High-performance Liquid Chromatography-mass Research Articles

Formation and Suppression of Toxic Organofluorophosphates in Lithium Ion Batteries: Making the High-Voltage Additive Lithium Difluorophosphate Viable for Commercial Applications

Organofluorophosphates (OFPs) are one of the major concerns regarding the safety of Lithium Ion Batteries (LIBs) due to their neurotoxic properties. The formation through the hydrolysis of the conducting salt LiPF6 and subsequent reactions (reductive/oxidative) with the cyclic and linear carbonates is a major drawback in terms of commercial application of LIBs. The additive Lithium Difluorophosphate, which is literature known and beneficial for high-voltage LIBs due to its transition metal (TM) capturing abilities, accelerates the formation of toxic OFPs even further as it also is a hydrolysis product of LiPF6. The suppression of the formation of toxic OFPs through a synergetic dual additive approach with fluoroethylene carbonate (FEC) is presented in this study. Here, the thermal- and electrochemical formation of OFPs are successfully inhibited with the addition of 2 wt.% of FEC to the electrolyte containing LiDFP (1 wt.%). Characterization of OFPs is conducted via high performance liquid chromatography mass spectrometry and the toxicological capabilities of the aged electrolyte is assed through an inhibition-evaluation of Acetylcholinesterase lyophilizate. Combined, these two methods illustrate the successful inhibition of OFP formation in FEC/LiDFP dual-additive electrolytes. Further, this dual-additive approach does not deteriorate the performance of LiDFP as single additive making the FEC/LiDFP additive combination a possible new benchmark for high-voltage LIBs.

Tamarind Seed Polysaccharide Hydrolysate Ameliorates Dextran Sulfate Sodium-Induced Ulcerative Colitis via Regulating the Gut Microbiota.

(1) Background: Ulcerative colitis (UC) is a disease caused by noninfectious chronic inflammation characterized by varying degrees of inflammation affecting the colon or its entire mucosal surface. Current therapeutic strategies rely on the suppression of the immune response, which is effective, but can have detrimental effects. Recently, different plant polysaccharides and their degradation products have received increasing attention due to their prominent biological activities. The aim of this research was to evaluate the mitigation of inflammation exhibited by tamarind seed polysaccharide hydrolysate (TSPH) ingestion in colitis mice. (2) Methods: TSPH was obtained from the hydrolysis of tamarind seed polysaccharide (TSP) by trifluoroacetic acid (TFA). The structure and physical properties of TSPH were characterized by ultraviolet spectroscopy (UV), thin-layer chromatography (TLC), fourier transform infrared spectroscopy (FT-IR), and High-Performance Liquid Chromatography and Electrospray Ionization Mass Spectrometry (HPLC-ESI/MS) analysis. Then, the alleviative effects of the action of TSPH on 2.5% dextran sodium sulfate (DSS)-induced colitis mice were investigated. (3) Results: TSPH restored pathological lesions in the colon and inhibited the over-secretion of pro-inflammatory cytokines in UC mice. The relative expression level of mRNA for colonic tight junction proteins was increased. These findings suggested that TSPH could reduce inflammation in the colon. Additionally, the structure of the gut microbiota was also altered, with beneficial bacteria, including Prevotella and Blautia, significantly enriched by TSPH. Moreover, the richness of Blautia was positively correlated with acetic acid. (4) Conclusions: In conclusion, TSPH suppressed colonic inflammation, alleviated imbalances in the intestinal flora and regulated bacterial metabolites. Thus, this also implies that TSPH has the potential to be a functional food against colitis.

The influence of a maternal vegan diet on carnitine and vitamin B2 concentrations in human milk.

The maternal diet greatly influences the nutritional composition of human milk. With the rise of vegan diets by lactating mothers, there are concerns about the nutritional adequacy of their milk. Two important nutrients, vitamin B2 and carnitine, are mostly ingested via animal products. We investigated the influence of a vegan diet on the vitamin B2 and carnitine concentrations in milk and serum of lactating women. In this case-control study, 25 lactating mothers following an exclusive vegan diet were comparted to 25 healthy lactating mothers with an omnivorous diet without use of supplements. High-performance liquid chromatography and liquid chromatography-tandem mass spectrometry were used to measure vitamin B2 and carnitine concentrations, respectively. A linear regression model was used to determine differences in human milk and serum concentrations between study groups. Vitamin B2 concentrations in human milk and serum did not differ between study groups. While the human milk free carnitine (C0) and acetyl carnitine (C2) concentrations did not differ between study groups, serum carnitine concentrations were lower in participants following a vegan diet than in omnivorous women (p < 0.0001). A maternal vegan diet did not affect human milk concentration of vitamin B2 and carnitine. Breastfed infants of mothers following an exclusive vegan diet therefore are likely not at increased risk of developing a vitamin B2 or carnitine deficiency.

Utility of Trimethylamine Oxide (TMAO) in Predicting Early Neurological Deterioration after Acute Ischemic Stroke.

To investigate whether plasma trimethylamine N-oxide (TMAO) levels might predict early neurological deterioration (END) in individuals with acute ischemic stroke. Cohort study. Place and Duration of the Study:Jiulongpo District Hospital of Traditional Chinese Medicine, Chongqing City, China, from January 2020 to December 2021. Patients presenting with ischemic stroke were classified into the END group and the non-END group. The National Institutes of Health Stroke Scale (NIHSS) total increasing by 2 points or more within 72 hours of admission was the definition of the END. Plasma TMAO levels were determined by high-performance liquid chromatographic and tandem mass spectrometry. Twenty-six (25%) of the 104 patients, diagnosed with END exhibited higher TMAO levels after admission (median 1.438 vs. 0.449 nmol/mL, p=0.001). Elevated plasma TMAO levels were significant predictors of END in univariate logistic analysis. After controlling for age, gender, and cardiovascular risk factors in the multivariate conditional logistic regression model, the plasma TMAO levels in the END group remained significantly higher than those in the non-END group (OR=6.646, 95% CI 2.434-18.147, p<0.001). In receiver operator characteristic (ROC) analysis, the sensitivity and specificity of TMAO in distinguishing the END group and the non-END group at 0.564 nmol/mL cutoff value were 0.885 and 0.679, respectively. According to this research, the development of END on admission in patients with acute ischemic stroke may be positively correlated with the elevation in plasma TMAO levels. Trimethylamine N-oxide level, Acute ischemic stroke, Early neurological deterioration, NIHSS score.

Serum amino acid profiling in differentiating clinical outcomes of multiple sclerosis.

Amino acid metabolism is crucial for regulating immune responses and can be monitored in blood serum samples. This study aimed to analyse serum amino acid profiles in people with multiple sclerosis (pwMS), taking into account differences depending on the disease outcomes. Serum amino acid profiling is a promising, reproducible and minimally invasive technology, available at different stages of the disease, enabling the search for a specific biomarker to differentiate MS clinical outcomes. The serum concentrations of 29 amino acids were determined using high-performance liquid chromatography mass spectrometry. A total of 121 pwMS (41 relapsing-remitting MS-RRMS; 55 secondary progressive MS - SPMS; and 25 primary progressive MS-RRMS) with a median Expanded Disability Status Scale (EDSS) score of 6 and 53 healthy controls (HCs) were included. We found significantly higher serum total amino acids concentrations in pwMS compared to HCs. Serum concentrations of arginine, 1-methyl-L-histidine and proline were higher in pwMS, while circulating citrulline, α-aminobutyric acid and tryptophan were lower in pwMS. We observed significant differences in serum total amino acids concentrations depending on MS type, with the highest level in the PPMS group and the lowest in the RRMS group. We found significantly higher serum levels of beta-aminoisobutyric acid in PPMS patients compared to those with RRMS and SPMS, and significantly higher serum levels of aspartic acid in PPMS patients compared to RRMS patients. From visual inspection, no trend was observed in total amino acids concentration with respect to the EDSS score. When analysing serum total amino acids concentration in pwMS with EDSS ≤ 5 compared to those with EDSS > 5, no significant differences were found. Amino acid metabolism is altered in pwMS and depends on the clinical type of the disease. Further studies are needed to determine whether serum metabolomic profiling of amino acids may have an application in the search for clinical phenotype-specific MS biomarkers.

Antiulcer activity and mechanism of action of the hydroethanolic extract of leaves of Terminalia argentea Mart. In different in vivo and in vitro experimental models

Ethnopharmacological relevanceTerminalia argentea Mart. (Combretaceae) is a deciduous tree commonly found in Brazil, Bolivia, and Paraguay. It occurs in all regions of Brazil and is widespread in the Amazon, Cerrado, Pantanal, Atlantic Rain Forest, and Caatinga Biomes. In the traditional medicine of Brazil, people widely use tea or decoction of its leaf materials for treating gastritis, ulcers, wound healing, and inflammation. Aim of the studyThe current study aims to evaluate the gastroprotective and ulcer-healing activities of the hydroethanolic extract of T. argentea leaves (HETa) and investigate the underlying mechanisms of action through in vivo and in vitro experiments. MethodsWe extracted the leaves of T. argentea with a 70% hydroethanolic solution (HETa) and performed phytochemical analysis using high-performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MSn). We researched the antiulcer activity using in vivo and in vitro experiments, administering three doses (2, 10, and 50 mg/kg) and different concentrations of 1, 5, and 20 μg/mL, respectively. We verified the acute antiulcer activity using chemical models (acidified ethanol (EtOH/HCl) and indomethacin (IND)) and physiological models (water-immersion stress (WRS)). To induce chronic ulcers, used acetic acid and treated the animals for seven days. To investigate the mechanism of action, conducted assays of antioxidant activity, measured the dosage of inflammatory cytokines, quantified mucus, treated with inhibitors (IND, L-NAME, glibenclamide, and yohimbine), performed histopathological analysis, and measured gastric acid secretion. Furthermore, we performed in vitro experiments on murine macrophage cell lines (RAW 264-7 cells) to quantify nitrite/nitrate and cytokine production and on V79-4 cells to verify cell proliferation/migration. ResultsWe conducted HPLC and ESI-MSn analyses to obtain a fingerprint of the chemical composition of the HETa, revealing the presence of phenolics (caffeoyl ellagic acid), flavonoids (rutin, quercetin xyloside, quercetin rhamnoside, quercetin glucoside, quercetin galloyl xyloside, quercetin), and tannins (terminalin), respectively. The three doses of HETa reduced acute and chronic ulcers in different models. The mechanism of action involves increasing mucus production and angiogenesis, and it partially involves prostaglandins, nitric oxide, K+ATP channels, and α2-adrenergic receptors. HETa also exhibited antioxidant potential, reducing myeloperoxidase (MPO) activity, and increasing glutathione (GSH) levels. Moreover, it demonstrated anti-inflammatory action by reducing nitrite/nitrate levels and pro-inflammatory cytokine concentrations in vivo, and it increased in vitro proliferation/migration of fibroblasts. ConclusionsThe study shows that HETa presents a potent preventive and curative antiulcer effect in different ulcer models, supporting the popular use of homemade preparations of T. argentea leaves. The preventive and gastric healing ulcer activity of HETa involves multiple targets, including increasing the gastric mucus barrier, antioxidant defenses, and anti-inflammatory effects on gastric mucosa repair. Phytochemical analysis identified the presence of phenolic compounds, flavonoids, and tannins in HETa, and the antiulcer activity may be attributable to the combined effect of these constituents.

Yang-Xin-Shu-Mai granule alleviates atherosclerosis by regulating macrophage polarization via the TLR9/MyD88/NF-κB signaling pathway

Ethnopharmacological relevancePrevious studies have found that Yang-Xin-Shu-Mai granule (YXSMG) has certain advantages in the treatment of stable coronary heart disease. However, YXSMG can inhibit the progression of atherosclerotic plaque and stabilize vulnerable plaque needs to be further explored and studied. This research, mass spectrometry analysis, network pharmacology, in vivo and in vitro experimental studies were conducted to explore the mechanism of YXSMG on atherosclerosis. Aim of the studyTo decipher the mechanism of atherosclerotic plaque, stabilization for YXSMG by analysis of its active ingredients and biological network and activity in whole animal and at cellular and molecular levels. MethodsThe active components of YXSMG were determined using high performance liquid chromatography-mass spectrometry/mass spectrometry (HPLC-MS/MS) analysis. The ‘Disease-Compound-Target-Pathway’ network diagram was constructed using network pharmacology, and the stability of binding between core targets and core compounds was analyzed with molecular docking. After intervention with YXSMG, the pathology of aortic plaque, inflammation in the surrounding tissue, expression of TLR9/MyD88/NF-κB pathway protein in plaque and M1/M2 polarization of plaque macrophages were evaluated in vivo in apolipoprotein E-deficient (ApoE−/−) mice fed with high-fat diet. To verify whether it suppressed inflammation by inhibiting Toll-like receptor 9 (TLR9) reprogramming of macrophage polarization, we used RAW264.7 macrophages treated with specific TLR9 agonist (ODN1826) and inhibitor (ODN2088). ResultsFive active compounds were identified in YXSMG: catechin, formononetin, tanshinone IIA, cryptotanshinone and glycitein. Network pharmacology studies revealed TLR9 as one of the core targets of YXSMG intervention in atherosclerosis. Computer simulation of molecular docking showed that TLR9 could interact with the core compound to form a stable complex. In vivo experiments confirmed that YXSMG could significantly inhibit atherosclerotic plaque, reduce levels of blood lipids and inflammatory factors, downregulate TLR9/MyD88/NF-κB pathway protein and inhibit aortic sinus macrophages polarization to M1, but promote their polarization to M2 to inhibit inflammation. In vitro experiments revealed that YXSMG could downregulate expression of TLR9 gene and protein in ODN1826-activated RAW264.7 macrophages. ODN2088 had a synergistic effect with YXSMG on the TLR9/MyD88/NF-κB signaling pathway, and reprogrammed macrophages polarization from M1 to M2 by inhibiting TLR9, thus reducing immuno-inflammatory response. ConclusionYXSMG can reduce the level of blood lipid and improve the size of atherosclerotic plaque and inflammatory infiltration in ApoE−/− mice fed with high fat. It is concluded that YXSMG can improve the mechanism of atherosclerotic plaque by inhibiting TLR9/MyD88/NF-κB pathway reprogramming macrophage M1/M2 polarization and reducing arterial inflammation.

Design, Fabrication, and Applications of SERS Substrates for Food Safety Detection: Review.

Sustainable and safe food is an important issue worldwide, and it depends on cost-effective analysis tools with good sensitivity and reality. However, traditional standard chemical methods of food safety detection, such as high-performance liquid chromatography (HPLC), gas chromatography (GC), and tandem mass spectrometry (MS), have the disadvantages of high cost and long testing time. Those disadvantages have prevented people from obtaining sufficient risk information to confirm the safety of their products. In addition, food safety testing, such as the bioassay method, often results in false positives or false negatives due to little rigor preprocessing of samples. So far, food safety analysis currently relies on the enzyme-linked immunosorbent assay (ELISA), polymerase chain reaction (PCR), HPLC, GC, UV-visible spectrophotometry, and MS, all of which require significant time to train qualified food safety testing laboratory operators. These factors have hindered the development of rapid food safety monitoring systems, especially in remote areas or areas with a relative lack of testing resources. Surface-enhanced Raman spectroscopy (SERS) has emerged as one of the tools of choice for food safety testing that can overcome these dilemmas over the past decades. SERS offers advantages over chromatographic mass spectrometry analysis due to its portability, non-destructive nature, and lower cost implications. However, as it currently stands, Raman spectroscopy is a supplemental tool in chemical analysis, reinforcing and enhancing the completeness and coverage of the food safety analysis system. SERS combines portability with non-destructive and cheaper detection costs to gain an advantage over chromatographic mass spectrometry analysis. SERS has encountered many challenges in moving toward regulatory applications in food safety, such as quantitative accuracy, poor reproducibility, and instability of large molecule detection. As a result, the reality of SERS, as a screening tool for regulatory announcements worldwide, is still uncommon. In this review article, we have compiled the current designs and fabrications of SERS substrates for food safety detection to unify all the requirements and the opportunities to overcome these challenges. This review is expected to improve the interest in the sensing field of SERS and facilitate the SERS applications in food safety detection in the future.

An insight into milt antioxidant, fatty acid, amino acid composition and testis histology of an anadromous euryhaline fish Tenualosa ilisha, Ham. 1822 for its conservation and aquaculture perspectives

Hilsa, Tenualosa ilisha, Ham. 1822, is the prime table fish and important commercial fish in the Indo-Pacific region. However, the species has recently declined drastically due to various factors. Our earlier studies recorded a significant association between the breeding season and its migration. Studies on milt and its biochemical properties are essential to ensure its successful conservation and artificial breeding. Here, milt samples of the hilsa of varied sizes were evaluated for their antioxidant property, fatty acid and amino acid content, and the histology of the testis. Analysis of milt antioxidants was done using free radicals DPPH, FRAPS & ABTS methods and compared with the free-radical quenching properties of the synthetic antioxidants. High performance liquid chromatography (HPLC) and gas chromatography and mass spectrometry (GC/MS) determined the composition of amino acids and fatty acids, respectively. The highest and lowest antioxidant activity was exhibited by hilsa milt samples M3 (b.wt 358.6 ± 0.75 g) i.e. 84.59 ± 0.48% and M12 (b.wt 168.35 ± 0.12 g) i.e. 27.53 ± 3.59%. Most notably, the antioxidant activity was found to follow a body weight gradient. Omega (ꙍ)-3 polyunsaturated fatty acids (PUFAs), docosahexaenoic acid (C22:6, DHA) and eicosapentaenoic acid (C20:5, EPA) were the predominant PUFAs and among the amino acids, arginine (0.70 g/100 g) was present in the highest quantity followed by glutamic acid (0.14 g/100 g) and proline (0.14 g/100 g). The histology study of the testis reveals the changes in the cells during the process of spermatogenesis. Histological images demonstrated the different stages of testis maturation of males sampled at the spawning sites. This baseline information generated is of its first kind in hilsa, a transboundary migratory fish in South Asian countries supporting conservation and artificial breeding for commercial production.

Enhanced electron channel via the interfacial heterotropic electric field in dual S-scheme g-C3N4/WO3/ZnS photocatalyst for year-round antibiotic degradation under sunlight

Widespread and persistent presence of antibiotic contaminants in natural aquatic environments has aroused all mankind concern due to their potential threat to human health. Photocatalysis represents a promising means to remediate polluted waters with the simple assistance of solar energy. In this context, the feasibility of treating antibiotic contaminated water with g-C3N4/WO3/ZnS dual S-scheme heterojunction driven by interfacial heterotropic electric field was investigated under year-round climate conditions. The optimum composite (5-CWZ) could degrade >85% of tetracycline within 1 h of summer sunlight and 1.5 h of winter sunlight irradiation. The results of electron spin resonance (ESR), chemical trapping experiment, High performance liquid chromatography mass spectrometry (HPLC-MS), ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) calculation reflected that in-situ anchoring of WO3 and ZnS on the surface of g-C3N4 facilitates the formation of interfacial heterotropic electric field which were effective towards low-resistance charge carrier channelization, resulting sufficient •O2–, h+, •OH species evolving for attacking the active atoms of contaminants with high Fukui index. Furthermore, the retention of superior photocatalytic properties in complex actual water matrices together with the non-toxicity of both 5-CWZ photocatalyst and treated TC solution proved by Pisum sativum bud radicle elongation and bacterial (E. coli and B. subtilis) cultivation further demonstrated the feasibility of the 5-CWZ to treat antibiotics in real water under irradiation of solar light.

Enhanced organic pollutant removal in saline wastewater by a tripolyphosphate-Fe0/H2O2 system: Key role of tripolyphosphate and reactive oxygen species generation

The effects of tripolyphosphate (TPP) on organic pollutant degradation in saline wastewater using Fe0/H2O2 were systematically investigated to elucidate its mechanism and the main reactive oxygen species (ROS). Organic pollutant degradation was dependent on the Fe0 and H2O2 concentration, Fe0/TPP molar ratio, and pH value. The apparent rate constant (kobs) of TPP-Fe0/H2O2 was 5.35 times higher than that of Fe0/H2O2 when orange II (OGII) and NaCl were used as the target pollutant and model salt, respectively. The electron paramagnetic resonance (EPR) and quenching test results showed that •OH, O2•−, and 1O2 participated in OGII removal, and the dominant ROS were influenced by the Fe0/TPP molar ratio. The presence of TPP accelerates Fe3+/Fe2+ recycling and forms Fe-TPP complexes, which ensures sufficient soluble Fe for H2O2 activation, prevents excessive Fe0 corrosion, and thereby inhibits Fe sludge formation. Additionally, TPP-Fe0/H2O2/NaCl maintained a performance similar to those of other saline systems and effectively removed various organic pollutants. The OGII degradation intermediates were identified using high-performance liquid chromatography–mass spectrometry (HPLC–MS) and density functional theory (DFT), and possible degradation pathways for OGII were proposed. These findings provide a facile and cost-effective Fe-based AOP method for removing organic pollutants from saline wastewater.

4-Hydroxybenzyl alcohol from Sinapis alba mustard seed meal extract for control of liverwort (Marchantia polymorpha)

Sinapis alba mustard seed meal extract is a by-product of mustard oil extraction, that is used for biodiesel and renewable jet fuel production. Recently, S. alba mustard seed meal has been shown to have herbicidal activity for a range of problematic weeds. The objectives of the present research were 1) to optimize the preparation of S. alba mustard seed meal extract; 2) to explore the applicability of S. alba mustard seed meal extract for control of liverwort, a common pest in ornamental plants greenhouses; and 3) to identify the major herbicidal compound(s) in these extracts. For extraction, methanol content in aqueous solution was optimized between 0% and 100%. Extracts prepared with 0–30% aqueous methanol provided 98–100% control of liverwort after single application and prevented liverwort plants from recovering. Extracts prepared using sequential extraction with 60% methanol provided an additional benefit of low particulate solutions. The efficiency of the produced S. alba mustard seed meal extract was comparable to two commercially available herbicides labeled for liverwort control under greenhouse conditions. Composition of S. alba mustard seed meal extracts was analyzed by high-performance liquid chromatography mass spectrometry and ion chromatography. 4-Hydroxybenzyl alcohol was identified as a main herbicidal compound based on the analysis and using commercially available reference solution. To the best of our knowledge, this is the first report of 4-hydroxybenzyl alcohol herbicidal activity toward nonvascular plants. The high concentrations of 4-hydroxybenzyl alcohol naturally produced from S. alba mustard seed meal, makes it a potential herbicide feedstock material.

Development and validation of a peptide-mapping procedure for a novel C1 esterase inhibitor

Peptide mapping is a key method for studying the primary structure of proteins. With its sensitivity to the slightest changes in the covalent structure of a protein, this method is applicable both to medicinal product identification at the control stage and to production process stability monitoring.The aim of the study was to develop and validate a peptide-mapping procedure for the identification of a novel highly glycosylated recombinant C1 esterase inhibitor.Materials and methods. The authors studied recombinant human C1 esterase inhibitor products and trypsin. The study involved peptide mapping using reverse-phase high-performance liquid chromatography and high-resolution mass spectrometry. The following statistics were calculated to evaluate the results: mean, standard deviation, and coefficient of variation. The validation parameters included specificity, precision, and robustness.Results. The authors tested several variants of sample preparation for tryptic digests, including additional N-glycanase treatment and complete deglycosylation, and established the optimal conditions for sample preparation and chromatographic separation of C1 esterase inhibitor peptides to obtain consistent chromatographic profiles (peptide maps). The authors identified characteristic peaks and the corresponding relative retention time and area ranges. The absolute retention time of the second (characteristic) peak was approximately 16.5–16.9 minutes. The relative retention times were 2.14–2.21 for peak 9, 2.55–2.64 for peak 12, 2.97–3.14 for peak 14, 3.11–3.29 for peak 15, and 6.20–6.63 for peak 28.Conclusions. The authors developed a peptide-mapping procedure for C1 esterase inhibitors and optimised the conditions to achieve an over 18-hour reduction in sample preparation time. This procedure met the established acceptance criteria for specificity, precision, and robustness.

HIGH SERUM TRIMETHYLAMINE N-OXIDE LEVEL IS ASSOCIATED WITH ENDOTHELIAL DYSFUNCTION IN PATIENTS WITH HYPERTENSION

Objective: Trimethylamine N-oxide (TMAO) is a metabolite derived from gut microbial metabolism and dietary intake and plays important roles in cardiovascular disease pathogenesis. Endothelial dysfunction is associated with risk factors of cardiovascular disease in patients with hypertension. The present study aimed to determine the correlation between serum TMAO and endothelial function, measured by vascular reactivity index (VRI) in patients with hypertension. Design and method: The present study collected fasting blood samples from 110 patients with hypertension. Serum TMAO levels were determination of by high-performance liquid chromatography–mass spectrometry. The endothelial function and VRI values were measured using digital thermal monitoring test, and VRI values of &gt;2.0, 1.0–1.9 and &lt;1.0 indicated good, intermediate and poor vascular reactivity, respectively. Results: Ten hypertensive patients (9.1%) were categorized as poor vascular reactivity (VRI &lt; 1.0), 57 hypertensive patients (51.8%) were categorized as intermediate vascular reactivity (1.0 &lt; VRI &lt; 2.0), and 43 hypertensive patients had good vascular reactivity. Older age (P = 0.010), higher levels of serum total cholesterol (TCH, P = 0.007), low-density lipoprotein cholesterol (LDL-C, P = 0.009), and TMAO levels (P &lt; 0.001) were associated with poor vascular reactivity. Furthermore, after multivariable forward stepwise linear regression analysis noted that logarithmically transformed serum level of TMAO (log-TMAO, adjusted R2 change = 0.274, P &lt; 0.001) was significantly and independently associated with VRI values in hypertensive patients. Compared with good vascular reactivity index, patients with vascular reactivity dysfunction (intermediate vascular reactivity and poor vascular reactivity; odds ratio (OR) = 1.100; 95% confidence interval (CI) = 1.047–1.155; P &lt; 0.001) or poor vascular reactivity (OR = 1.580, 95% CI = 1.002–2.492, P = 0.049) also noted TMAO was positively associated with poor vascular reactivity after multivariate logistic regression analysis. Conclusions: Serum TMAO levels were negatively associated with VRI and associated with endothelial dysfunction in patients with hypertension.

Isolation and identification of a polyester-polyurethane degrading bacterium Bacillus altitudinis YX8-1

Although polyurethane (PUR) plastics play important roles in daily life, its wastes bring serious environmental pollutions. Biological (enzymatic) degradation is considered as an environmentally friendly and low-cost method for PUR waste recycling, in which the efficient PUR-degrading strains or enzymes are crucial. In this work, a polyester PUR-degrading strain YX8-1 was isolated from the surface of PUR waste collected from a landfill. Based on colony morphology and micromorphology observation, phylogenetic analysis of 16S rDNA and gyrA gene, as well as genome sequence comparison, strain YX8-1 was identified as Bacillus altitudinis. The results of high performance liquid chromatography (HPLC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) showed that strain YX8-1 was able to depolymerize self-synthesized polyester PUR oligomer (PBA-PU) to produce a monomeric compound 4, 4'-methylene diphenylamine. Furthermore, strain YX8-1 was able to degrade 32% of the commercialized polyester PUR sponges within 30 days. This study thus provides a strain capable of biodegradation of PUR waste, which may facilitate the mining of related degrading enzymes.

Transcriptome Analysis Reveals the Genes Involved in Oxidative Stress Responses of Scallop to PST-Producing Algae and a Candidate Biomarker for PST Monitoring.

Paralytic shellfish toxins (PST) could be accumulated in bivalves and cause safety problems. To protect public health, bivalves are examined for PST contamination before entering the market, usually by high-performance liquid chromatography (HPLC) or LC-tandem mass spectrometry (LC-MS/MS) in the lab, which needs PST standards not all available and is time-consuming for large sample sizes. To detect PST toxicity in bivalves rapidly and sensitively, a biomarker gene is highly demanded, but the related study is very limited. In this study, we fed a commercially important bivalve, Patinopecten yessoensis, with the PST-producing dinoflagellate Alexandrium catenella. After 1, 3, and 5 days of exposure, both PST concentrations and toxicity levels in the digestive gland continuously increased. Transcriptome analysis revealed that the differentially expressed genes were significantly enriched in oxidation-reduction process, which included the cytochrome P450 genes (CYPs), type I iodothyronine deiodinase (IOD1s), peroxidasin (PXDN), and acyl-Coenzyme A oxidase 1 (ACOX1) at day 1 and a superoxide dismutase (SOD) at day 5, highlighting the crucial roles of these genes in response to oxidative stress induced by PST. Among the 33 continuously upregulated genes, five showed a significant correlation between gene expression and PST concentration, with the highest correlation present in PyC1QL4-1, the gene encoding Complement C1Q-like protein 4, C1QL4. In addition, the correlation between PyC1QL4-1 expression and PST toxicity was also the highest. Further analysis in another aquaculture scallop (Chlamys farreri) indicated that the expression of CfC1QL4-1, the homolog of PyC1QL4-1, also exhibited significant correlations with both PST toxicity and concentration. Our results reveal the gene expression responses of scallop digestive glands to PST-producing algae and indicate that the C1QL4-1 gene might be a potential biomarker for PST monitoring in scallops, which may provide a convenient way for the early warning and sensitive detection of PST contamination in the bivalves.

Serum lipidomics reveals phosphatidylethanolamine and phosphatidylcholine disorders in patients with myocardial infarction and post-myocardial infarction-heart failure

BackgroundMyocardial infarction (MI) and post-MI-heart failure (pMIHF) are a major cause of death worldwide, however, the underlying mechanisms of pMIHF from MI are not well understood. This study sought to characterize early lipid biomarkers for the development of pMIHF disease.MethodsSerum samples from 18 MI and 24 pMIHF patients were collected from the Affiliated Hospital of Zunyi Medical University and analyzed using lipidomics with Ultra High Performance Liquid Chromatography and Q-Exactive High Resolution Mass Spectrometer. The serum samples were tested by the official partial least squares discriminant analysis (OPLS-DA) to find the differential expression of metabolites between the two groups. Furthermore, the metabolic biomarkers of pMIHF were screened using the subject operating characteristic (ROC) curve and correlation analysis.ResultsThe average age of the 18 MI and 24 pMIHF participants was 57.83 ± 9.28 and 64.38 ± 10.89 years, respectively. The B-type natriuretic peptide (BNP) level was 328.5 ± 299.842 and 3535.96 ± 3025 pg/mL, total cholesterol(TC) was 5.59 ± 1.51 and 4.69 ± 1.13 mmol/L, and blood urea nitrogen (BUN) was 5.24 ± 2.15 and 7.20 ± 3.49 mmol/L, respectively. In addition, 88 lipids, including 76 (86.36%) down-regulated lipids, were identified between the patients with MI and pMIHF. ROC analysis showed that phosphatidylethanolamine (PE) (12:1e_22:0) (area under the curve [AUC] = 0.9306) and phosphatidylcholine (PC) (22:4_14:1) (AUC = 0.8380) could be potential biomarkers for the development of pMIHF. Correlation analysis showed that PE (12:1e_22:0) was inversely correlated with BNP and BUN, but positively correlated with TC. In contrast, PC (22:4_14:1) was positively associated with both BNP and BUN, and was negatively associated with TC.ConclusionsSeveral lipid biomarkers were identified that could potentially be used to predict and diagnose patients with pMIHF. PE (12:1e_22:0) and PC (22:4_14:1) could sufficiently differentiate between patients with MI and pMIHF.

An interference-free SERS-based aptasensor for chlorpyrifos detection

In this study, we propose an interference-free SERS-based aptasensor for trace detection of chlorpyrifos (CPF) in real samples. In the aptasensor, gold nanoparticles coated with Prussian blue (Au@PB NPs) were employed as SERS tags to provide a sole and intense Raman emission at 2160 cm−1, which could avoid overlapping with the Raman spectrum of the real samples in 600–1800 cm−1 to improve the anti-matrix effect ability of the aptasensor. Under the optimum conditions, this aptasensor displayed a linear response for CPF detection in the range of 0.1–316 ng mL−1 with a low detection limit of 0.066 ng mL−1. In addition, the prepared aptasensor shows excellent application to determine CPF in cucumber, pear and river water samples. The recovery rates were highly correlated with high-performance liquid chromatography‒mass spectrometry (HPLC‒MS/MS). This aptasensor shows interference-free, specific and sensitive detection for CPF and offers an effective strategy for other pesticide residue detection.

Identification of human in vitro metabolites of the haemoglobin S polymerization inhibitor voxelotor for doping control purposes.

Voxelotor (GBT440) is a haemoglobin S polymerization inhibitor used to treat anaemia in sickle cell disease. Due to an increase of arterial oxygen saturation as well as serum erythropoietin and haemoglobin, the World Anti-Doping Agency included voxelotor in the list of prohibited substances and methods in 2023. The objective of the present study was to identify and characterize metabolites of voxelotor to detect a potential misuse by athletes. The biotransformation was studied in vitro using the human hepatocellular cell line HepG2 and pooled human liver microsomes. The metabolites were analysed using high-performance liquid chromatography (high-resolution) mass spectrometry. In total, three phase I metabolites and six phase II metabolites (resulting from glucuro-conjugation and O-methylation) were formed by the HepG2 cells in a time-dependent manner, and two phase I metabolites were generated by the liver microsomes, among them one also found in the HepG2 incubations. A reduced metabolite and the glucuro-conjugate of a reduced metabolite were the most abundant formed by HepG2 cells. In addition, metabolites resulting from mono-hydroxylation, reduction and O-methylation in different combinations were identified. Voxelotor was also found as glucuro-conjugate with a low abundance. With the spectrometric behaviour of voxelotor and its in vitro metabolites described herein, an implementation in doping control screening and, consequently, a detection of an abuse in an athlete urine sample might be possible.

Benzoin Resin: An Overview on Its Production Process, Phytochemistry, Traditional Use and Quality Control.

Benzoin is a pathologic exudation produced by plants of the family Styrax. It is secreted by traumatic resin ducts after injury, which are derived from parenchymal cells in secondary xylem by schizolysigeny. Some 63 chemical constituents have been isolated and identified from this resin, including balsamic acid esters, lignans and terpenoids. It has a long history of applications, including as incense along with olibanum, a flavor enhancer in the food industry, materials in the daily chemistry industry as well as therapeutic uses. Up to now, high-performance liquid chromatography (HPLC) and gas chromatography mass spectrometry (GC-MS) have been widely used in qualitative and quantitative analysis of benzoin. Other technologies, including near-infrared reflectance spectroscopy (NIR), proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and Fourier-transform infrared spectroscopy (FT-IR), have also been used to distinguish different resins. Herein, this paper provides a comprehensive overview of the production process, phytochemistry, traditional uses and quality control of benzoin and looks to the future for promoting its further research and applications.