols exclusively in DgM compared to other HG17 extracts, which possibly contributing in its high antioxidant potential. The overall differential extraction and LCMS data of HG17 strongly depict that it may be used as an alternative of SMG under diverse medical applications. HG17 higher antioxidant potential and rich array of unique phytochemicals make it valuable for food and pharmaceutical industries to integrate into functional foods/therapeutics. PRACTICAL APPLICATION: Garlic unique phytochemical composition and its remarkable ability to scavenge different radicals make it valuable therapeutic asset to mitigate diseases associated with oxidative stress. SMG is well known for its anti-arthritic and anti-inflammatory properties. HG17 showed higher antioxidant potential than SMG and can be used as an alternative of SMG for anti-arthritic properties.

A strategy integrating GC–MS, UPLC profiling, and DNA metabarcoding for characterization and discrimination of the medicinal and culinary pieces from four Curcuma species

Curcumae pieces prepared in ready-to-use forms, consumed extensively for their significant medicinal and culinary benefits, present a challenge in discrimination due to their heterogeneous origins, analogous morphologies, and varied components. This study explored the metabolites of nine Curcumae pieces (NCPs) by Gas Chromatography-Mass Spectrometry (GC–MS) and Ultra-Performance Liquid Chromatography/Ultra High-Performance Liquid Chromatography–Quadrupole Time of Flight–Mass Spectrometry (UPLC/UHPLC–QTOF–MS) technologies, augmented by multivariate statistical analysis (Principal Component Analysis, PCA; Orthogonal Partial Least Squares Discriminant Analysis, OPLS–DA) and machine learning algorithms (Random Forest, RF). Twenty-six key differential markers in volatile and non-volatile metabolites each were found subsequently. Additionally, DNA metabarcoding was employed to develop specific Single Nucleotide Polymorphism (SNP) markers for the precise identification of Curcuma species in single and mixed samples, and for CRa even contained in Chinese patent prescriptions. The integration of these three methodologies facilitates a more reliable authentication of NCPs, enhancing the overall strategy for their global discrimination. This research contributes to the advancement of quality control and the development of functional foods or products derived from Curcumae pieces, tailored to meet specific health and dietary requirements.

Exploring the mechanism of diabetic cardiomyopathy treated with Qigui Qiangxin mixture based on UPLC-Q/TOF-MS, network pharmacology and experimental validation.

Despite its effectiveness in treating diabetic cardiomyopathy (DCM), Qigui Qiangxin Mixture (QGQXM) remains unclear in terms of its active ingredients and specific mechanism of action. The purpose of this study was to explore the active ingredients and mechanism of action of QGQXM in the treatment of DCM through the comprehensive strategy of serum pharmacology, network pharmacology and combined with experimental validation. The active ingredients of QGQXM were analyzed using Ultra-performance liquid chromatography coupled with quadrupole time of flight mass spectrometry (UPLC-Q/TOF-MS). Network pharmacology was utilized to elucidate the mechanism of action of QGQXM for the treatment of DCM. Finally, in vivo validation was performed by intraperitoneal injection of STZ combined with high-fat feeding-induced DCM rat model. A total of 25 active compounds were identified in the drug-containing serum of rats, corresponding to 121 DCM-associated targets. GAPDH, TNF, AKT1, PPARG, EGFR, CASP3, and HIF1 were considered as the core therapeutic targets. Enrichment analysis showed that QGQXM mainly treats DCM by regulating PI3K-AKT, MAPK, mTOR, Insulin, Insulin resistance, and Apoptosis signaling pathways. Animal experiments showed that QGQXM improved cardiac function, attenuated the degree of cardiomyocyte injury and fibrosis, and inhibited apoptosis in DCM rats. Meanwhile, QGQXM also activated the PI3K/AKT signaling pathway, up-regulated Bcl-2, and down-regulated Caspase9, which may be an intrinsic mechanism for its anti-apoptotic effect. This study preliminarily elucidated the mechanism of QGQXM in the treatment of DCM and provided candidate compounds for the development of new drugs for DCM.

Effect of the storage process on quality characteristics of hemp-enriched "tsoureki" a rich-dough baked Greek product.

The effects of the storage process on the quality characteristics of a hemp-enriched "tsoureki" (a rich-dough baked Greek product, rich-dough baked product [RDBP]) were investigated. The wheat flour was substituted with defatted hemp flour at selected ratios (0%-50% hemp:wheat flour). The baked products were stored at 25°C and at specific time intervals (0, 1, 4, 7, 10, and 14 days), and their properties were determined, including moisture content, water activity, structure, texture, color, total phenolic content (TPC), and antioxidant activity. Moreover, analyses of phenolic compounds were performed using quadrupole time of flight liquid chromatography-mass spectroscopy, identifying 14 compounds. Both the first-order kinetic model and modified Avrami equation, including the hemp-to-wheat ratio effect in the rate constant, well described the changes in the quality characteristics. The results showed that storage time and hemp incorporation significantly affected the quality of the product. Water activity decreased from 0.901 to 0.859, whereas moisture content decreased from 30.52%-32.33% (0 days) to 26.97%-27.02% w.b. (14 days) with storage time for all hemp additions. Hardness was greatly affected by hemp flour addition and approached 14.72 and 17.85 N after 14 days of storage for 30% and 50% substitutions, respectively. Springiness and cohesiveness decreased with hemp addition and storage time. The color difference of the hemp-enriched products compared to the control sample increased during storage. TPC increased due to the addition of hemp flour, whereas 14 compounds were identified. Based on property correlation, the hemp-enriched RDBP-tsoureki held its high-quality characteristics for 7 days of storage and contained a significant amount of bioactive compounds. PRACTICAL APPLICATION: Industrially produced, defatted hemp is a promising byproduct that can be used to nutritionally enhance baked goods. Modeling results can be used for the prediction of the properties that define product storage ability and also that the hemp-enriched, rich dough-baked Greek "tsoureki" could be produced while maintaining total phenolic content and antioxidant activity during 7 days of storage. These findings are expected to be used in the future in baked goods industry applications to produce goods with an improved nutritional profile.

LC-qTOF-MS/MS phytochemical profiling of Tabebuia impetiginosa (Mart. Ex DC.) Standl. leaf and assessment of its neuroprotective potential in rats

Ethnopharmacological relevanceTabebuia impetiginosa (Bignoniaceae) was traditionally used for memory enhancement and central nervous system (CNS) stimulation.Aim of the study: This study aims to create a metabolic profile of the ethyl acetate fraction of T. impetiginosa (TEF) and investigate for the first time its neuroprotective potential on cyclophosphamide (CP)-induced chemobrain, validating its traditional use. Materials and methodsMetabolite profiling of TEF was performed using Liquid Chromatography coupled with Quadrupole Time of Flight-Mass/Mass Spectrometry (LC-qTOF-MS/MS). For the in vivo study, CP (200 mg/kg, i.p.) was administered to induce cognitive impairment in rats; TEF (30 mg/kg, p.o.) was administered throughout the 14 days of the experiment to assess its role in mitigating CP-induced neuronal deficits. Behavioral tests including locomotor, Y-maze, and passive avoidance tests were conducted. Additionally, biochemical markers such as reduced glutathione (GSH), malondialdehyde (MDA), tumor necrosis factor-α (TNF-α), and caspase-3 immunoexpression were assessed in the hippocampus area. ResultsForty-four phytoconstituents were tentatively identified in TEF, mainly iridoids and organic acids. TEF showed significant memory enhancement as evidenced by the increase in step-through latency in the passive avoidance test by 1.5 folds and the increase in sequence alternation percentage (SAP) in the Y-maze test by 67.3%, as compared to CP-group. Moreover, it showed pronounced antioxidant and anti-inflammatory potentials evidenced by the significant elevation in reduced glutathione (GSH) levels by 80% and a pronounced decline in MDA and TNF-α levels by 24% and 45%, respectively relative to the CP group. TEF treatment restored normal hippocampal histological features and attenuated apoptotic caspase-3 expression by 70% compared to the CP group. ConclusionsTEF can act as a promising natural scaffold in managing the chemobrain induced by CP in cancer patients.

Nanoplastic contamination: Impact on zebrafish liver metabolism and implications for aquatic environmental health

Nanoplastics (NPs) are increasingly pervasive in the environment, raising concerns about their potential health implications, particularly within aquatic ecosystems. This study investigated the impact of polystyrene nanoparticles (PSN) on zebrafish liver metabolism using liquid chromatography hybrid quadrupole time of flight mass spectrometry (LC-QTOF-MS) based non-targeted metabolomics. Zebrafish were exposed to 50 nm PSN for 28 days at low (L-PSN) and high (H-PSN) concentrations (0.1 and 10 mg/L, respectively) via water. The results revealed significant alterations in key metabolic pathways in low and high exposure groups. The liver metabolites showed different metabolic responses with L-PSN and H-PSN. A total of 2078 metabolite features were identified from the raw data obtained in both positive and negative ion modes, with 190 metabolites deemed statistically significant in both L-PSN and H-PSN groups. Disruptions in lipid metabolism, inflammation, oxidative stress, DNA damage, and amino acid synthesis were identified. Notably, L-PSN exposure induced changes in DNA building blocks, membrane-associated biomarkers, and immune-related metabolites, while H-PSN exposure was associated with oxidative stress, altered antioxidant metabolites, and liver injury. For the first time, L-PSN was found depolymerized in the liver by cytochrome P450 enzymes. Utilizing an analytical approach to the adverse outcome pathway (AOP), impaired lipid metabolism and oxidative stress have been identified as potentially conserved key events (KEs) associated with PSN exposure. These KEs further induced liver inflammation, steatosis, and fibrosis at the tissue and organ level. Ultimately, this could significantly impact biological health. The study highlights the PSN-induced effects on zebrafish liver metabolism, emphasizing the need for a better understanding of the risks associated with NPs contamination in aquatic ecosystems.

Lipidomic changes occurring in platelets during extended cold storage.

Cold storage is being implemented as an alternative to conventional room-temperature storage for extending the shelf-life of platelet components beyond 5-7 days. The aim of this study was to characterise the lipid profile of platelets stored under standard room-temperature or cold (refrigerated) conditions. Matched apheresis derived platelet components in 60% PAS-E/40% plasma (n = 8) were stored at room-temperature (20-24°C with agitation) or in the cold (2-6°C without agitation). Platelets were sampled on day 1, 5 and 14. The lipidome was assessed by ultra-pressure liquid chromatography ion mobility quadrupole time of flight mass spectrometry (UPLC IMS QToF). Changes in bioactive lipid mediators were measured by ELISA. The total phospholipid and sphingolipid content of the platelets and supernatant were 44 544 ± 2915 μg/mL and 38 990 ± 10 880 μg/mL, respectively, and was similar over 14 days, regardless of storage temperature. The proportion of the procoagulant lipids, phosphatidylserine (PS) and phosphatidylethanolamine (PE), increased by 2.7% and 12.2%, respectively, during extended cold storage. Cold storage for 14 days increased sphingomyelin (SM) by 4.1% and decreased ceramide by 1.6% compared to day 1. Further, lysophosphatidylcholine (LPC) species remained unchanged during cold storage for 14 days. The concentration of 12- and 15-hydroxyeicosatetraenoic acid (HETE) were lower in the supernatant of cold-stored platelets than room-temperature controls stored for 14 days. The lipid profile of platelets was relatively unchanged during storage for 5 days, regardless of temperature. However, during extended cold storage (14 days) the proportion of the procoagulant lipids, PS and PE, increased, while LPC and bioactive lipids were stable.

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

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

Determination of twelve neonicotinoid pesticides in chili using an improved QuEChERS method with UPLC-Q-TOF/MS

In this study, a QuEChERS method based on citrate was developed and utilized for the analysis of twelve neonicotinoid pesticides in fresh red chilies, fresh green chilies, and dried chilies, coupled with ultra-high performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF/MS). In the sample preparation, acetonitrile containing 1% formic acid was used as the extraction solvent. Anhydrous sodium sulfate replaced the traditional anhydrous magnesium sulfate for water removal, effectively eliminating the issues of salt caking. Graphitized carbon black, octadecyl silica, and primary secondary amine were used as cleaning agents. The method showed good sensitivity, with the limits of quantification below 0.03 mg/kg for fresh chilies and below 0.15 mg/kg for dried chilies. Values of matrix effects ranged from −19.5% to 8.4%, and the recovery was 86.9% - 105.2%. The analytical method provided an effective tool for the high throughput detection of neonicotinoid pesticide residues in multiple chili matrices.