New applications of boron-doped diamond electrode for voltammetric determination of ascorbic acid

An unmodified boron-doped diamond electrode was used for the voltammetric determination of ascorbic acid (AA). The measurements were carried out in an acetate buffer solution of pH = 4.6 by differential pulse voltammetry (DPV). Under the optimized experimental conditions, AA gaves linear response in a broad concentration range from 5 · 10–7 to 2· 10–3 mol/dm3. The detection limit was 1.63 · 10–7 mol/dm3. The proposed procedure was applied for simple and fast voltammetric determination of ascorbic acid in human urine samples and commercially available dietary supplements

Electrochemical Determination of Kynurenine Pathway Metabolites—Challenges and Perspectives

In recent years, tryptophan metabolism via the kynurenine pathway has become one of the most active research areas thanks to its involvement in a variety of physiological processes, especially in conditions associated with immune dysfunction, central nervous system disorders, autoimmunity, infection, diabetes, and cancer. The kynurenine pathway generates several metabolites with immunosuppressive functions or neuroprotective, antioxidant, or toxic properties. An increasing body of work on this topic uncovers a need for reliable analytical methods to help identify and quantify tryptophan metabolites at physiological concentrations in biological samples of different origins. Recent methodological advances in the fabrication and application of electrochemical sensors promise a rise in the future generation of novel analytical systems. This work summarizes current knowledge and provides important suggestions with respect to direct electrochemical determinations of kynurenine pathway metabolites (kynurenines) in complex biological matrices. Measurement challenges, limitations, and future opportunities of electroanalytical methods to advance study of the implementation of kynurenines in disease conditions are discussed

The Influence of Exercise Intensity on Tryptophan Metabolites in Thoroughbred Horses

Catabolism of tryptophan (Trp) is modulated by physical activity and provides a pool of active compounds: Trp is considered a calmative agent, kynurenine (Kyn) and 3-hydroxykynurenine (3-HKyn) show neurotoxic effects, kynurenic acid (Kyna) and xanthurenic acid (XA) have neuroprotective properties like nicotinamide (NAm), while serotonin is the neurotransmitter. The study was conducted to investigate the dependence of exercise intensity, measured by plasma lactic acid (LA) concentration, on the level of Trp, its catabolites (serotonin, Kyn, 3-HKyn, Kyna and XA), and NAm in Thoroughbred horses. A total of 18 young race Thoroughbred horses were investigated during exercise tests. Blood samples for analysis were collected: at rest, 10 min after the end of the exercise, and 60 min after the end of the exercise. Plasma LA was determined by the enzymatic method, Trp, and other metabolites using liquid chromatography coupled with mass spectrometry. In horses performing intense exercise, the concentration of LA, Kyn, XA and NAm was increased, while Trp was decreased. Significant correlations were detected for exercise-induced increase in LA and 3-HKyn, XA, and NAm. Considering the scope of changes in analyzed data, there is an expected neutral effect on the health status of exercised horses

UHPLC-ESI-MS/MS Quantification of Relevant Substrates and Metabolites of the Kynurenine Pathway Present in Serum and Peritoneal Fluid from Gastric Cancer Patients—Method Development and Validation

Metabolites and enzymes involved in the kynurenine pathway (KP) are highly promising targets for cancer treatment, including gastrointestinal tract diseases. Thus, accurate quantification of these compounds in body fluids becomes increasingly important. The aim of this study was the development and validation of the UHPLC-ESI-MS/MS methods for targeted quantification of biologically important KP substrates (tryptophan and nicotinamide) and metabolites(kynurenines) in samples of serum and peritoneal fluid from gastric cancer patients. The serum samples were simply pretreated with trichloroacetic acid to precipitate proteins. The peritoneal fluid was purified by solid-phase extraction before analysis. Validation was carried out for both matrices independently. Analysis of the samples from gastric cancer patients showed different accumulations of tryptophan and its metabolites in different biofluids of the same patient. The protocols will be used for the evaluation of tryptophan and kynurenines in blood and peritoneal fluid to determine correlation with the clinicopathological status of gastric cancer or the disease’s prognosis

The Kynurenine Pathway in Obese Middle-Aged Women with Normoglycemia and Type 2 Diabetes

We examined the relationships of tryptophan (Trp) and the metabolites of the kynurenine pathway (KP) to the occurrence of type 2 diabetes (T2D) and metabolic risk factors in obese middle-aged women. The study included 128 obese women divided into two subgroups: a normoglycemic group (NG, n = 65) and a T2D group (n = 63). The concentrations of serum tryptophan (Trp), kynurenine (Kyn), 3-hydroxykynurenine (3HKyn), quinolinic acid (QA), and kynurenic acid (Kyna) were analyzed using ultra-high-performance liquid chromatography coupled with electrospray ionization/triple quadrupole mass spectrometry. Blood biochemical parameters and anthropometric parameters were measured. The women with T2D had significantly higher Trp, Kyna, Kyna/QA ratio, and Kyna/3HKyn ratio values than the NG women. Logistic regression analysis showed that the concentrations of Trp and Kyna and the values of the Kyna/3HKyn ratio were most strongly associated with T2D occurrence, even after controlling for confounding factors. The model with Trp level and Kyna/3HKyn ratio accounted for 20% of the variation in the presence of T2D. We also showed a different pattern of correlations between kynurenines and metabolic factors in the NG and T2D women, which was mostly reflected in the stronger relationship between BMI and KP metabolites in the NG obese women. An increase in Trp and Kyna levels with an accompanying increase in Kyna/3HKyn ratio value is associated with the occurrence of T2D in obese middle-aged women

A Screen-Printed Sensor Coupled with Flow System for Quantitative Determination of a Novel Promising Anticancer Agent Candidate

A carbon nanofibers modified screen-printed carbon sensor (SPCE/CNFs) was applied for the determination of a novel promising anticancer agent candidate (ethyl 8-(4-methoxyphenyl)-4-oxo-4,6,7,8-tetrahydroimidazo[2,1-c][1,2,4]triazine-3-carboxylate, EIMTC) using square-wave voltammetry (SWV). It is the first method for the quantitative determination of EIMTC. The modified screen-printed sensor exhibited excellent electrochemical activity in reducing EIMTC. The peak current of EIMTC was found to be linear in two concentration ranges of 2.0 × 10−9 – 2.0 × 10−8 mol L−1 and 2.0 × 10−8 – 2.0 × 10−7 mol L−1, with a detection limit of 5.0 × 10−10 mol L−1. The connection of flow-cell for the SPCE/CNFs with SWV detection allowed for the successful determination of EIMTC in human serum samples. Ultra-high-performance liquid chromatography coupled to electrospray ionization triple quadrupole mass spectrometry (UHPLC-ESI-MS/MS) acted as a comparative method in the serum samples analysis

Jednoduchý a nenáročný způsob zvýšení citlivosti stanovení Sn(IV) na bismutových filmových elektrodách s použitím mediátoru

For the first time an in situ-plated bismuth film electrode prepared with the use of a reversibly deposited mediator (Zn) was applied to anodic stripping voltammetry of the metal ions. This simple and easy way of the electrode surface modification by metal films was suggested to increase the voltammetric signal of Sn(IV) and, consequently, to improve the sensitivity and tin detection limit. The structural and chemical information about the bismuth films plated with and without the use of the mediator were derived from AFM and XPS data analysis.Bismutová filmová elektroda připravená in situ s využitím reverzibilně deponovaného mediátoru (Zn) byla použita pro anodickou rozpouštěcí voltametrii iontů kovů. Tento jednoduchý způsob modifikace elektrodového povrchu filmy kovů byl navržen ke zvýšení voltametrického signálu Sn(IV) a tím zlepšení citlivosti a detekčního limitu stanovení. Charakterizace bismutových filmů připravených s a bez použití mediátoru byla provedena pomocí AFM a XPS

A validated LC–MS/MS method for simultaneous determination of key glucocorticoids in animal hair for applications in conservation biology

Abstract A new method for the determination of main glucocorticoids (cortisol, cortisone, and corticosterone) in hair by liquid chromatography-tandem mass spectrometry was developed. Glucocorticoids were extracted from hair shafts using methanol followed by solid-phase extraction. A validation test was performed using hair from three species of wild mammals with different body size (0.2–800 kg), lifestyle (terrestrial, burrowing and arboreal species), social organization (living in herds or solitary), and different predicted type of hair glucocorticoids: European bison (Bison bonasus), European hamster (Cricetus cricetus), and Eurasian red squirrel (Sciurus vulgaris). Regardless of the species evaluated, the method shows good linearity for all analytes accompanied by satisfactory accuracy (91–114%) and precision (RSD < 13%). Depending on the analyte and hair origin, the calculated limits of quantification were between 0.05 and 1.19 ng/mL, which corresponds to 1.28–31.51 pg/mg. Using cortisol and cortisone as examples, we have demonstrated that measuring multiple glucocorticoids simultaneously provides more comprehensive information than solely concentrating on one, thereby contributing to a more balanced and reliable interpretation of the acquired results. However, the utility of cortisol metabolites as markers of stress response in keratinized tissues should be substantiated by additional experimental studies on targeted animals. We posit that this paper could serve as a crucial catalyst to prompt such experiments

A Comprehensive Analysis Using Colorimetry, Liquid Chromatography-Tandem Mass Spectrometry and Bioassays for the Assessment of Indole Related Compounds Produced by Endophytes of Selected Wheat Cultivars

Liquid chromatography–tandem mass spectrometry (LC–MS/MS), colorimetry, and bioassays were employed for the evaluation of the ability of endophytic bacterial strains to synthesize indole-related compounds (IRCs) and in particular indole-3-acetic acid (IAA). A total of 54 endophytic strains belonging to seven bacterial genera isolated from tissues of common and spelt wheat cultivars were studied. The endophytic bacteria isolated from different tissues of the tested wheat types were capable of IRCs production, including IAA, which constituted from 1.75% to 52.68% of all IRCs, in in vitro conditions via the tryptophan dependent pathway. The selected post-culture medium was also examined using a plant bioassay. Substantial growth of wheat coleoptile segments treated with the bacterial post-culture medium was observed in several cases. Our data suggest that the studied endophytic bacteria produce auxin-type compounds to support plant development. Summarizing, our approach to use three complementary methods for estimation of IRCs in different endophytic strains provides a comprehensive picture of their effect on wheat growth

Unlocking the effect of Zn2+ on crystal structure, optical properties, and photocatalytic degradation of perfluoroalkyl substances (PFAS) of Bi2WO6

Bismuth tungstate (Bi2WO6) with a layered structure and visible light response exhibits excellent photocatalytic activity. To enhance its photocatalytic activity for the degradation of perfluoroalkyl substances (PFAS), Zn2+ is partially substituted for Bi3+ in the Bi2WO6 lattice in this study. Particularly, the effect of Zn2+ content (0-22.5 at%) on the crystal structure, optical property, and photocatalytic activity for the photodegradation of PFAS of Bi2WO6 is investigated. According to the Le Bail fits, the unit-cell volume is slightly reduced from 487.7 Å3 to 480.8 Å3 by the partial substitution of smaller Zn2+ (0.74 Å for CN = 6) for larger Bi3+ (1.03 Å for CN = 6) in the Bi2WO6 crystal lattice, and the solubility of Zn2+ in the Bi2WO6 lattice is found to be below 17.5 at%. The partial substitution of Zn2+ influences the self-aggregation of nanoparticles, Ostwald ripening, and self-organization of nanoplates, resulting in different morphologies. Although the optical bandgap energy of Bi2WO6 is not significantly altered upon the partial substitution of Zn2+, the conduction and valence bands simultaneously shift upward. Among the Bi2−xZnxWO6+δ photocatalysts, 2.5 at% Zn2+-substituted Bi2WO6 exhibits larger water oxidation photocurrent density (0.316 mA cm−2 at 1.23 VRHE) and the highest photocatalytic activity for the photodegradation of PFHxA (k1 = 0.012 min−1). The trapping experiments confirm that the photo-excited holes (h+) and superoxide radicals (O2˙−) are the major reactive species involved in the photodegradation of PFHxA. Liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF/MS) reveals that decarboxylation and defluorination are the main possible routes for the photodegradation of PFHxA over Bi2−xZnxWO6+δ photocatalysts. Our findings suggest that the partial Zn2+-to-Bi2+ substitution can enhance the photocatalytic activity of Bi2WO6 for the degradation of PFAS.Fil: Hojamberdiev, Mirabbos. Technishe Universitat Berlin; AlemaniaFil: Larralde, Ana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Instituto Nacional de Tecnologia Industrial. Gerencia Operativa de Desarrollo Tecnologico E Innovacion. Sub Gerencia Operativa de Energia y Movilidad.; ArgentinaFil: Vargas Balda, Ronald Eduardo. Universidad Nacional de San Martin. Instituto Tecnologico de Chascomus. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - la Plata. Instituto Tecnologico de Chascomus.; ArgentinaFil: Madriz Ruiz, Lorean Mercedes. Universidad Nacional de San Martin. Instituto Tecnologico de Chascomus. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - la Plata. Instituto Tecnologico de Chascomus.; ArgentinaFil: Yubuta, Kunio. Kyushu University; JapónFil: Sannegowda, Lokesh Koodlur. Vijayanagara Sri Krishnadevaraya University; IndiaFil: Sadok, Ilona. Medical University Of Lublin (medical University Of Lublin);Fil: Krzyszczak Turczyn, Agnieszka. Medical University Of Lublin (medical University Of Lublin); . Maria Curie-Skłodowska University in Lublin; PoloniaFil: Oleszczuk, Patryk. Medical University Of Lublin (medical University Of Lublin); . Maria Curie-Skłodowska University in Lublin; PoloniaFil: Czech, Bożena. Medical University Of Lublin (medical University Of Lublin); . Maria Curie-Skłodowska University in Lublin; Poloni