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Caffeine is an ergogenic substance that is consumed globally in many forms. The use of buccally absorbable formulations instead of gastrointestinal uptake has become increasingly popular over the years, especially when accelerated absorption with minimal gastrointestinal stress is desired. This study investigated the impact of five different formulations and administration routes of caffeine on the whole blood concentrations of caffeine, paraxanthine, and theobromine: caffeinated capsules, tablets, shots, pouches, and chewing gums. A uniform dose of caffeine (200 mg) was administered to 16 healthy recreational athletes (26.0 ± 2.1 years) using a randomized crossover design. Samples were taken in the form of dried blood spots at 16 different time points in a 2-hr timeframe after drug administration. The samples were analyzed using a validated liquid chromatography–tandem mass spectrometry method. The results for caffeine showed no significant differences in the overall bioavailability (area under the concentration–time curve), maximal concentration, and time to maximum concentration. However, when analyzing the bioavailability of caffeine in the first 5, 10, and 15 min, the liquid caffeine formulation was superior to other administered forms (p <.05). This indicates that caffeine solubility has a major influence on its absorption rate. In sports, the rate of caffeine absorption must be considered, not only when ingesting anhydrous caffeine, but also when choosing buccal absorption. These findings imply that general guidelines for ergogenic caffeine use should consider the formulation used and, accordingly, the corresponding route of absorption. [ABSTRACT FROM AUTHOR]

Liquid chromatography with mass spectrometry (LC-MS)-based metabolomics detects thousands of molecular features (retention time-m/z pairs) in biological samples per analysis, yet the metabolite annotation rate remains low, with 90% of signals classified as unknowns. To enhance the metabolite annotation rates, researchers employ tandem mass spectral libraries and challenging in silico fragmentation software. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) may offer an additional layer of structural information in untargeted metabolomics, especially for identifying specific unidentified metabolites that are revealed to be statistically significant. Here, we investigate the potential of hydrophilic interaction liquid chromatography (HILIC)-HDX-MS in untargeted metabolomics. Specifically, we evaluate the effectiveness of two approaches using hypothetical targets: the post-column addition of deuterium oxide (D2O) and the on-column HILIC-HDX-MS method. To illustrate the practical application of HILIC-HDX-MS, we apply this methodology using the in silico fragmentation software MS-FINDER to an unknown compound detected in various biological samples, including plasma, serum, tissues, and feces during HILIC-MS profiling, subsequently identified as N1-acetylspermidine.

Rationale: Hypoxen is a medication known for providing individuals with a "second wind," by lowering the threshold for muscle fatigue and enhancing the body's efficiency under challenging conditions. Athletes who have used this medication report enhanced training outcomes and increased physical endurance. It is crucial to emphasize that hypoxen is not categorized as a prohibited substance as yet and is thus assumed safe for use in competitive sports. However, the polymeric nature of hypoxen presents challenges in detection and identification. Methods: To prevent the potential misuse of this substance as a doping agent, doping control laboratories must therefore develop a detection method. This study aimed to address this gap by developing a comprehensive detection method for the polymeric mixtures within hypoxen, employing liquid chromatography‐electrospray ionization‐mass spectrometry. Results: Among the different columns tested, the Accucore and Syncronis HILIC columns demonstrated exceptional performance, yielding excellent separation with high‐quality results. The study found that the hypoxen consisted of between 1 and 6 repetitions of 2,4‐dihydroxyphenylene units. It was crucial to highlight that each unit contained multiple isomers due to the incorporation of the sulfonic acid group at both the ‐SH and ‐OH positions. Conclusions: The results of this study will significantly contribute to the precise identification of hypoxen use, thereby aiding in the scrutiny of its abuse in competitive sports. [ABSTRACT FROM AUTHOR]

Expanded polystyrene is widely produced and used due to its properties and, recently, its ability to present π–π interactions has been described. Therefore, this work proposed to use recycled polystyrene for solid phase extraction of 12 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Recycled polystyrene films were formed and characterised by Fourier transform infrared spectroscopy, scanning electron microscopy and affinity experiments. A moderate interaction was found, which allowed its integration in pipette tip-solid phase extraction followed by HPLC-FLD analysis. The method presents limits of detection in the range of 0.05–0.14 ng mL−1 for 12 PAHs analytes, with a precision (expressed as relative standard deviation) <10%. The methodology was applied to tap water samples, and the results were compared to those obtained using the official methodology, with no statistically significant differences. The proposed method is efficient, fast and has a low consumption of organic solvent. [ABSTRACT FROM AUTHOR]

Dissolved organic matter (DOM) is a complex mixture of thousands of molecular formulas comprised of an unknown number of chemical compounds, the concentration and composition of which are critical to ecosystem function and biogeochemical cycling. Despite its importance, our understanding of the DOM composition is lacking. This is principally due to its molecular complexity, which means that no single method is capable of describing DOM in its entirety. Quantification is typically done by proxy (e.g., relative to carbon content) and does not necessarily match well to compositional data, due to incomplete analytical windows and selectivity of different analytical methods. We present an integrated liquid chromatography (LC)–diode array detector (DAD)–charged aerosol detector (CAD)–mass spectrometry (MS) pipeline designed to both characterize and quantify solid-phase extractable DOM (SPE-DOM) in a single analysis. We applied this method to a set of eight Swedish water bodies sampled in the summer and winter. Chromophoric SPE-DOM was proportionally higher in samples with higher SPE-DOM concentrations but remained relatively consistent between sampling occasions. Ionizable SPE-DOM was relatively consistent across sites but was proportionally higher in summer. Overall, the carbon content of DOM was very consistently ∼40% across sites in both summer and winter. These findings suggest that SPE-DOM concentration at these sites is driven by (presumably allochthonous) chromophoric inputs, with an increased relative contribution in summer of material that is more ionizable and less chromophoric and may be either autochthonous or selectively enriched from allochthonous sources. Thus, with minimal additional effort, this method provided further compositional insights not attained by any single analysis in isolation. [ABSTRACT FROM AUTHOR]

Liquid chromatography with a metal–organic framework (MOF) as the stationary phase enables nanopore threading-based recognition of polymers and identification of single-point isomeric structural differences in the polymer main chain. The polymer adsorption affinity to the MOF and transient kinetics of polymer insertion into the nanopores play crucial roles in the recognition process. [ABSTRACT FROM AUTHOR]

Introduction and objectives: The application of untargeted metabolomics assays using ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) to study metabolism in biological systems including humans is rapidly increasing. In some of these studies there is a requirement to collect and analyse low sample volumes of biofluids (e.g. tear fluid) or low cell and tissue mass samples (e.g. tissue needle biopsies). The application of microflow, capillary or nano liquid chromatography (≤ 1.0 mm column internal diameter (i.d.)) theoretically should accomplish a higher assay sensitivity compared to analytical liquid chromatography (2.1–5.0 mm column internal diameter). To date, there has been limited research into microflow UHPLC-MS assays that can be applied to study samples of low volume or mass. Methods: This paper presents three complementary UHPLC-MS assays (aqueous C18 reversed-phase, lipidomics C18 reversed-phase and Hydrophilic Interaction Liquid Chromatography (HILIC)) applying 1.0 mm internal diameter columns for untargeted metabolomics. Human plasma and urine samples were applied for the method development, with porcine plasma, urine and tear fluid used for method assessment. Data were collected and compared for columns of the same length, stationary phase and stationary phase particle size but with two different column internal diameters (2.1 mm and 1.0 mm). Results and conclusions: All three assays showed an increase in peak areas and peak widths when applying the 1.0 mm i.d. assays. HILIC assays provide an advantage at lower sample dilutions whereas for reversed phase (RP) assays there was no benefit added. This can be seen in the validation study where a much higher number of compounds were detected in the HILIC assay. RP assays were still appropriate for small volume samples with hundreds of compounds being detected. In summary, the 1.0 mm i.d. column assays are applicable for small volume samples where dilution is required during sample preparation. [ABSTRACT FROM AUTHOR]

The list of standard abbreviations for JDS is available at adsa.org/jds-abbreviations-24. Nonstandard abbreviations are available in the Notes. The influence of diet composition on the degree of adipose and lean muscle mobilization and concentrations of circulating AA has been demonstrated during the transition period. Altering the MP supply might offer a strategy to control tissue mobilization and increase circulating AA availability, but the optimum supply of MP fed pre- and postpartum remains unknown. We investigated the effect of increasing the MP supply in the prepartum, postpartum, or both diets on plasma AA concentrations and ultrasound and circulating indicators of tissue mobilization. Multiparous Holstein cows (n = 96) were assigned to 1 of 4 treatment groups at 28 d before expected calving following a randomized block design. Prepartum diets were formulated to contain either a control (CON; 85 g of MP/kg DM; 1,175 g of MP/d) or high (HI; 113 g of MP/kg DM; 1,603 g of MP/d) level of estimated MP. From calving to 21 DIM, fresh diets were formulated to contain either a control (CON; 104 g of MP/kg DM; 2,044 g of MP/d) or high (HI; 131 g of MP/kg DM; 2,685 g of MP/d) level of estimated MP. To control the potential confounding effect of Met and Lys supply, diets were formulated to supply an equal amount at 1.24 and 3.84 g/Mcal of ME in both prepartum diets and 1.15 and 3.16 g/Mcal of ME in both postpartum diets, respectively. The combination of a pre- and postpartum diet resulted in 4 treatment groups: (1) CON-CON (CC; n = 23), (2) CON-HI (CH; n = 24), (3) HI-CON (HC; n = 22), and (4) HI-HI (HH; n = 23). A common lactation diet (113 g of MP/kg DM; 2,956 g of MP/d) was fed from 22 DIM to the end of the observation period at 42 DIM. Transcutaneous ultrasonography was used to determine the longissimus dorsi muscle diameter and backfat thickness. Concentrations of plasma AA, 3-methylhistidine (3MH), and creatinine were determined on a subset of cows (n = 60) using ultra-high-performance liquid chromatography and MS. Treatment did not affect the longissimus dorsi muscle diameter from −14 to 21 d relative to calving, but the diameter was greater in CH compared with HH at 40 DIM. Backfat thickness and the ratio of 3MH to creatinine did not differ by treatment. Concentrations of EAA were greater at −13 d relative to calving in HH compared with CC and CH and at −6 d relative to calving EAA concentrations were higher in HC compared with CC. Cows fed the HI diet postpartum had elevated EAA concentrations at 6 and 20 DIM compared with cows fed the CON postpartum diet but EAA concentration did not differ at 40 DIM. Total NEAA concentrations were higher in CH compared with HC and HH at −6 d relative to calving, but NEAA concentration did not differ by treatment at −13, 6, 20, or 40 d relative to calving. In conclusion, increasing the supply of MP fed prepartum, postpartum, or both had minimal effects on tissue mobilization but influenced concentrations of plasma AA. [ABSTRACT FROM AUTHOR]

Objective: This study aims to delineate the clinical profiles of the hereditary transthyretin amyloid polyneuropathy (ATTRv-PN) patients with A97S variant from southern China and the molecular characteristics of this mutant protein. Methods: Fifteen ATTRv-PN patients with heterozygous A97S and one patient with homozygous A97S were included in the study. Serum TTR tetramer concentration was quantified through ultra-performance liquid chromatography. Stabilities of A97S-TTR were assessed through in vitro urea-mediated tryptophan fluorescence experiments, and nephelometry was employed in drug response assessment. Results: All patients were late-onset (≥50 years) with a mean age of onset at 59.26 ± 5.06 years old. Patients displayed a mixed phenotype featuring sensory-motor neuropathy with autonomic dysfunction and cardiac involvement, such as palpitations and chest pain. Electrophysiological studies showed generally axonal impairment of sensory and motor nerves. Tafamidis-treated patients showed significantly higher TTR tetramer concentrations, approaching healthy controls' levels. In vitro assessment showed that A97S-TTR was more kinetically stable than the V122I-TTR, and tetramer stabilisers inhibited A97S-TTR amyloid formation by more than 70%. Conclusion: This study provides valuable insights into the clinical and molecular characteristics of ATTRv-PN patients with A97S from South China, particularly regarding the differences in disease progression and stability features. [ABSTRACT FROM AUTHOR]

Gnaphalium affine is a plant with various active properties and has been approved for use as a traditional medicine and food ingredient. In this study, liquid chromatography with electrochemical detection was utilized to separate the antioxidant compounds of G. affine, in conjunction with liquid chromatography-triple quadrupole mass spectrometry for identification. The in vitro antioxidant activity of G. affine was evaluated using DPPH and ABTS radical scavenging capacity assays, as well as the ferric reducing antioxidant power assay. The results showed that a total of 25 antioxidant compounds were screened and identified, among which 14 compounds were quantitatively analyzed. G. affine was found to be rich in phenolic substances, with the total phenolic content ranging from 14.62 to 59.30 mg GAE/g DW, which exhibited high antioxidant potential. The antioxidant activities showed a strong positive correlation with the total phenolic content (r > 0.9). The predominant phenolic compounds in G. affine were 5-O-caffeoylquinic acid, 3-O-caffeoylquinic acid, ferulic acid, luteolin-7-O-glucoside, 3,5-O-dicaffeoylquinic acid, 1,5-O-dicaffeoylquinic acid, and luteolin, with 3,5-O-dicaffeoylquinic acid and 1,5-O-dicaffeoylquinic acid exhibiting the highest levels. Statistical analysis indicated that monosubstituted caffeoylquinic acids, disubstituted caffeoylquinic acids, and luteolin derivatives strongly correlated with the antioxidant potential. This study identified and quantified the major chemical constituents responsible for the antioxidant properties of G. affine, demonstrating its potential as a natural source of antioxidants for the use in foods, pharmaceuticals, and health products. [ABSTRACT FROM AUTHOR]

Introduction: Acute lymphoblastic leukaemia (ALL) is the most common type of childhood leukaemia with effective chemotherapeutic treatment. However, obesity has been associated with higher ALL chemoresistance rates and lower event‐free survival rates. The molecular mechanism of how obesity promotes chemotherapy resistance is not well delineated. Objectives: This study evaluated the effect of adipocyte maturation on sequestration and metabolism of chemotherapeutic drug daunorubicin (DNR). Methods: Using targeted LC‐MS/MS multi‐analyte assay, DNR sequestration and metabolism were studied in human preadipocyte and adipocyte cell lines, where expressions of DNR‐metabolizing enzymes aldo‐keto reductases (AKR) and carbonyl reductases (CBR) were also evaluated. In addition, to identify the most DNR‐metabolizing AKR/CBR isoforms, recombinant human AKR and CBR enzymes were subject to DNR metabolism. The results were further validated by AKR‐, CBR‐specific inhibitors. Results: This report shows that adipocyte maturation upregulates expressions of AKR and CBR enzymes (by 4‐ to 60‐ folds, p <.05), which is positively associated with enhanced sequestration and metabolism of DNR in adipocytes compared to preadipocytes (by ~30%, p <.05). In particular, adipocyte maturation upregulates AKR1C3 and CBR1, which are the predominate metabolic enzyme isoforms responsible for DNR biotransformation to its metabolites. Conclusion: Fat is an expandable tissue that can sequester and detoxify DNR when stimulated by obesity, likely through the upregulation of DNR‐metabolizing enzymes AKR1C3 and CBR1. Our data partially explains why obese ALL patients may be more likely to become chemoresistant towards DNR, and provides evidence for potential clinical investigation targeting obesity to reduce DNR chemoresistance. [ABSTRACT FROM AUTHOR]

Summary: Neltuma ruscifolia, a neglected underutilised species (NUS) within the Fabaceae family, lacks formal commercial recognition, despite its nutritional richness and endemic status. The objective of this study was to evaluate the antioxidant and antiglycating properties, as well as to identify associated bioactive compounds, in extracts (ultrasound and agitation) of different grinding fractions of N. ruscifolia seeds. Bioactivity varied depending on the extraction procedure and milling fraction, with the highest value in ultrasound‐extracted residue (exocarp, mesocarp). Some additional polyphenolic compounds (like hydroxybenzoic/ellagic acids) only appeared upon ultrasound‐assisted extraction. It was possible to identify some polyphenols (such as chrysin, rutin, kaempferol and cinnamic, coumaric, protocatechuic, ellagic and caffeic acids) that were highly related to the bioactivity. The antioxidant, antiglycating, colourant and technological properties of the extracts different fractions of N. ruscifolia pods are mainly dependent on the selected milling fraction. The extraction method, in a second place, significantly affects the resulting quantity and the type of extracted compounds, defining their potential applications. [ABSTRACT FROM AUTHOR]

Retention prediction through Artificial intelligence (AI)-based techniques has gained exponential growth due to their abilities to process complex sets of data and ease the crucial task of identification and separation of compounds in most employed chromatographic techniques. Numerous approaches were reported for retention prediction in different chromatographic techniques, and consistent results demonstrated that the accuracy and effectiveness of deep learning models outclassed the linear machine learning models, mainly in liquid and gas chromatography, as ML algorithms use fewer complex data to train and predict information. Support Vector machine-based neural networks were found to be most utilized for the prediction of retention factors of different compounds in thin-layer chromatography. Cheminformatics, chemometrics, and hybrid approaches were also employed for the modeling and were more reliable in retention prediction over conventional models. Quantitative Structure Retention Relationship (QSRR) was also a potential method for predicting retention in different chromatographic techniques and determining the separation method for analytes. These techniques demonstrated the aids of incorporating QSRR with AI-driven techniques acquiring more precise retention predictions. This review aims at recent exploration of different AI-driven approaches employed for retention prediction in different chromatographic techniques, and due to the lack of summarized literature, it also aims at providing a comprehensive literature that will be highly useful for the society of scientists exploring the field of AI in analytical chemistry. [ABSTRACT FROM AUTHOR]

Polyether antibiotics (PAs) are the anti-coccidiosis drugs used for treating and preventing coccidiosis. Studies show the residues of these antibiotics in food cause adversities and threaten human health. PAs thus need robust, rugged, and accurate methods for their analysis. This review encompasses pretreatment and detection methods of PAs in diverse matrices since 2010. Both conventional and developed methods are part of the pretreatments, such as dispersive liquid-liquid microextraction, solid-phase extraction, solid-phase microextraction, solvent front position extraction, QuEChERS (Quick Easy Cheap Effective Rugged and Safe), supercritical fluid extraction, and others. The analysis methods involve liquid chromatography coupled with detectors, sensors, etc. The pros and cons of various techniques for PAs have been discussed and future tendencies are proposed. HIGHLIGHTS: Progress of pretreatment and analytical methods for PAs are summarized. Comparisons between different mass analyzers are discussed in detail. Novel materials in microextraction methods are depicted. [ABSTRACT FROM AUTHOR]

Chiral separation techniques play a crucial role in the pharmaceutical industry, where the enantiomeric purity of drugs can have a significant impact on their efficacy and safety. Macrocyclic antibiotics are highly effective chiral selectors used in various chiral separation techniques, including LC, HPLC, SMB, and TLC, offering reproducible results and a wide range of applications. However, developing robust and efficient immobilization mechanisms for these chiral selectors remains a challenge. This review article focuses on various immobilization approaches, such as immobilization, coating, encapsulation, and photosynthesis, that have been applied to immobilize macrocyclic antibiotics on their support. Commercially available macrocyclic antibiotics for conventional liquid chromatography include Vancomycin, Norvancomycin, Eremomycin, Teicoplanin, Ristocetin A, Rifamycin, Avoparcin, Bacitracin, and others. In addition, capillary (nano) liquid chromatography has also been used in chiral separation utilizing Vancomycin, Polymyxin B, Daptomycin, and Colistin Sulfate. Macrocyclic antibiotic-based CSPs have been extensively applied due to their reproducible results, ease of use, and broad range of applications, capable of separating a large number of racemates. [ABSTRACT FROM AUTHOR]

Chlorination of seawater forms a range of secondary oxidative species – collectively called "chlorine-produced oxidants" (CPOs) – having different biocidal, environmental and ecotoxicological properties. The chemical speciation of these compounds is an important step in attempts to assess the effectiveness of chlorination and the potential impacts of its releases. However, comprehensive determination of CPOs represents a significant analytical challenge for many reasons, including the following: CPO species are numerous, highly reactive, with short-lifetimes, difficult to isolate and generally present at low concentrations in a complex salt matrix. Literature review reveals the development of a wide variety of analytical approaches for analysis of CPOs, either collectively via group parameters or individually. A first category of these approaches was the subject of article II (also including sampling and sample preparation) of a trilogy devoted to the chemical speciation of CPOs in seawater. In this third article – which closes the trilogy – emphasis is placed on chromatographic- and mass spectrometric-based approaches. It reviews more than 80 methods, reported from 1981 to date, and thoroughly discusses their principles and performances. Methodologies involving chemical derivatization of CPOs prior to their analysis by gas or liquid chromatography coupled to mass spectrometry provide the best sensitivities, achieving sub-ppb detection limits for species for which suitable derivatization reagents are available. Online mass spectrometry approaches are attracting increasing interest for their ability to analyze multiple CPO species in real time without extensive sample preparation steps, reaching detection limits of about ppb for less polar oxidants. At the current state of metrological development, neither the methodologies based on chromatography nor those based on online mass spectrometry allow complete speciation of CPOs. Future trends and major challenges related to these approaches are discussed. [ABSTRACT FROM AUTHOR]

In the present review article, different advanced liquid chromatographic techniques and the advanced techniques other than liquid chromatography that are used to estimate the pesticide residues from different plant-based samples are presented. In the beginning of the article, details of pesticides, their health effects and various cell lines used for the related study has been outlined. Afterward, detailed descriptions regarding pesticides classification are inscribed. In the end, recent advancements in the area of analysis of pesticides for herbal drugs are explained. Solid phase micro extraction (SPME) and solid-phase extraction (SPE) are considered as most common method of sample preparation for pesticides and its residual analysis. The most commonly used analytical separation technique for pesticide analysis is liquid chromatography (LC) integrated with mass spectrometry (MS) and MS/MS as Triple Quadrupole Mass Spectrometer (QqQ) for the samples analysis where high level of sensitivity and accuracy is required in quantification. [ABSTRACT FROM AUTHOR]

Breast cancer stem cells (CSC), as a kind of tumor cells, are able to regenerate themselves, leading to apoptosis resistance and cancer relapse. In this study, we investigated the potential of Hyptis Capitata and Hyptis Brevipes compounds in preventing apoptosis resistance and inducing targeted cell cycle arrest in CSC. The cytotoxic effects of the compounds were evaluated using 3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide (MTT) assay and the cell cycle distribution and apoptosis induction were assessed through flow cytometry analysis. The phytochemical characterization of Hyptis bravipes extract (HBE) and Hyptis capitata extract (HCE) conducted under thin layer chromatography (TLC) and highperformance liquid chromatography (HPLC) analysis. The results revealed that Hyptis Brevipes extract (HBE) exhibited strong cytotoxicity towards CSCs, with an IC50 value of 89 µg/mL. In contrast, Hyptis Capitata extract (HCE) showed weak growth inhibition, with an IC50 value greater than 500 µg/mL. Subsequent analysis demonstrated that HBE induced cell cycle arrest in the G2/M and S phases and significantly increased apoptosis in the CSC population. Furthermore, phytochemical characterization using TLC and HPLC revealed that HBE and HCE share similar constituent compounds, with HBE exhibiting a more diverse compound content and stronger cytotoxic effects. These findings provide valuable insights into the potential of Hyptis Capitata and Hyptis Brevipes compounds as targeted agents against breast cancer stem cells and contribute to understanding their chemical profiles and pharmacological properties. [ABSTRACT FROM AUTHOR]

Background: Formaldehyde is a common cause of contact allergy. Hidden formaldehyde, that is, formaldehyde in products without formaldehyde releasers, has previously been detected in cosmetic products. Objectives: The objective of this study was to investigate the content and causes of hidden formaldehyde in leave‐on cosmetic products. Methods: The formaldehyde release from 142 cosmetic products, primarily creams, was analysed using the chromotropic acid (CA) method. The study included 130 products with no formaldehyde releasers on the ingredient list and 12 products with formaldehyde releasers. Products without formaldehyde releasers positive to CA, that is, with formaldehyde ≥2.5 ppm, were additionally analysed using high‐performance liquid chromatography (HPLC). Formaldehyde release from selected raw materials and packaging were also investigated. Results: Hidden formaldehyde was found in 23 of the 130 products (18%) without formaldehyde releasers on the ingredient list. The average formaldehyde content was 105 ppm (range: 0.5–507 ppm) in products with hidden formaldehyde and 355 ppm (range: 75–637 ppm) in eight products with formaldehyde releasers, selected for HPLC analysis. Impurities of formaldehyde in dihydroxyacetone may be a cause of hidden formaldehyde in self‐tanners. No clear pattern was found for the other products with hidden formaldehyde. Conclusions: Changes in regulation are needed to prevent allergic contact dermatitis from hidden formaldehyde in cosmetic products. [ABSTRACT FROM AUTHOR]

A highly efficient method for the detection and quantification of 55 veterinary antibiotics (VAs) in chicken manure belonging to six drug classes using solid-phase extraction (SPE) and ultrahigh-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) was developed. The mixture of EDTA–McIlvaine buffer (pH 3.0) and the organic extractant (methanol–acetonitrile, 1:3, v/v) was used to isolate the target VAs from freeze-dried chicken manure. The extract was purified by a hydrophile–lipophile balance cartridge. All antibiotics showed excellent linear relationships in the range between 1 and 100 µg/kg with the coefficients of determination of the standard curves above 0.990. The recoveries of antibiotics were between 35.66% and 103.54% using matrix-matched calibration for quantification. The limits of detection and quantification were from 0.01 to 1.59 µg/kg and 0.04 to 4.76 µg/kg, respectively. The method was demployed to determine VAs in chicken manure from 12 farms, revealing contamination in all samples. A total of 13 VAs belonging to six classes were detected with concentrations up to 41.47 mg/kg. The presence of high concentrations of antibiotic residues in poultry manure poses a potential risk for environmental contamination. This work has identified significant differences in the types of VAs compared to literature reports. Additionally, it detected pleuromutilin antibiotics in chicken manure for the first time. [ABSTRACT FROM AUTHOR]

Watermelon is a rich natural source of Citrulline, an amino acid with potential antioxidant and vasodilation effects in the human body. An efficient Microwave-assisted aqueous two-phase extraction (MA-ATPE) technique was developed to extract and enrich L-Citrulline from watermelon rind in a one-step procedure. The aqueous two-phase system (ATPS) consisted of the ionic liquid 1-Butyl-3-methylimidazolium bromide [C4mim] [Br], and the salt dipotassium hydrogen phosphate (K2HPO4) was used as the extracting solvent. MA-ATPE conditions, such as the compositions of ATPS, particle size, liquid-solid ratio, irradiation power, and extraction time were investigated. The results indicated that the optimal conditions were as follows: salt concentration 35%, ionic liquid concentration 1.6 M, particle sizes 60 mesh, irradiation power 300 W, and extraction time 10 min. Under the optimized conditions, the extraction yields of L-Citrulline reached 87.74%. According to the DPPH results, at a concentration of 2 mg/mL, the DPPH radical-scavenging activity of the MA-ATPE extract from watermelon rind (0.388 mg/ml) was greater than that of the MAE (Microwave-assisted extraction) extract (0.456 mg/ml) and the conventional extract (0.468 mg/ml). DLS and TEM were used together to examine the microstructure of the top phase and explore the potential extraction mechanism. The findings revealed that the aggregation and embrace phenomenon were the primary driving forces for the separation. Compared with the conventional method and regular MAE, MA-ATPE exhibited a higher extraction yield and a shorter extraction time. In conclusion, MA-ATPE is an efficient, rapid, eco-friendly, and economical technique, representing an excellent alternative for the extraction of bioactive compounds. [ABSTRACT FROM AUTHOR]

In this work, an aqueous two-phase system (ATPS) based on a green deep eutectic solvent (DES) and inorganic salt is presented and applied for the simultaneous determination of heterocyclic aromatic amines (HAAs) in the marinating juice via ultra performance liquid chromatography (UPLC). First, six different betaine-based DESs were prepared, and betaine/1,4-butanediol (Bet/Buta) was chosen as the suitable extractant for the ATPS. Their structures were confirmed via Fourier transform infrared (FT-IR) spectroscopy and proton nuclear magnetic resonance (1H-NMR) spectroscopy. Subsequently, the factors influencing the ATPS were systematically investigated, and the optimal extraction parameters were obtained with a trichloroacetic acid concentration of 5% (w/v), 0.2 g of Bet/Buta, 0.6 g of an inorganic salt (K2HPO4), an extraction time of 1 min and a centrifugation time of 2 min. Under optimal extraction conditions, good linearities were obtained, with the correlation coefficient (R) ≥ 0.9995. The inter- and intraday precisions were 2.4–4.9% and 2.9–5.3%, respectively. The recoveries for the targeted HAAs ranged between 91.6 and 111.9%. The limits of detection (LODs) of 5.0–14.6 ng/g were obtained. In contrast to the frequently used solid-phase extraction (SPE) technique, the developed DES‒ATPS method, which has higher accuracy and better precision, has advantages of simplicity, speed, good environmental friendliness and low cost per sample. Finally, it was utilized to determine the four selected HAAs in actual samples of marinating juice to evaluate its applicability. Analytical GREEnness metric (AGREE), a novel greenness assessment tool, was tested to verify that this work was a relatively green analytical procedure. These findings demonstrate that the green and efficient DES−ATPS composed of the Bet/Buta DES and K2HPO4 shows great potential for extracting and enriching HAAs or other harmful substances from liquid food in pilot or large-scale operations. [ABSTRACT FROM AUTHOR]

Coloring agents in foods and drinks have been popular for centuries. This study aims to analyze the presence of ten synthetic colors (namely, (allura red (E129), amaranth (E123), sunset yellow (E110), tetrazine (E102), fast green (E143), ponceau 4R (New Coccine) (E124), erythrosin B (E127), brilliant blue FCF (E133), brilliant black (E151) and carmoisine (E122))) in food and drink samples using ultra-high-performance liquid chromatography diode array detection (UHPLC-DAD). The present analytical method was carried out using Agilent Poroshell 120 HPH-C18 column, 3 × 100 mm, 2.7 µm, and a mobile phase consisting of 10 mM Na2HPO4, pH 7, mixed with methanol as a time-increment gradient solution until the time was 20 min, then decreased with time until the time was 26 min. The pH was set by orthophosphoric acid at 7 and 5 μL injection volume, 0.50 mL flow rate, and the elution systems were monitored at 428 nm for E102, 518 nm for E124, E110, E129, E122, 530 nm for E151, E127, 622 nm for E143, and E133, respectively. The limit of detection and quantification for all colors ranged from 0.017 to 0.025 and 0.057 and 0.082 mg L−1, respectively. The correlation coefficient values ranged between 0.9991 and 1.0. The selectivity of the assay revealed no interference from other components in the analyzed samples. The percent recovery and precision (intra- and inter-day) of the spiked samples were within the acceptable limits of the ICH guidelines. Five analytical parameters were employed, and the results showed a new, novel, and robust method according to ICH guidelines for analyzing these colors. While most of the investigated food and drinks fell within the accepted range, some fell outside. The current sample preparation and analytical methods are comprehensive and universal for extracting and measuring synthetic colors in various food and drink samples. [ABSTRACT FROM AUTHOR]

Context Serum thyroglobulin (Tg) measured by immunometric assay (IMA) is prone to underestimation due to Tg autoantibody (TgAb) interference, often prompting reflex Tg measurement by liquid chromatography/tandem mass spectrometry (MS) or radioimmunoassay (RIA). Objective IMA, MS, and RIA methodologies were used to measure serum Tg in TgAb-negative (TgAb−) and TgAb-positive (TgAb+) patients with either distant metastatic differentiated thyroid cancer (DTC) or hyperthyroidism (HY)—patients in whom a detectable serum Tg would be expected. Results When TgAb was absent , all methodologies detected Tg in the sera of all DTC and HY patients and reported appropriate Tg trends and treatment responses for DTC patients with progressive distant metastatic disease, albeit with high between-method variability (> 30% coefficient of variability). When TgAb was present , all methodologies reported lower serum Tg levels for both DTC and HY groups vs their respective TgAb− group. No Tg was detected by IMA or MS in ∼50% TgAb+ DTC patients (6% had no Tg detected by RIA). Surprisingly, 5% of TgAb+ HY patients also had no Tg detected by IMA or MS. The inverse log TgAb/log Tg correlations seen for the TgAb+ HY patient group with all methods suggested the presence of a TgAb-associated serum Tg-lowering effect. Conclusion (i) Between-method Tg variability necessitates method continuity when monitoring the Tg trends of TgAb− DTC patients. (ii) The presence and concentration of TgAb appeared to have a lowering effect on serum Tg measured by all methodologies (IMA, MS, and RIA). (iii) Since the reliability of Tg measured in the presence of TgAb is often uncertain, the TgAb trend (measured by the same method) may be a useful surrogate DTC tumor marker. [ABSTRACT FROM AUTHOR]

Advanced glycation end‐products (AGEs), formed endogenously or obtained exogenously from diet, may contribute to chronic inflammation, intracellular signaling alterations, and pathogenesis of several chronic diseases including colorectal cancer (CRC). However, the role of AGEs in CRC survival is less known. The associations of pre‐diagnostic circulating AGEs and their soluble receptor (sRAGE) with CRC‐specific and overall mortality were estimated using multivariable‐adjusted Cox proportional hazards regression among 1369 CRC cases in the European Prospective Investigation into Cancer and Nutrition (EPIC) study. Concentrations of major plasma AGEs, Nε‐[carboxy‐methyl]lysine (CML), Nε‐[carboxy‐ethyl]lysine (CEL) and Nδ‐[5‐hydro‐5‐methyl‐4‐imidazolon‐2‐yl]‐ornithine (MG‐H1), were measured using ultra‐performance liquid chromatography mass‐spectrometry. sRAGE was assessed by enzyme‐linked immunosorbent assay. Over a mean follow‐up period of 96 months, 693 deaths occurred of which 541 were due to CRC. Individual and combined AGEs were not statistically significantly associated with CRC‐specific or overall mortality. However, there was a possible interaction by sex for CEL (Pinteraction =.05). Participants with higher sRAGE had a higher risk of dying from CRC (HRQ5vs.Q1 = 1.67, 95% CI: 1.21–2.30, Ptrend =.02) or any cause (HRQ5vs.Q1 = 1.38, 95% CI: 1.05–1.83, Ptrend =.09). These associations tended to be stronger among cases with diabetes (Pinteraction =.03) and pre‐diabetes (Pinteraction <.01) before CRC diagnosis. Pre‐diagnostic AGEs were not associated with CRC‐specific and overall mortality in individuals with CRC. However, a positive association was observed for sRAGE. Our findings may stimulate further research on the role of AGEs and sRAGE in survival among cancer patients with special emphasis on potential effect modifications by sex and diabetes. [ABSTRACT FROM AUTHOR]

The synthesis of optically active compounds requires determination of ee, er, and enantiomeric purity. The aim of the present paper is to review the synthesis of several chiral derivatizing reagents (CDRs) in a rational manner, which were successful for the separation and isolation of enantiomers of a variety of active pharmaceutical ingredients and other important and useful racemates. Besides, the application of (i) certain enantiomerically pure amines, either directly or by incorporating each of them as chiral auxiliary in difluorodinitrobenzene or cyanuric chloride moieties to construct the CDR, (ii) (S)‐ketoprofen and (S)‐levofloxacin as chiral platforms, and (iii) a few isothiocyanates, have been suitably included. Attention is drawn to the use of water micellar mobile phase as the "green" RP‐HPLC method and the use of simple achiral derivatization with ninhydrin, particularly. Synthesis of CDRs and their application for enantioseparation of racemates and detagging of certain chromophoric reagent components for obtaining native enantiomers are other interesting features included herein. The methods can be easily used to determine and control enantiomeric purity with advantages over a variety of commercial chiral phases. This comprehensive review not only highlights innovative methodologies for enantioseparation but also underscores their practical applications in controlling and ensuring the enantiomeric purity of pharmaceutical compounds. [ABSTRACT FROM AUTHOR]

Six polysaccharide‐based chiral stationary phases were screened to separate the enantiomers of six chloro‐containing derivatives and one derivative bearing electron donating mesomeric substituents, chosen for comparison. These compounds are expected to be P2X7 receptor antagonists with potential anti‐inflammatory activity. The study was carried out with four different mobile phases composed of n‐heptane and ethanol or isopropanol. Thus, a total of 168 experiments were implemented to find the best conditions aimed at scaling‐up the separation of these anti‐inflammatory compounds. Chiralpak AD‐H separated half of them, i.e., 1, 2, and 6; Chiralpak AS separated also three out of the six compounds, i.e., 1, 2, and 3; Lux Cellulose‐5 separated 2, 4, and 6; Lux Cellulose‐2 separated 1, 2, and 4; Chiralcel OD‐H separated compounds 2 and 5; and finally Chiralcel OJ separated only 3, thus having the lowest rate of success. Additionally, the influence of (i) the stationary and mobile phases and (ii) the chemical structure of the analytes on retention and resolution was investigated. [ABSTRACT FROM AUTHOR]

Background: The increasing diversity of psychoactive substances on the unregulated drug market poses significant health, psychological, and social risks to people who use drugs (PWUD). To address these risks, various harm reduction (HR) policies have been implemented, including drug checking services (DCS). Many analytical methods are used for DCS. While qualitative methods (e.g., thin layer chromatography, spectroscopy) are easier to implement, they are not as accurate as quantitative methods (e.g., LC-UV, LC-MS). Some HR programmes have implemented high-performance liquid chromatography coupled with UV detection (LC-UV). This article presents the cross-validation of this quantitative method with a reference liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) method. Methods: Drug samples were provided by PWUD to a DCS called DrugLab in Marseille, France. The samples were weighed and prepared through dissolution in methanol, followed by ultrasonic bathing. Samples were analysed onsite using LC-UV analysis. They were then subsequently analysed with the reference LC-HRMS method. The LC-UV instrument in DrugLab was calibrated after being purchased; analysis of standard solutions was routinely performed once a month and after maintenance operations. For the LC-HRMS instrument, calibration and quality control procedures followed European Medicines Agency (EMA) guidelines. Statistical analyses were conducted including Spearman correlation tests using IBM® SPSS® Statistics version 20. Results: A total of 102 samples representing different product classes and cutting agents were cross-validated. Differences between both analyses methods for each molecule analysed were ≤ 20%, with significant correlations between both methods' results for most substances. Notably, LC-HRMS provided lower concentration values for cocaine and acetaminophen, whereas it provided higher values for other substances. Correlations were significant for cocaine, ketamine, MDMA, heroin, amphetamine, caffeine, acetaminophen, and levamisole. Conclusions: This study demonstrates that the results provided by DrugLab were accurate and reliable, making LC-UV an adaptable, stable, and suitable analytical method for simple matrices like drugs in a DCS context. However, this cross validation does not guarantee accuracy over time. A proficiency test project in HR laboratories across France is currently under development in order to address potential drifts in LC-UV accuracy. [ABSTRACT FROM AUTHOR]

ABSTRACT The analytical findings concerning the red pigments used on various decorative features originating from a Macedonian, as well as the purple dye from the deceased's attire, are presented. The cist tomb, discovered in 1987 at the area of Lakkoma Chalcidice (Macedonia, Greece), dated to the 4th century bc and featured a wooden funeral couch with intricate ornaments, such as clay “eyes,” colored plaster, and clay gorgoneions. Vermilion and red ochre served as the main pigments of these decorative features. The pigments were applied in various combinations to produce a range of red hues, from deep to bright red. Furthermore, the precious vermilion was also used in every element of the couch. The stucco on the decoration was gypsum, whereas the preparation layers over clay and stucco elements consisted of calcite and lead white, respectively. The cloth covering the deceased was dyed with the most expensive organic dye of antiquity, the Tyrian (shellfish) purple. In this research, the preliminary identification of the chromophoric minerals in the colors of the samples was carried out with the examination of their optical characteristics in thin sections using polarizing light microscope (PLM) and with portable XRF. Physicochemical techniques, Raman and HPLC, were also used to definitively identify the pigments. Portable Raman spectrometer was used for the in situ analysis of the inorganic colorants of the decorative materials, whereas laboratory Raman spectrometer served for the identification of inorganic and organic colorants of the grain samples and the dye. High‐pressure liquid chromatography with diode array detector (HPLC‐DAD) was applied for the identification of the coloring components of the purple organic dye from the deceased's clothes. The samples examined (0.5‐ to 1.5‐mm diameter) were collected during the initial cleaning of the surface. [ABSTRACT FROM AUTHOR]

Background: Ponatinib, a third-generation tyrosine kinase inhibitor, is employed in the management of adult chronic myeloid leukemia. Nevertheless, the presence of process impurities and degradation impurities linked to ponatinib may potentially influence its effectiveness and safety. Therefore, the objective of this research was to establish a robust liquid chromatography method and systematically validate it for the detection of substances related to ponatinib. Methods: The separation of ponatinib and its impurities was conducted using an Agilent 5HC-C18 chromatographic column (4.6 mm × 250 mm, 5 μm). The mobile phase A comprised a mixture of water and acetonitrile in a 9:1 ratio, with an aqueous solution of pH 2.4 containing 2 mM potassium dihydrogen phosphate and 0.4% triethylamine. Mobile phase B, consisting of acetonitrile, was eluted in a gradient fashion. The flow rate was set at 1.0 mL/min, detection wavelength at 250 nm, column temperature at 40°C, and injection volume at 10 μL. Results: The method demonstrated high specificity, sensitivity, solution stability, linearity, precision, accuracy, and robustness. Additionally, this research unveiled a novel compound, imp-B, generated via the oxidative degradation of ponatinib. The molecular structure of the newly discovered product was elucidated through the utilization of nuclear magnetic resonance (NMR) and high-resolution mass spectrometry (HRMS). Conclusion: In conclusion, the chromatographic method developed in this study has the potential to be utilized for the detection of ponatinib and its impurities, thereby offering significant insights for quality assessment in ponatinib research. [ABSTRACT FROM AUTHOR]

Fluorinated organic compounds (FOCs) represent a class of synthetic chemicals distinguished by their resilient carbon–fluorine bonds, which demonstrate an ability to withstand environmental degradation over an extended period. The integration of FOCs into cutting-edge applications, including lithium-ion batteries (LiBs), presents considerable potential for environmental harm that has not yet been sufficiently addressed. This study focuses on the environmental fate of two fluorinated aromatics, tris(pentafluorophenyl)borane (TPFPB) and tris(pentafluorophenyl)phosphine (TPFPP), given their important role in improving the performance of LiBs. To achieve this, laboratory simulation methods including total oxidizable precursor assay, electrochemistry (EC), Fenton reaction, UV-C irradiation, and hydrolysis were employed. Liquid chromatography and gas chromatography coupled with high-resolution mass spectrometry were used for identification of transformation products (TPs) and prediction of their molecular formulae. Despite the structural similarity between TPFPB and TPFPP, distinct differences in electrochemical behavior and degradation pathways were observed. TPFPB readily underwent hydroxylation and hydrolysis, resulting in a wide range of 49 TPs. A total of 28 TPs were newly identified, including oligomers and highly toxic dioxins. In contrast, TPFPP degraded exclusively under harsh conditions, requiring the development of innovative conditioning protocols for EC. In total, the simulation experiments yielded nine structurally different compounds, including seven previously undescribed, partially defluorinated TPs. This study highlights the potential risks associated with the use of FOCs in LiBs and provides insight into the complex environmental behavior of FOCs. [ABSTRACT FROM AUTHOR]

Pharmaceuticals released into the aquatic and soil environments can be absorbed by plants and soil organisms, potentially leading to the formation of unknown metabolites that may negatively affect these organisms or contaminate the food chain. The aim of this study was to identify pharmaceutical metabolites through a triplet approach for metabolite structure prediction (software-based predictions, literature review, and known common metabolic pathways), followed by generating in silico mass spectral libraries and applying various mass spectrometry modes for untargeted LC-qTOF analysis. Therefore, Eisenia fetida and Lactuca sativa were exposed to a pharmaceutical mixture (atenolol, enrofloxacin, erythromycin, ketoprofen, sulfametoxazole, tetracycline) under hydroponic and soil conditions at environmentally relevant concentrations. Samples collected at different time points were extracted using QuEChERS and analyzed with LC-qTOF in data-dependent (DDA) and data-independent (DIA) acquisition modes, applying both positive and negative electrospray ionization. The triplet approach for metabolite structure prediction yielded a total of 3762 pharmaceutical metabolites, and an in silico mass spectral library was created based on these predicted metabolites. This approach resulted in the identification of 26 statistically significant metabolites (p < 0.05), with DDA + and DDA − outperforming DIA modes by successfully detecting 56/67 sample type:metabolite combinations. Lettuce roots had the highest metabolite count (26), followed by leaves (6) and earthworms (2). Despite the lower metabolite count, earthworms showed the highest peak intensities, closely followed by roots, with leaves displaying the lowest intensities. Common metabolic reactions observed included hydroxylation, decarboxylation, acetylation, and glucosidation, with ketoprofen-related metabolites being the most prevalent, totaling 12 distinct metabolites. In conclusion, we developed a high-throughput workflow combining open-source software with LC-HRMS for identifying unknown metabolites across various sample types. [ABSTRACT FROM AUTHOR]

Chiral separation plays a pivotal role in both practical applications and industrial productions. However, traditional chiral stationary phases (CSPs) exhibit inherent instability in alkaline environments, presenting a significant challenge despite their importance. Herein, basophilic alcalase is creatively developed to fabricate ultrastable protein‐based CSPs that can efficiently work under alkaline conditions. An in‐depth theoretical simulation is conducted to unveil the unique three‐dimensional conformation of alcalase, showing selective affinity towards various enantiomers of chiral amino acids and drugs, especially acidic substrates. Subsequently, an in situ assembly strategy is used to immobilize alcalase within a hydrazone‐linked covalent organic framework (COF) platform. The generated protein‐based CSPs enable successful baseline separation (Rs≥1.50) for various value‐added compounds (e.g., non‐steroidal drug, RS‐flurbiprofen; nucleotide analog, RS‐tenofovir) via high‐performance liquid chromatography, surpassing the commercial chiral column. Furthermore, a systematic study reveals that increasing hydrophilicity and pore sizes of COFs can enhance the separation performance. Remarkably, the obtained CSPs demonstrated exceptional durability, maintaining performance for >2,400 runs. This study provides a new member to the protein library for CSPs, and represents an innovative and effective platform for CSPs with immense potential for the enantioseparation of acidic drugs. [ABSTRACT FROM AUTHOR]

Yiyi decoction is a Chinese herbal formula for the treatment of acute pancreatitis that has been used in clinical practice for decades. A previous study has suggested that resveratrol, emodin, rhein and their derivatives might be the potential pharmacodynamic components in Yiyi decoction, and researchers have proposed that resveratrol, emodin and rhein are candidate markers for quality control. The present study investigated the intervention effect of Yiyi decoction and its effective components on murine acute pancreatitis using metabolomic approach that integrated global and unique metabolic characteristics. First, serum metabolomics based on the platform of ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry was performed to assess metabolic changes in experimental acute pancreatitis. Second, an in-depth analysis of bile acid metabolism was performed based on an in-house database. Finally, an integrated analysis of the intervention effect of Yiyi decoction and its effective components in response to these metabolic perturbations was performed. As a result, 39 potential biomarkers for the pathogenesis of acute pancreatitis, mainly phospholipids, fatty acids, bile acids and lipoylcarnitines, were screened and annotated. Integrated analysis revealed that the metabolic disorders in acute pancreatitis mice were reversed by Yiyi decoction primarily via regulating glycerophospholipid metabolism, bile acid biosynthesis, carnitine synthesis and fatty acid metabolism. Yiyi decoction components may effectively target the migratory metabolome. Histopathological and biochemical analyses suggested that Yiyi decoction maintained the gut barrier function and inhibited inflammatory cytokines, thus exert anti-acute pancreatitis effects. The present study utilized an approach that integrated global and unique metabolic characteristics to elucidate the underlying mechanisms of Chinese herbal formulas from a metabolomics perspective. [ABSTRACT FROM AUTHOR]

Objective: Taste is one of the vital indicators for the quality evaluation of Coptis rhizome (CR), but the traditional taste evaluation lacks objectivity. By establishing the correlation between CR's tastes and alkaloids, an objective basis for the taste evaluation was established. Methods: Ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometry (UHPLC-QQQ-MS/MS) and electronic tongue technique were performed to determine ten alkaloid contents and eight tastes from Coptis chinensis rhizome, Coptis deltoidea rhizome, Coptis teeta rhizome, and Coptis japonica rhizome, respectively. Combined with multivariate statistical analysis, we established models to discriminate the alkaloid contents and tastes of CR, screened the differential alkaloids and tastes, and performed Pearson's correlation analysis on the results of alkaloids and tastes. Results: 1) According to the previous UHPLC-QQQ-MS/MS method established by our research group, the contents of ten alkaloids of the four species of CR were quantified, of which jatrorrhizine, columbamine, and magnoflorine were the differential alkaloids of the four species. 2) The electronic tongue technique realized the objectification of CR's tastes and distinguished the species of CR based on the tastes of aftertaste-A, sourness, bitterness, and richness. 3) Pearson's correlation analysis shows the bitterness of CR was mainly manifested as aftertaste-B, indicating the higher the aftertaste-B value, the higher the berberrubine content. Astringency and aftertaste-A could be suggested as quality evaluation indexes of CR, due to the positively correlated or significantly positively correlated with coptisine, epiberberine, berberine, and palmatine, respectively. Conclusion: Electronic tongue technique has successfully achieved the objectification of the tastes of CR, and combined with UHPLC-QQQ-MS/MS technique for alkaloid quantification and correlation research, it provides a new idea for the quality evaluation of CR. [ABSTRACT FROM AUTHOR]

Mexico is considered one of the countries with the greatest diversity of the Salvia genus. A significant percentage of its species are known for their use in traditional medicine, highlighting their use as an analgesic. The objective of this work was to determine the chemical composition of the methanolic extracts of S. cinnabarina, S. lavanduloides and S. longispicata through untargeted metabolomics, as well as the in vivo evaluation of the antinociceptive effect and acute oral toxicity. The chemical profiling was performed using ultra-high performance liquid chromatography coupled with a high-resolution mass spectrometry (UPLC-ESI+/−-MS-QTOF) system and tentative identifications were performed using a compendium of information on compounds previously isolated from Mexican species of the genus. Pharmacological evaluation was carried out using the formalin test and OECD guidelines. The analysis of the spectrometric features of the mass/charge ratios of the three salvias shows that a low percentage of similarity is shared between them. Likewise, the putative identification allowed the annotation of 46 compounds, mainly of diterpene and phenolic nature, with only four compounds shared between the three species. Additionally, the extracts of the three salvias produced a significant antinociceptive effect at a dose of 300 mg/kg administered orally and did not present an acute oral toxicity effect at the maximum dose tested, indicating a parameter of LD50 > 2000 mg/kg. The exploration of the chemical profile of the three salvias by untargeted metabolomics shows that, despite being species with antinociceptive potential, they have different chemical profiles and therefore different active metabolites. [ABSTRACT FROM AUTHOR]

Sorghum is a significant source of polyphenols, whose content, antioxidant properties and bioaccessibility may be modulated by digestion. Studies have reported sorghum polyphenol changes after simulated digestion. However, the effects of simulated digestion on processed, pigmented sorghum are unknown. This study investigated the bioaccessibility and bioavailability of black (BlackSs and BlackSb), red (RedBa1, RedBu1, RedBa2, RedBu2) and white (WhiteLi2 and White Li2) sorghum samples using a Caco-2 in vitro model. Ultra high performance liquid chromatography—online 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (UHPLC–online ABTS)—and quadrupole time-of-flight liquid chromatography mass spectra (QTOF LC–MS) facilitated the identification of digested and transported compounds. Simulated digestion showed increased bioaccessibility and total phenolic content (TPC) for BlackSs by 2-fold. BlackSs and BlackSb exhibited high antioxidant capacities, with variations dependent on processing in other varieties. Kaempferol-3-O-xyloside exhibited a 4-fold increase in TPC following digestion of processed BlackSs and BlackSb but was absent in the others. BlackSs, BlackSb, and RedBu1 revealed twelve bioaccessible and Caco-2 transported compounds not previously reported in sorghum, including trans-pinostilbene, tryptophan and maackin a. This study demonstrates that in vitro digestion increases the bioaccessiblity of sorghum polyphenols through the process of cellular biotransformation, possibly improving transport and bioactivity in vivo. [ABSTRACT FROM AUTHOR]

In neuroscience research, chiral metabolomics is an emerging field, in which D-amino acids play an important role as potential biomarkers for neurological diseases. The targeted chiral analysis of the brain metabolome, employing liquid chromatography (LC) coupled to mass spectrometry (MS), is a pivotal approach for the identification of biomarkers for neurological diseases. This review provides an overview of D-amino acids in neurological diseases and of the state-of-the-art strategies for the enantioselective analysis of chiral amino acids (AAs) in biological samples to investigate their putative role as biomarkers for neurological diseases. Fluctuations in D-amino acids (D-AAs) levels can be related to the pathology of neurological diseases, for example, through their role in the modulation of N-methyl-D-aspartate receptors and neurotransmission. Because of the trace presence of these biomolecules in mammals and the complex nature of biological matrices, highly sensitive and selective analytical methods are essential. Derivatization strategies with chiral reagents are highlighted as critical tools for enhancing detection capabilities. The latest advances in chiral derivatization reactions, coupled to LC-MS/MS analysis, have improved the enantioselective quantification of these AAs and allow the separation of several chiral metabolites in a single analytical run. The enhanced performances of these methods can provide an accurate correlation between specific D-AA profiles and disease states, allowing for a better understanding of neurological diseases and drug effects on the brain. [ABSTRACT FROM AUTHOR]

Introduction: Hexahydrocannabinol or HHC has recently appeared on the Internet and in cannabidiol (CBD) stores in various forms. Although the abuse and dependence potential of HHC consumption has not yet been established, HHC has been reported by consumers to have effects similar to delta-9-tetrahydrocannabinol (THC) and has been classified as narcotics in France since June 12, 2023. Methods: We conducted a retrospective study of all cases of oral fluid samples collected from drivers by traffic police officers and sent to our laboratory to confirm the presence of illicit substances between June 12, 2023 and December 31, 2023. The presence of 33 psychoactive substances, including HHC, THC, and CBD, in the oral fluid samples was assessed by an ultra-high performance liquid chromatography system coupled to a triple quadrupole mass spectrometer. Results: Of the 867 oral fluid samples analyzed, 16 were positive for HHC and involved only male drivers aged between 19 and 58. The mean and median HHC concentrations found in oral fluid were 35 ± 69 ng/mL and 10 ng/mL, respectively. In these preliminary data, HHC was always associated with THC, but the THC/HHC and CBD/HHC ratios were very broad. Although the kinetics of HHC and THC in saliva are different, the 11 cases with the highest THC/HHC ratios (>300) support that impaired alertness in drivers may be mainly due to THC. In these 11 cases, a linear correlation was found between THC and HHC concentrations in oral fluid. Conclusion: Further large-scale studies are required to extend these preliminary data, but the emerging detection of HHC in oral fluid of drivers may illustrate its spreading use in the general population. [ABSTRACT FROM AUTHOR]

ABSTRACT Bioelectrochemical systems (BESs) offer a sustainable method for chemical production, including the enhanced production of succinic acid. By combining fermentation with BES, it could be possible to achieve sustainable succinic acid production and CO2 fixation using Actinobacillus succinogenes. In literature, the potential application of BES is commonly associated with increased succinate yields, as it is expected to enhance the availability of NADH, thereby influencing the intracellular nicotinamide adenine dinucleotide (NADH/NAD+) balance. However, it remains unclear whether BES can improve NADH regeneration and achieve higher NADH/NAD+ ratios across all growth phases of A. succinogenes. This study investigates the impact of an applied electrical potential on the intracellular NADH/NAD+ ratio during an electrochemical‐assisted fermentation process. Using an adapted high‐performance liquid chromatography method with a Supelcosil LC‐18‐T column, it was demonstrated that NADH availability in BES, particularly during the stationary growth phase, improved by up to 1.98‐fold compared to the control. This enhancement in reducing power led to a succinate yield of 0.747 ± 0.01 g g−1, representing a 15.65% increase compared to a fermentation without electrochemical assistance. These findings support the expectation that the use of BES could enhance the competitiveness of bio‐based succinate production. [ABSTRACT FROM AUTHOR]

So far, the metabolic differences between tree-ripened and postharvest-ripened mangoes have largely remained unexplored. The aim of this study was to evaluate the chemical composition of nutrient substances in mangoes subjected to different ripening methods. An untargeted metabolomic approach based on ultra performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) was carried out to investigate the differences between artificially ripened and naturally ripened mangoes. The principal component analysis results indicate a clear separation between the different treatment groups. Variance analysis, fold change, and orthogonal partial least squares discriminant analysis (OPLS-DA) were employed to find potential markers. In total, 69 metabolites were identified, with significant variations in the abundance of organic acids, vitamins, carbohydrates, and polyphenols closely related to the ripening methods of mangoes. These results contribute to a better understanding of the metabolic changes in mangoes due to different ripening methods, which could be used to assist in evaluating the quality of mango fruit. [ABSTRACT FROM AUTHOR]

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Withania somnifera (common name: ashwagandha; WS) is an Ayurvedic botanical that has become popular for its reputed effects on stress and insomnia. Research into the bioactive compounds responsible for the biological effects of WS has largely focused on withanolides, a group of steroidal lactones commonly found in the Solanaceae family. Until recently, however, it was unclear which, if any, withanolides were present in the plasma after the ingestion of WS products. The aim of this review is to summarize current knowledge regarding the plasma pharmacokinetics of withanolides found in WS and the analytical methods developed to detect them in plasma. Twenty studies (sixteen animal, four human) were identified in which isolated withanolides or withanolide-containing products were administered to animals or humans and quantified in plasma. Withanolides were commonly analyzed using reversed-phase liquid chromatography coupled to mass spectrometry. Plasma concentrations of withanolides varied significantly depending on the substance administered, withanolide dose, and route of administration. Plasma pharmacokinetics of withaferin A, withanolide A, withanolide B, withanoside IV, 12-deoxywithastramonolide, and withanone have been reported in rodents (Cmax range: 5.6–8410 ng/mL), while withaferin A, withanolide A, 12-deoxywithastramonolide, and withanoside IV pharmacokinetic parameters have been described in humans (Cmax range: 0.1–49.5 ng/mL). [ABSTRACT FROM AUTHOR]

In this work, the rapid and efficient preparation of isolated galloyl glucoside tautomer free radical inhibitors was investigated using Saxifraga tangutica as a raw material. Four highly polar galloyl glucoside tautomers, 3-O-galloyl-α-d-glucose ⇌ 3-O-galloyl-β-d-glucose (Fr2-1-1), 2-O-galloyl-α-d-glucose ⇌ 2-O-galloyl-β-d-glucose (Fr2-1-2/2-1-3), 1-O-galloyl-β-d-glucose (Fr2-2-1), and 6-O-galloyl-α-d-glucose ⇌ 6-O-galloyl-β-d-glucose (Fr2-3-1/Fr2-3-2), were obtained via two-step medium-pressure liquid chromatography (with solid loading instead of conventional liquid injection) and one-step high-performance chromatography coupled with on-line RPLC-DPPH techniques for targeted isolation. This separation integration technique not only increases sample intake and reduces time cost but also visualizes each step of targeted separation. All four compounds were isolated from the plant for the first time. In vitro antioxidant activity assays by DPPH (1,1‑diphenyl-2-picrylhydrazyl) revealed that Fr2-1-2/Fr2-1-3 (IC50: 5.52 ± 0.32 μM), Fr2-2-1 (IC50: 7.22 ± 0.57 μM), and Fr2-3–1/Fr2-3-2 (IC50: 7.36 ± 0.25 μM) had superior free radical scavenging abilities and that both were superior to that of quercetin (IC50: 18.61 ± 3.55 μM). Oxidative stress assays revealed that Fr2-1-2/Fr2-1-3 significantly inhibited oxidative stress damage in H2O2-induced HepG2 cells, decreased the level of ROS (P < 0.01) and protected hepatocytes. Combined with the current results, gallic acid showed greater antioxidant activity when H atoms were replaced at d-glucose –OH (C-2) than at the other three sites [–OH (C-1), –OH (C-6) and –OH (C-3)]. [ABSTRACT FROM AUTHOR]

BACKGROUND RESULTS CONCLUSION Radix Bupleuri has been widely used for its plentiful pharmacological effects. But it is hard to evaluate their safety and efficacy because the concentrations of components are tightly affected by the surrounding environment. Thus, Radix Bupleuri samples from different regions and varieties were collected. Based on the experimental and computational Raman spectrum, machine learning is emphasized for certain obscured characteristics; for example, linear discriminant analysis (LDA), support vector machine (SVM), eXtreme gradient boosting (XGBoost) and light gradient boosting machine (LightGBM).After dimension reduction by LDA, models of SVM, XGBoost and LightGBM were trained for classification and regression prediction of Bupleurum production regions. Support vector classifiers achieved the best accuracy of 98% and an F1 score above 0.96 on the test set. Support vector regression has a good fitting performance with an R2 score above 0.90 and a relatively low mean square error. However, complex models were prone to overfitting, resulting in poor generalization ability.Among these machine learning models, the typical LDA‐SVM models, consistent with the high‐performance liquid chromatography results, demonstrate great performance and stability. We envision that this rapid classification and regression technique can be extended to predictions for other herbs. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Mass spectrometry is broadly employed to study complex molecular mechanisms in various biological and environmental fields, enabling 'omics' research such as proteomics, metabolomics, and lipidomics. As study cohorts grow larger and more complex with dozens to hundreds of samples, the need for robust quality control (QC) measures through automated software tools becomes paramount to ensure the integrity, high quality, and validity of scientific conclusions from downstream analyses and minimize the waste of resources. Since existing QC tools are mostly dedicated to proteomics, automated solutions supporting metabolomics are needed. To address this need, we developed the software PeakQC, a tool for automated QC of MS data that is independent of omics molecular types (i.e., omics-agnostic). It allows automated extraction and inspection of peak metrics of precursor ions (e.g., errors in mass, retention time, arrival time) and supports various instrumentations and acquisition types, from infusion experiments or using liquid chromatography and/or ion mobility spectrometry front-end separations and with/without fragmentation spectra from data-dependent or independent acquisition analyses. Diagnostic plots for fragmentation spectra are also generated. Here, we describe and illustrate PeakQC's functionalities using different representative data sets, demonstrating its utility as a valuable tool for enhancing the quality and reliability of omics mass spectrometry analyses. [ABSTRACT FROM AUTHOR]

AbstractGlyphosate stands out in the eucalyptus management, which makes it essential to know its behavior, its effects on the plant, and possible environmental impacts. This study aimed to identify and quantify the root exudation of glyphosate and aminomethylphosphonic acid (AMPA) by Eucalyptus urophylla with chromatographic and biological methods. The five glyphosate doses were tested (0, 360, 720, 1080 and 1440 g a.e ha−1) on E. urophylla plants. The physiological and intoxication evaluations were performed after herbicide application. Water samples remaining from the pots were used for chemical quantification of root exudation of glyphosate and AMPA in high-performance liquid chromatography. Cucurbita pepo plants were used as bioindicators of glyphosate in the water remaining in the pots after applying herbicide. The increase in glyphosate doses promoted linear growth in E. urophylla intoxication and significantly reduced total dry mass and root production. E. urophylla plants had their photosynthetic, transpiratory, and stomatal conductance rates reduced as the herbicide doses increased. The AMPA root exudation was not detected, but it was possible to identify the presence of glyphosate by bioassay and chemical methods. Root exudation of glyphosate by eucalyptus can result in lesser herbicide action in plant control and cause contamination of deeper soil layers. [ABSTRACT FROM AUTHOR]

We established a method based on ultra performance liquid chromatography tandem mass spectrometry (UPLC‒MS/MS) to quantitatively measure tepotinib, which was validated as acceptable and used in the evaluation of food-drug interactions between tepotinib and naringenin in rats. We used pemigatinib as the internal standard (IS), and acetonitrile and 0.1% formic acid aqueous solution constituted the mobile phase. To extract the target analyte, acetonitrile was used for protein precipitation (PPT). For UPLC‒MS/MS, we performed liquid chromatography using a C18 column, and mass spectrometry was performed in positive multiple reaction monitoring (MRM) mode. Excellent linearity was shown in the range of 0.1–500 ng/mL, and the coefficient of correlation was > 0.99. Notably, the lower limit of quantification (LLOQ) for tepotinib was determined to be 0.1 ng/mL. The intra- and inter-day accuracy of tepotinib ranged from − 1.7 to 7.3%, while the precision was ≤ 8.4%, at three concentrations except LLOQ. The recovery of each substance was ≥ 81.2%, and the matrix effects were within 90.5-98.6%. The stabilities of all analytes under different conditions met all requirements for quantitation in plasma samples. The relevant parameters, such as LLOQ, were evaluated in accordance with the principles of the Food and Drug Administration (FDA) biological verification method. Food-drug interaction study had shown that the plasma concentration of tepotinib could be significantly increased, accompanied by a decrease in clearance rate when administered with 50 mg/kg naringenin. The results showed that naringenin could increase the plasma concentration and decrease the clearance rate of tepotinib when naringenin and tepotinib were administered at the same time. [ABSTRACT FROM AUTHOR]

Dark chocolates were characterized according to geographical origin, cocoa variety, and cocoa content using the methylxanthine and polyphenolic composition and antioxidant activity as the data. The main study objective was to uncover sample patterns and identify possible markers of quality, variety, or origin to deal with authentication or fraud detection issues. In the study, a set of 26 dark chocolates from different varieties (e.g., Criollo, Forastero, and Trinitario) harvested in Africa, America, and Asia was analyzed. The optimized sample treatment consisted of defatting the chocolate (1 g of sample with 5 mL of cyclohexane for 15 min, three times) and then extracting the analytes by sonication with methanol/water 60:40 (v:v) for 15 min. The filtered extracts were analyzed by reversed‐phase high‐performance liquid chromatography with UV and spectrophotometric methods (Folin–Ciocalteu, ferric reducing antioxidant power, and aluminum methods) to determine individual phenolics and overall indexes of antioxidant and flavonoid content. Results from this chocolate set indicated that American samples are richer than African counterparts in alkaloids and phenolics (e.g., 1.7 vs. 1.1 mg g−1 caffeine and 14.5 vs. 12.5 mg g−1 total flavanols, respectively). Regarding cocoa varieties, Criollo cocoa was richer in bioactive compounds and antioxidant capacity (e.g., 16, 15, and 12 mg g−1 total flavanols for Criollo, Forastero, and Trinitario, respectively). These results indicate that the analytes resulted in potential descriptors of varietal or geographical attributes. [ABSTRACT FROM AUTHOR]

A study was carried out on the feasibility of obtaining a modified lignosulfonate reagent by dispersing an additive synthesized using acrylamide, formalin, and malic acid. We determined the optimal component ratios for the preparation of this modifier and the modified lignosulfonate reagent through mathematical modelling using the Statistica 12 program package. The composition of the additive to the lignosulfonate drilling reagent was studied by high-performance liquid chromatography. Analysis of the two-dimensional correlation of the homo- and heteronuclear spectra, integral intensities in the 1H NMR spectra and the mass spectra of an experimental sample of the synthesized additive indicated the structure of this compound. Comparative analysis of the surface tension of the samples studied was carried out by the stalagmometric droplet counting method. The effectiveness of the synthesized additive and the modified lignosulfonate reagent for improving the parameters of the drilling mud at high temperature up to 180°C was demonstrated experimentally. [ABSTRACT FROM AUTHOR]