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Acetaminophen, also known as paracetamol (APAP), is a highly utilized pharmaceutical agent on a global scale, particularly in the field of pediatrics. Regrettably, an overdose of APAP, resulting from the predominant oxidation, has the potential to trigger acute liver injury. The study's goal was to find an easy, accurate, and selective way to measure APAP, N-acetyl para benzoquinone imine (NAPQI) (an APAP metabolite that is harmful), and N-acetyl-l-cysteine (NAC) (an antidote). Two different chromatographic methods were used. The HPTLC method, which used silica gel 60 F254 as a stationary phase and a developing liquid made up of methanol, ethyl acetate, and glacial acetic acid (8:2:0.2, v/v/v) and a UV detection at 254 nm. The HPLC method was developed using a mobile phase consisting of water, methanol, and formic acid in a proportion of (70:30:0.15, v/v/v). The stationary phase used in the approach was a C18 column. Analytes quantification was established utilizing a UV detector operating at a wavelength of 254 nm. The present methods make it possible to measure the amount of APAP in plasma samples. When it comes to pharmacokinetics or medication levels in children's plasma, for example, this may be also very helpful. The current methods can quantify NAPQI, which is helpful in figuring out drug concentrations in individuals with APAP intoxication diagnoses. Additionally, the current approaches can estimate NAC as an antidote; as a result, this study is a complete study because it can analyse drug, toxic metabolite, and antidote in one analytical run. Using the innovative blue applicability grade index software, which measures the practicality of procedures, both methodologies were compared with a reported methods. Additionally, the achievement of the eco-friendliness profile of the designed procedures was assessed. Both techniques passed the ICH validation tests. [ABSTRACT FROM AUTHOR]

The process of aging was crucial in enhancing the aroma quality of Huangjiu. Gas chromatography electronic nose (GC-E-Nose), gas chromatography-mass spectrometry (GC–MS), and gas chromatography-ion mobility spectrometry (GC-IMS) were employed to detect the variations in aroma among five samples aged for varying years (5–11). A comprehensive analysis revealed the presence of 85 compounds in the Shaoxing Huangjiu, twenty of which were identified as crucial contributors to its flavor profile through odor activity values analysis. The volatile aroma components of Huangjiu exhibited notable variations among different aging years. Additionally, the concentration and diversity of key aroma compounds increased with prolonged aging. At the same time, quantitative descriptive sensory analysis showed that aging could enhance the ester and acid aroma of Huangjiu. Moreover, based on variable importance for the projection, seven potential aroma markers such as diethyl succinate, ethyl butyrate, and furfural were screened out, which were the major compounds that caused the flavor differences of aged Huangjiu. The results offer valuable theoretical support for illustrating and regulating the quality of Huangjiu during its aging process. [ABSTRACT FROM AUTHOR]

Background: The attribution of drug-induced liver injury (DILI) to specific herbal and dietary supplements (HDS) is confounded by inaccurate labels and undisclosed ingredients. The US Drug-Induced Liver Injury Network (DILIN) determines the attribution of injury to an agent through its structured expert opinion causality assessment process, but without the use of chemical analysis data of HDS. We aimed to determine the impact of chemical analysis of HDS products on prior causality assessment scores. Methods: Obtained samples of HDS consumed by DILIN-enrolled patients were analyzed by high-performance liquid chromatography-mass spectrometry (HPLC-MS). Chemical analysis data were compared to label accuracy and detect whether the product contained botanical and non‐botanical compounds. A comparison of the causality scores reassessed with chemical analysis was compared with the original scores. Results: A total of 54 previously adjudicated cases with chemical analysis available were reassessed for causality with chemical analysis data; reviewers were blinded to original causality scores. Using the chemical analysis data, 37% (n = 20) of the 54 cases were scored with a higher likelihood of DILI compared with the original causality scores; 14 of the 20 (70%) moved from probable to highly likely; 52% had no change in causality score; and 11% of cases were scored as a lower likelihood of DILI. Conclusions: Our study demonstrates that there is value in using HDS chemical analysis data in the causality assessment process for DILI. In more than a third of cases, chemical analysis of products led to an increased confidence in DILI attribution to HDS. These findings suggest that chemical analysis is an important tool in causality assessment for HDS agents, specifically in challenging situations, and further studies are needed to confirm its applicability in clinical practice. [ABSTRACT FROM AUTHOR]

Bruton's tyrosine kinase inhibitors (BTKis) exhibit significant interindividual pharmacokinetics, making therapeutic drug monitoring (TDM) a promising approach for personalized therapy. However, simultaneous quantification of multiple BTKis poses technical challenges. A unified protocol for BTKis detection would be clinically desirable. Herein, we developed and validated a novel LC-MS/MS method for the simultaneous analysis of four BTKis including ibrutinib (IBR), zanubrutinib (ZAN), orelabrutinib (ORE), and acalabrutinib (ACB) and active metabolite of IBR and ACB (DIH and ACBM, respectively) in human plasma. The samples were prepared by liquid-liquid extraction using tert-butyl methyl ether. Ibrutinb-d4 (IS) was used as an internal standard. Chromatographic separation was obtained on an XBridge C18 column and connected to an LC-30AD system coupled to an API 4000+ mass spectrometer. The mobile phase comprised 10 mM ammonium acetate containing 0.1% formic acid and acetonitrile containing 0.1% formic acid. The optimized multiple reaction monitoring transitions of m/z 441.4 → 138.3, 475.4 → 304.2, 472.5 → 455.5, 428.3 → 411.5, 466.1 → 372.2, 482.2 → 388.4, and 445.5 → 142.5 were selected to inspect IBR, DIH, ZAN, ORE, ACB, ACBM, and IS, respectively. The method exhibited linearity from 1 to 1000 ng/mL (r > 0.99) for all analytes, with intra-day and inter-day precision of 1.8 to 9.7% and accuracy below 15%. Recovery ranged from 90.4 to 113.6%, and matrix effect varied from 89.3 to 111.0%. All compounds demonstrated stability under relevant conditions. Application of the method to 57 blood samples from 18 patients demonstrated high interpatient variability, with ORE plasma concentrations ranging from 25.6 to 89.9%. The validated LC-MS/MS method provides a feasible, specific, and rapid approach for quantification of BTKis in clinical settings. Simultaneous determination of four BTKis and their metabolites in a single extraction process and chromatographic run reduces analysis time, cost, and resources. The observed variability among individuals highlights the value of TDM for personalized treatment. [ABSTRACT FROM AUTHOR]

Dried urine spots have recently been proposed as an alternative matrix in the anti-doping field. Drying urine may open the opportunity to limit microbial and thermal degradation of the prohibited substances during transportation to the anti-doping laboratories without the need for refrigeration or freezing. In this study, a multi-targeted initial testing procedure was developed for the determination of 237 prohibited drugs/metabolites from 11 different classes in dried urine spots. The comparability between two different microsampling techniques (i.e., Whatman® FTA DMPK-C cards and Mitra® tips) was evaluated. The developed method was then used to evaluate the stability of the target compounds in urine for 7 days under different environmental conditions to simulate the transportation of the urine samples from the collection sites to anti-doping laboratories. Sample preparation consists of (i) extraction of the analytes from the collection device using a mixture of acetonitrile/methanol (1/1) for 30 min at 40 °C, (ii) enzymatic hydrolysis, and (iii) sample concentration by solid-phase extraction. Analysis was performed using liquid chromatography coupled to high-resolution mass spectrometry. The entire workflow was validated in terms of specificity (analytes were distinguishable from the matrix interferences), sensitivity (only with the Mitra® tips the limits of detection comply with the World Anti-Doping Agency's requirements for the majority of the target compounds), carry-over (no signals in the negative urine injected after the positive urine), matrix effect (16–28% for Mitra® tips and 22–35% for DMPK-C cards), and extraction yield (Mitra® tips: 51–88%; DMPK-C cards: 40–76%). As proof of concept, authentic urine samples were analyzed: results obtained in dried urine were compared with those of fluid urine, providing good agreement. Stability studies showed that the target compounds were stable for the whole duration of the study (7 days) at −20 and 4 °C in both fluid and dried urine. At 50 °C or at 20–25 °C, several thiazide-based compounds were completely degraded to their degradation product in the first 24 h or after 3–4 days in fluid urine, whereas in dried urine the compounds were detectable for the entire duration of the study. [ABSTRACT FROM AUTHOR]

The wide range of mass spectrometry imaging (MSI) technologies enables the spatial distributions of many analyte classes to be investigated. However, as each approach is best suited to certain analytes, combinations of different MSI techniques are increasingly being explored to obtain more chemical information from a sample. In many cases, performing a sequential analysis of the same tissue section is ideal to enable a direct correlation of multimodal data. In this work, we explored different workflows that allow sequential lipid and elemental imaging on the same tissue section using atmospheric pressure laser desorption/ionisation-plasma post-ionisation-MSI (AP-MALDI-PPI-MSI) and laser ablation-inductively coupled plasma-MSI (LA-ICP-MSI), respectively. It is found that performing lipid imaging first using matrix-coated samples, followed by elemental imaging on matrix-coated samples, provides high-quality MSI datasets for both lipids and elements, with the resulting distributions being similar to those obtained when each is performed in isolation. The effect of matrix removal prior to elemental imaging, and of performing elemental imaging first were also investigated but found to generally yield lower quality elemental imaging data but comparable lipid imaging data. Finally, we used the ability to acquire both elemental and lipid imaging data from the same section to investigate the spatial correlations between different lipids (including ceramides, phosphatidylethanolamine, and hexosylceramides) and elements within mouse brain tissue. [ABSTRACT FROM AUTHOR]

The analysis of the volatile compounds released by biological samples represents a promising approach for the non-invasive diagnosis of a disease. The present study, focused on a population of dogs infected with canine leishmaniasis, aimed to decipher the volatolomic profile associated with this disease in dogs, which represent the main animal reservoir for Leishmania pathogen transmission to humans. The volatiles emitted by the breath and hair of dogs were analysed employing the gas chromatography-mass spectrometry (GC–MS) technique. The acquired chromatograms were investigated using a novel algorithm developed in this study for automated chromatographic peak detection and matching in untargeted GC–MS analysis, which includes various steps that comprise noise reduction, m/z filtering, background subtraction, peak detection, peak matching, and generation of a peak table for compounds identification. The results revealed one tentative breath volatile biomarker and five tentative hair volatile biomarkers for the cutaneous form of the disease, which is characterised by skin ulcerations. Additionally, nine tentative breath volatile biomarkers and four tentative hair volatile biomarkers were found for the visceral form of the disease, which affects internal organs such as spleen, liver and bone marrow. All tentative biomarkers identified in this study were upregulated in cutaneous leishmaniasis, while in visceral leishmaniasis, all tentative biomarkers were upregulated in the breath and only one out of four in the hair. Only one compound (glyceryl monooleate) was identified as tentative volatile biomarker for both forms of the disease, in the hair of dogs. [ABSTRACT FROM AUTHOR]

Recently in the USA, kratom consumers increasingly report use of the plant for self-treatment of mood ailments, the lack of energy, chronic pain, and opioid withdrawal and dependence. Several alkaloids are present in kratom leaves, but limited data are available on their pharmacokinetics/pharmacodynamics, except for mitragynine. To support clinical studies, a high-performance liquid chromatography-tandem mass spectrometry assay for the simultaneous quantification of 11 kratom alkaloids in human plasma was developed and validated. For calibration standards and quality control samples, human plasma was fortified with alkaloids at varying concentrations, and 200 µL were extracted employing a simple one-step protein precipitation procedure. The extracts were analyzed using LC-MS/MS including electrospray ionization (ESI) in positive multiple reaction monitoring (MRM) mode. The lower limit of quantification was 0.5 ng/mL, and the upper limit of quantification was 400 ng/mL for all analytes. Inter-day analytical accuracy and imprecision ranged from 98.4 to 113% of nominal and from 3.9 to 14.7% (coefficient of variance), respectively. The analysis of plasma samples collected during a clinical trial administering capsules containing kratom leaf extract showed that most samples had quantifiable concentrations of mitragynine, 7-OH-mitragynine, speciogynine, speciociliatine, and paynantheine and that mitragynine, speciogynine, and speciociliatine accumulated in human plasma after daily administration over 15 days. An LC-MS/MS assay for the specific quantification of kratom alkaloids including mitragynine and its main metabolites was developed and successfully validated in human plasma. Human plasma samples collected following multiple oral administrations of a controlled Kratom extract documented accumulation of kratom alkaloids over 15 days. [ABSTRACT FROM AUTHOR]

Interest in bile acids (BAs) is growing due to their emerging role as signaling molecules and their association with various diseases such as colon cancer and metabolic syndrome. Analyzing BAs requires chromatographic separation of isomers, often with long run times, which hinders BA analysis in large studies. Here, we present a high-throughput method based on liquid chromatography-tandem mass spectrometry to quantify BAs in mouse samples. After acidic protein precipitation in the presence of a comprehensive mixture of stable isotope-labeled internal standards (SIL-ISs), BAs are separated on a biphenyl column by gradient elution at basic pH. Quantification is performed using a six-point calibration curve. Except for the separation of β- and ω-muricholic acid (MCA) species, a rapid separation of 27 BA species was achieved in a run time of 6.5 min. Plasma quality controls (QCs) were used to evaluate intra- and inter-day precision. The CV was less than 10% for most BA species and exceeded 20% only for glycohyodeoxycholic (GHDCA) and taurohyodeoxycholic acid (THDCA) due to the lack of a corresponding SIL-IS. The limit of quantification (LoQ) was tested using diluted QCs and was found to be compromised for some BA species as a result of insufficient isotopic purity of the SIL-IS, leading to significant interference with the respective analyte. Finally, we tested the mouse sample material requirements for plasma, bile, and liver samples and determined BA concentrations in C57/BL6N wild-type mice. In conclusion, the LC–MS/MS method presented here permits a rapid and reproducible quantification of the major murine BAs. [ABSTRACT FROM AUTHOR]

Developing new sensors presenting low-cost, portability, and disposability features is of paramount in the electrochemical field. Thus, this work proposes the fabrication of lab-made composite electrodes using acrylonitrile butadiene styrene, graphite, and aluminum oxide. In this investigation, the amount of aluminum oxide (0 to 12.25 w/w) was carefully optimized, and its impact on the electrochemical performance of the electrode was observed using the ferri-ferro redox probe and dopamine (DOP) as a proof of concept. This innovative electrode was characterized by spectroscopy, morphological, elemental, and electrochemical techniques. Using the alumina-loaded electrode, significantly improved cyclic voltammetric responses regarding peak currents and peak-to-peak separation were obtained for both evaluated species. This sensor was integrated into the batch injection analysis system for amperometric monitoring of DOP in synthetic biological fluids (saliva and urine) and tap water. The developed method showed a wide linear range (10 to 1000 µmol L−1), a low detection limit (2.6 µmol L−1), and a high analytical frequency (182 analyses per hour). Furthermore, it was precise (RSD < 5%), accurate (recoveries between 90.5 and 107.3%), and selective. Therefore, it can be considered a low-cost alternative analytical tool for electrochemical sensing of DOP in samples of clinical and environmental interest. [ABSTRACT FROM AUTHOR]

Introduction: Rapid detection and identification of pathogens and antimicrobial susceptibility is essential for guiding appropriate antimicrobial therapy and reducing morbidity and mortality associated with sepsis. Objectives: The metabolic response of clinical isolates of Klebsiella oxytoca exposed to different concentrations of ciprofloxacin (the second generation of quinolones antibiotics) were studied in order to investigate underlying mechanisms associated with antimicrobial resistance (AMR). Methods: Metabolomics investigations were performed using Fourier-transform infrared (FT-IR) spectroscopy as a metabolic fingerprinting approach combined with gas chromatography-mass spectrometry (GC-MS) for metabolic profiling. Results: Our findings demonstrated that metabolic fingerprints provided by FT-IR analysis allowed for the differentiation of susceptible and resistant isolates. GC-MS analysis validated these findings, while also providing a deeper understanding of the metabolic alterations caused by exposure to ciprofloxacin. GC-MS metabolic profiling detected 176 metabolic features in the cellular extracts cultivated on BHI broth, and of these, 137 could be identified to Metabolomics Standards Initiative Level 2. Data analysis showed that 40 metabolites (30 Level 2 and 10 unknown) were differentiated between susceptible and resistant isolates. The identified metabolites belonging to central carbon metabolism; arginine and proline metabolism; alanine, aspartate and glutamate metabolism; and pyruvate metabolism. Univariate receiver operating characteristic (ROC) curve analyses revealed that six of these metabolites (glycerol-3-phosphate, O-phosphoethanolamine, asparagine dehydrate, maleimide, tyrosine, and alanine) have a crucial role in distinguishing susceptible from resistant isolates (AUC > 0.84) and contributing to antimicrobial resistance in K. oxtytoca. Conclusion: Our study provides invaluable new insights into the mechanisms underlying development of antimicrobial resistance in K. oxytoca suggests potential therapeutic targets for prevention and identification of AMR in K. oxytoca infections. [ABSTRACT FROM AUTHOR]

A series of supported Ni phosphide bifunctional hydroisomerization catalysts (Ni2P/ZSM-23/Al2O3) was synthesized by means of Ni hypophosphite reduction at different temperatures. The structure and morphology of Ni phosphide phase were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The surface chemical analysis was performed using X-ray photoelectron spectroscopy (XPS). The hydro/dehydrogenation and acid functions of catalysts were characterized by CO chemisorption, NH3-TPD and IR-spectroscopy of adsorbed pyridine (IR-Py). The reduction of supported precursor at the temperature lying in the range of 550–650 ⁰С resulted in high activity and iso-selectivity in n-decane conversion. The reduction of the supported component at 500 ⁰C or re-reduction of ex-situ reduced and passivated catalysts at 450 ⁰C led to the formation of impurities of other Ni phosphides such as NiP and Ni5P4 and had a negative impact on n-decane conversion. Both the Brønsted acidity and Ni2P dispersion of the catalysts declined with increasing Ni2P content which were accompanied by a drop in their activity without loss of iso-selectivity. [ABSTRACT FROM AUTHOR]

The presence of natural and synthetic toxic compounds in the environment requires the development of advanced detection methods. Here we review proteomics technologies for toxicity screening, with focus on principles, current status, mass spectrometry-based proteomics, protein microarray, and in-frame tagging method. Concerning mass spectrometry-based proteomics, we detail liquid chromatography-tandem mass spectrometry, label-free quantification, and thermal proteome profiling. We discuss the integration of the latest advances in proteomics technologies, such as single-cell proteomics, data-independent acquisition, and multi-omics approaches. [ABSTRACT FROM AUTHOR]

A comprehensive investigation was undertaken on the mineralogy of ordinary magnetite concentrate to achieve ultra-pure iron concentrate. Various analytical methods, including chemical analysis, X-ray fluorescence spectroscopy, optical microscopy, scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM-EDS), and mineral liberation analysis were employed. The analysis revealed that the ordinary magnetic concentrate had a TFe grade of 65.56%, accompanied by Al2O3 and SiO2 contents of 0.38% and 8.28%, respectively. The valuable mineral identified in the sample was magnetite, constituting 89.01%, exhibiting a liberation degree of 90.66%. The predominant gangue minerals, quartz and amphibole, exhibited low liberation degrees of 24.11% and 20.94%, respectively. Subsequently, a combined beneficiation process involving shaking table separation and reverse flotation was conducted. Experimental results demonstrated that ultra-pure concentrate with a TFe grade of 72.20% and recovery of 51.54% was obtained through one stage of shaking table separation, roughing flotation, and four cleaning flotation stages. The ultra-pure magnetite was further confirmed by XRD analysis, magnetic susceptibility measurement, and SEM-EDS analysis. The successful implementation of this process will provide a benchmark for producing similar ultra-pure magnetite concentrates. [ABSTRACT FROM AUTHOR]

Contamination by arsenic (As) is a pressing environmental and public health issue requiring urgent remediation strategies. One cost-effective and eco-friendly method involves adding stabilizing agents to soils to reduce As mobility. However, remediation projects must also address potential ecotoxicological effects. These effects may include harmful impacts on both aquatic and terrestrial organisms, including plants, disruption of ecosystem balance, and the potential bioaccumulation of toxic substances in the food chain. Biochar from organic fraction of municipal solid waste (OFMSW) shows promise for As-contaminated soil remediation. Pot experiments were conducted with soil contaminated with As (100 mg kg−1) and amended with biochar produced at three different temperatures (300, 500, and 700 °C) and addition rates (1 and 5%, w/w). Chemical fractionation showed higher As concentration in a less accessible fraction (F4). Biochar amendments did not significantly differ from the control in As immobilization, but enhanced maize (Zea mays) growth and reduced As uptake, with the most promising results seen with 1% of biochar produced at 700 °C. The bioaccumulation factor (BCF) and translocation factor (TF) were both lower than 1, indicating a low absorption of As and minimal translocation from the root to the shoot. The bioaccessible percentage was higher in the samples treated with biochar compared to the control. According to the results, biochar showed no satisfactory potential for As immobilization and its approach of pretreatment/modification should be tested regarding possible improvements in the immobilization performance of As. Since most contaminations involve multiple contaminants simultaneously, it is essential to test the interactions between arsenic and other pollutants to understand the effects of biochar in such complex scenarios, which will be explored in future studies. [ABSTRACT FROM AUTHOR]

Sanghuangporus vaninii. mycelial polysaccharides (SIP) are difficult to apply in food and pharmaceuticals due to their high molecular weight and low bioavailability. Therefore, a method is urgently needed to reduce its molecular weight to improve its bioactivity. In this study, the response surface methodology was used to optimize the process conditions for ultrasonic modification of SIP (SIP concentration of 0.5 mg/mL, ultrasonic power of 510 W, and ultrasonic time of 3.5 h) to prepare ultrasonic-Sanghuangporus vaninii. mycelial polysaccharides (USIP). The analysis of physical and chemical properties and biological activities of SIP and USIP confirmed that compared with SIP, the total sugar, uronic acid, and sulfuric acid groups in USIP increased, while the protein content decreased slightly. Ultrasound did not alter the primary structure of the polysaccharides, which have longer side chains and more branched chains, and neither has a triple helical structure. The molecular weight of USIP is significantly lower and exhibits a degree of homogeneity compared to SIP, while the monosaccharide composition of USIP is altered. The apparent morphology of USIP is more fragmented than that of SIP, with the appearance of pores and grooves. The antioxidant and bacteriostatic properties of USIP were significantly improved compared to SIP, and ultrasound improved the biological activity of polysaccharides. These results indicate that ultrasound is an efficient and green polysaccharide modification method to produce value-added polysaccharides for use in functional foods or pharmaceuticals, providing a theoretical basis for applying SIP. [ABSTRACT FROM AUTHOR]

In the present research, a novel and effective electrochemical sensing strategy for the trace measurement of zearalenone (ZEA) was investigated. The sensing platform is based on a Vulcan XC-72R carbon (VC)-Metal azolate framework (MAF) composite, which was utilized to modify a low expense carbon paste electrode (VC-MAF/CPE). The electrochemical characterization of the VC-MAF/CPE was studied using cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry and electrical impedance spectroscopy (EIS) analyses. The effect of buffer pH, modifier dosage and buffer type were also optimized using differential pulse voltammetry (DPV) method. The calibration range for ZEA detection was found to be 0.8 to 110 ng mL− 1 under optimal experimental conditions. The detection limit was calculated to be 0.15 ng mL− 1, based on S/N = 3. The selectivity of the sensor was evaluated against various interferents, including dopamine, ascorbic acid, glucose, fructose, and sucrose. Real sample analysis was successfully conducted using the suggested assay, demonstrating its applicability for ZEA detection in corn and wheat samples. In addition, the sensor exhibited good reproducibility with RSD value of 3.25%. This work shows the effectiveness of the VC-MAF/CPE sensor for ZEA determination in agricultural samples. [ABSTRACT FROM AUTHOR]

Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied toward the development of luminescent materials. However, previous studies have mainly focused on CT transitions between d- and π-orbitals. Herein, we report the demonstration of CT emission from 4f- to π-orbitals using a trivalent europium (Eu(III)) complex, supported by both experimental and theoretical analyses. The Eu(III) complex exhibits an eight-coordination structure, comprising three anionic nitrates and two neutral electron-donating ligands containing a carbazole unit. The diffuse reflectance spectrum of the complex displays an absorption band at 440 nm and time-resolved emission analyses reveal a characteristic emission band at 550 nm. Comparative studies employing a trivalent gadolinium (Gd(III)) complex, alongside quantum chemical analyses, confirm that the observed absorption and emission bands are associated with CT transitions between π- and 4f-orbitals. The observation of CT emission based on the 4f-orbital offers novel insights into the field of molecular luminescence science and technology. Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied, but primarily limited to CT transitions between d- and π-orbitals. Here, CT emission from 4f- to π-orbitals is demonstrated using a trivalent europium complex. [ABSTRACT FROM AUTHOR]

This study presents an investigation of the chemical composition of Aloe vera leaf tissue with a focus on the spatial distribution of compounds. The composition was studied using two mass spectrometry imaging techniques: silver-109 nanoparticles assisted laser desorption/ionization mass spectrometry imaging (109AgNPs-LDI-MSI) and laser ablation-remote atmospheric pressure photoionization/chemical ionization mass spectrometry imaging (LARAPPI/CI-MSI) and the identification was aided by ultra-high-performance liquid chromatography and ultra-high-resolution mass spectrometry (UHPLC-UHRMS) analysis. The results showed an abundance of phenolic compounds with antioxidant, antimicrobial, and anti-inflammatory properties, making it a beneficial food additive and food packaging material. Analysis of the results of mass spectrometry imaging provided information about the potential changes in metabolic pathway expression in different regions of the leaf. [ABSTRACT FROM AUTHOR]

In the present study, dispersive solid phase extraction – hydride generation integrated with micro–sampling gas–liquid separator – flame atomic absorption spectrometry was proposed to determine lead in lake water samples taken in the Horseshoe Island, Antarctica. In scope of this study, microwave assisted NiFe2O4 nanoparticles were synthesized, and the characterization of nanoparticles were carried out by FT-IR, XRD and SEM. All influential parameters of dispersive solid phase extraction and hydride generation were optimized to enhance signal intensity belonging to the analyte. System analytical performance studies were performed, and limit of detection and limit of quantitation were calculated as 2.16 µg kg–1 and 7.19 µg kg–1, respectively. Recovery studies were conducted to the spiked lake water samples and two different calibration strategies were applied. Percent recovery results were calculated between 102.0 and 169.5% by external calibration strategy while matrix matching calibration strategy provided recovery results in the range of 78.8–142.9%. [ABSTRACT FROM AUTHOR]

Aflatoxin B1 (AFB1) is a highly strong mycotoxin that contaminates cereals and other stored grains. It causes immune-suppressive effects, raising the risk of mutagenicity, carcinogenicity, teratogenicity, hepatotoxicity, and embryonic toxicity, as well as increasing illness and death. Liver damage is a result of prolonged exposure to AFB1, which raises the prevalence of liver cancer and cirrhosis. Different biosensors have been fabricated using various nanoparticles to detect aflatoxins in food. This review provides the recent developments on the occurrence of AFB1 in cereals, different biosensors based on nanomaterials applied for AFB1 detection in cereals, and offers future directions for the production of affordable analytical equipment for detection of AFB1, based on nanomaterials to address some open questions regarding their limit of detection, stability, and affordability. Electrochemical biosensors are more reliable, selective, and affordable analytical tools with better detection limits and shorter response times than other biosensors. However, more studies are needed to address the automatic simultaneous detection of various aflatoxins in real samples and a biosensing system that integrates with microarray technology. [ABSTRACT FROM AUTHOR]

Urinary proteomics is emerging as a potent tool for detecting sensitive and non-invasive biomarkers. At present, the comparability of urinary proteomics data across diverse liquid chromatography−mass spectrometry (LC-MS) platforms remains an area that requires investigation. In this study, we conduct a comprehensive evaluation of urinary proteome across multiple LC-MS platforms. To systematically analyze and assess the quality of large-scale urinary proteomics data, we develop a comprehensive quality control (QC) system named MSCohort, which extracted 81 metrics for individual experiment and the whole cohort quality evaluation. Additionally, we present a standard operating procedure (SOP) for high-throughput urinary proteome analysis based on MSCohort QC system. Our study involves 20 LC-MS platforms and reveals that, when combined with a comprehensive QC system and a unified SOP, the data generated by data-independent acquisition (DIA) workflow in urine QC samples exhibit high robustness, sensitivity, and reproducibility across multiple LC-MS platforms. Furthermore, we apply this SOP to hybrid benchmarking samples and clinical colorectal cancer (CRC) urinary proteome including 527 experiments. Across three different LC-MS platforms, the analyses report high quantitative reproducibility and consistent disease patterns. This work lays the groundwork for large-scale clinical urinary proteomics studies spanning multiple platforms, paving the way for precision medicine research. Urinary proteomics offers sensitive, non-invasive biomarkers, but cross-platform LC-MS data comparability requires investigation. Here, the authors evaluate 20 LC-MS platforms, developing MSCohort, a QC system with 81 metrics, and a unified SOP, paving the way for precision medicine research. [ABSTRACT FROM AUTHOR]

The presence of traces of herbicides in ground and surface waters can have adverse impacts on humans and the environment. Therefore, developing a highly selective and reusable adsorbent for monitoring water quality has become important. This article describes smart green molecularly imprinted polymers (MIPs) as selective sorbents of S-metolachlor herbicide for solid phase extraction (SPE). Combining the MIP-SPE column with HPLC chromatography provided a quick and accurate method for determining the real concentration of S-metolachlor in water samples. The sorption capacity of the MIP-SPE column was almost twice that of the non-imprinted polymer column for SPE extraction. The bed can be regenerated up to three times before it loses its original sorption properties. A method has been developed whereby 6 ml of water can achieve an average recovery rate of 98% for sorbent. During the selectivity study from multicomponent solution, the calculate imprinting factor for MIPs was calculated to be 10, while MIPs sorb S-metolachlor 10 times better than atrazine, 12 times better than fenoxaprop-P-ethyl and 33 times better than glyphosate. The pseudo-second-order kinetic model was in good agreement with the experimental values obtained. [ABSTRACT FROM AUTHOR]

The widespread use of sub-therapeutic antibiotics may lead to treatment failures, increased resistance to antibiotics, and even the encouragement of the formation of superbugs. Fraudulent herbal medicines that actually contain unlabeled active ingredients are a global problem. Therefore, streamlined and accurate analytical techniques that can identify and quantify a variety of antimicrobials in suspected illegal products are required. In the present work, we developed a sensitive, robust, and accurate method that involves multi-step extraction, EMR-lipid-based pass-through cleanup, and UHPLC-Q/HRMS with an orbital ion trap instrument analysis for the simultaneous detection of ten illicit antifungal drugs (flucytosine, fluconazole, ketoconazole, naftifine hydrochloride, griseofulvin, bifonazole, econazole nitrate, elubiol, clotrimazole, and miconazole nitrate) in herbal disinfection products. This validated method was then applied to 210 authentic samples, resulting in 25% of the samples being positive for the drugs. The results suggested the need to strengthen controls in this field to detect illicit antifungal drugs in herbal bacteriostatic products, which represents a potential health risk for the consumer. On a global scale, more and more frequent routine monitoring is being carried out in this area. This study provides valuable insights into large-scale complex sample chemical profiling, and the method developed appears to be promising and applicable for high-throughput routine multiple antibiotic analysis in a complex sample matrix. [ABSTRACT FROM AUTHOR]

In crime investigations, the unambiguous identification of biological traces can be decisive for framing the events. In this study, we applied proteomics to analyze scant amounts of biological residues in the context of an alleged rape case, focusing on the detection of traces of vomit. We used high-performance liquid chromatography-tandem mass spectrometry (HPLC–MS/MS) and two distinct proteomic workflows to identify proteins and possible proteolytic peptides in biological residues from clothing, bedding, and car upholstery from the alleged crime scene. Specifically, a fragment of pillowcase contained a protein pattern indicative of human saliva and a complex panel of peptides resulting from extensive hydrolysis of salivary proteins. The presence of partly digested proteins from bovine meat, wheat, and eggs, along with salivary and gastric enzymes, demonstrated the presence of vomit on the alleged victim's trousers, also providing insights into the recently consumed meal. A drop of cow's milk on the seat of the suspect's car was likely irrelevant to the criminal act. Other fabric samples showed only common contaminants, excluding significant biological traces or food-derived proteins. These findings support the judicial decision regarding consent to sexual intercourse, for which DNA individualization lacks evidentiary power, and establish a reference for annotating saliva and vomit traces in forensic investigations. [ABSTRACT FROM AUTHOR]

Ubiquitous environmental occurrence of per- and polyfluoroalkyl substances (PFAS) underscores the critical need to broaden investigative efforts in effective screening, risk assessment, and remediation. Owing to the broad spectrum of PFAS, various analytical techniques have been extensively utilized to attain inclusivity, with notable attention given to methods such as extractable organic fluorine (EOF), adsorbable organic fluorine (AOF), and the total oxidizable precursor (TOP) assay. These techniques expand the scope of PFAS analysis by estimating perfluoroalkyl acid precursors or the total organochlorine fraction. This review offers a comprehensive comparative overview of up-to-date methodologies, alongside acknowledging the inherent limitations associated with their applications. When coupled with target analysis via low-resolution tandem mass spectrometry, these techniques offer a potential estimation of total PFAS concentrations. Yet, analytical challenges such as the limited availability of reference analytical standards, partial PFAS adsorption, and the entrapment of fluorinated inorganic anions on adsorbent materials often restrict the comprehensiveness of PFAS analysis. So, integrating nontarget analysis using high-resolution mass spectrometry (HRMS) tools fortifies these PFAS mass balance approaches, enabling the development of a more holistic approach for an environmental analysis framework. This review provides additional insights into the comparative advantages of PFAS analytical approaches and explores various data prioritization strategies in nontarget screening methods. It advocates for the necessary optimization of PFAS extraction methods, asserting that integrating the nontarget approach would foster the establishment of a comprehensive monitoring framework across diverse environmental matrices. Such integration holds promise for enhancing scientific comprehension of PFAS contamination across diverse environmental matrices. [ABSTRACT FROM AUTHOR]

The rapid increase in the production and global use of chemicals and their mixtures has raised concerns about their potential impact on human and environmental health. With advances in analytical techniques, in particular, high-resolution mass spectrometry (HRMS), thousands of compounds and transformation products with potential adverse effects can now be detected in environmental samples. However, identifying and prioritizing the toxicity drivers among these compounds remain a significant challenge. Effect-directed analysis (EDA) emerged as an important tool to address this challenge, combining biotesting, sample fractionation, and chemical analysis to unravel toxicity drivers in complex mixtures. Traditional EDA workflows are labor-intensive and time-consuming, hindering large-scale applications. The concept of high-throughput (HT) EDA has recently gained traction as a means of accelerating these workflows. Key features of HT-EDA include the combination of microfractionation and downscaled bioassays, automation of sample preparation and biotesting, and efficient data processing workflows supported by novel computational tools. In addition to microplate-based fractionation, high-performance thin-layer chromatography (HPTLC) offers an interesting alternative to HPLC in HT-EDA. This review provides an updated perspective on the state-of-the-art in HT-EDA, and novel methods/tools that can be incorporated into HT-EDA workflows. It also discusses recent studies on HT-EDA, HT bioassays, and computational prioritization tools, along with considerations regarding HPTLC. By identifying current gaps in HT-EDA and proposing new approaches to overcome them, this review aims to bring HT-EDA a step closer to monitoring applications. [ABSTRACT FROM AUTHOR]

The disinfection of drinking water, while critical for public health, leads to the formation of disinfection byproducts (DBPs). Toxicological and epidemiological studies have demonstrated that exposure to disinfected water samples may pose adverse effects on human health. Recent research highlights the potential greater toxicity contribution of DBP fractions with high molecular weight (MW) (with more than two carbon atoms) compared to regulated low MW DBPs, emphasizing the need for advanced analytical techniques to identify and characterize these fractions. In this review, we summarize different analytical techniques for indirectly assessing DBP precursors and directly analyzing DBPs, discussing their advantages and limitations. Additionally, since identifying DBP toxicity agents in complex water mixtures is crucial for further optimizing water disinfection and controlling DBP formation, key DBP identification methods based on both chemical and bioassay metrics are also included and discussed. Finally, we highlight three important aspects for the future development of analytical methods to enhance the understanding of high MW DBP formation. [ABSTRACT FROM AUTHOR]

Ciprofloxacin (CIP) is an extensively used broad-spectrum, fluoroquinolone antibiotic used for treating diverse bacterial infections. Effluent treatment plants (ETPs) worldwide lack technologies to detect or remediate antibiotics. CIP reaches the aquatic phase primarily due to inappropriate disposal practices, lack of point-of-use sensing, and preloaded activated charcoal filter at ETPs. The co-existence of bacteria and CIP in such aqueous pools has promoted fluoroquinolone resistance in bacteria and should be minimized. The worldwide accepted standard detection methodologies for the detection of CIP are high-performance liquid chromatography and mass spectrometry, which are lab-based, require state-of-the-art equipment, and are expensive. Hence, it is difficult to integrate them for on-site monitoring. Further, the current remediation technologies like conventional sludge-treatment techniques fail to remove antibiotics such as CIP. Several point-of-use technologies for the detection of CIP are being investigated. These typically involve the development of electrochemical sensors where substrates, modifiers, biorecognition elements, and their chemistries are designed and optimized to enable robust, point-of-use detection of CIP. Similarly, remediation techniques like adsorption, membrane filtration, ion exchange, photocatalysis, ozonation, oxidation by Fenton's reagent, and bioremediation are explored, but their onsite use is limited. The use of these sensing and remediation technologies in tandem is possibly the only way the issues related to antimicrobial resistance may be effectively tackled. This article provides a focused critical review on the recent advances in the development of such technologies, laying out the prospects and perspectives of their synergistic use to curb the menace of AMR and preserve antibiotics. [ABSTRACT FROM AUTHOR]

The deployment of liquid chromatography-mass spectrometry-based plasma proteomics experiments in a large cohort is sparse, leading to a lack of data available for benchmarking, method development or validation. Comprised of 6,426 plasma analyses, The Environmental Determinants of Diabetes in the Young (TEDDY) proteomics validation study constitutes one of the largest targeted proteomics experiments in the literature to date. The proteomics data from this study were generated over the course of 2.5 years from over 900 study subjects, each providing up to 29 longitudinal samples. The data also includes 916 quality control samples. The targeted mass spectrometry assay was comprised of 694 peptides mapping to 167 proteins and the panel was measured in each subject and QC sample. The targeted proteomic dataset presented here can be used as a resource for new computational methods development, such as for batch correction, as well as for benchmarking and comparing the performance of different methods/tools. [ABSTRACT FROM AUTHOR]

White and Green Analytical Chemistry are innovative approaches in analytical chemistry that prioritize both sustainability and efficiency. Together, these approaches aim to advance scientific research while minimizing environmental impact and enhancing safety. This integration of environmental consciousness into analytical practices represents a significant step forward in achieving sustainable scientific progress. In the present study, a sensitive eco-friendly HPLC-DAD method was carried out and validated to allow concurrent determination of Donepezil HCl (DPZ) and Curcumin (CUR) in their pure form and laboratory made nano-liposome formulation. Optimum seperation was accomplished by utilising Zobrax Eclipse Plus C18 column (4.6*100 mm,5 μm) with gradient elution of the mobile phase composed of 0.02 M phosphate buffer at pH 3.2 and ethanol at flow rate of 1.5 ml/min. A diode array detector (DAD) was implemented for detection at 273 nm and 435 nm for DPZ and CUR, respectively, with the column oven set at 40 °C. The method was validated according to ICH specifications in terms of accuracy, precision, linearity range, detection and quantification limit. The calibration plots were linear with correlation coefficients (r2) = 0.999 over the range (0.1–100 µg/ml) and (0.1–100 µg/ml) for DPZ and CUR, successively. The validated HPLC-DAD approach was adopted to analyse both medications in laboratory prepared nano-liposomal formulation in which the analytes were successfully quantified with good recovery values and no disrubtion from the added excipients. The investigation of whiteness, blueness, and greenness metrics revealed a major benefit of the suggested approach over previous reported ones. [ABSTRACT FROM AUTHOR]

Background: As the common antibacterial drugs in folic acid oral liquid, parabens are listed as mandatory substances in the quality standard. Both the Chinese Pharmacopoeia and the United States Pharmacopoeia use high performance liquid chromatography for the determination of folic acid, but the quantitative methods of parabens are different. Pharmacopoeias use different instruments to quantify folic acid and parabens, resulting in cumbersome and cumbersome detection methods. Objective: Without changing the type of instrument and mobile phase, two methods were established for the determination of folic acid and parabens (methyl paraben; ethyl paraben; propyl paraben) using respective wavelengths and flow comparisons Propyl benzoate) high performance liquid chromatography method. Method: Chromatographic separation was achieved on an Agilent 5 TC-C18 HPLC column (5 μm; 250 μm × 4.6 mm) maintained at 25 °C (column temperature). The mobile phase consisted of phosphate buffer (pH 4.0)-methanol. When the ratio is 99:1, it is used to determine the content of folic acid, and when the ratio is 79:21, it is used to determine the content of antimicrobial agents. The flow rate used was 1.2 mL/min, the injection volume of folic acid was 20 µL, and the injection volume of bacteriostatic agent was 50 µL. In addition, the blue applicability grade index (BAGI) and analytical greenness (AGREE) metric tools were used to evaluate the greenness and environmental friendliness of the developed methods. Results: The method has a good linear relationship with R2 ≥ 0.9995, the average recovery rate of the two methods is ≥ 95%, and the relative standard deviation (RSD%) accuracy is less than 0.21%. The BAGI tool characterizes the developed method as green. The AGREE score is around 0.5, and the method is also largely consistent with the principles of green analytical chemistry. Conclusions: The HPLC method was established for the rapid determination of folic acid and antibacterial agent of parabens in folic acid. The method has high accuracy, strong specificity, high recovery rate, good stability and environmental friendliness. Compared with the method in the pharmacopoeia, it has strong resistance to complex matrix interference, greatly shortens the detection time, and has little damage to the instrument and chromatographic column. It can be used for the quality standard of folic acid oral liquid. [ABSTRACT FROM AUTHOR]

A simple, rapid, and reproducible high-performance liquid chromatography (HPLC) method has been developed and validated for the determination of β-sitosterol in the pharmaceutical dosage form of moist exposed burn ointment (MEBO). This method involved an effective sample procedure for extraction of β-sitosterol from MEBO using an alkali saponification agent composed of 0.8 N ethanolic NaOH and diethyl ether. The chromatographic separation was achieved on a C18 column (50 × 3.0 mm, 2.5 μm), using a mobile phase composed of methanol and acetonitrile (70:30 v/v) pumped in an isocratic mode at a flow rate of 0.7 mL/min. The column temperature was maintained at 40 °C, the injection volume was 10 µL, and the detection wavelength was 203 nm. Employing these conditions, the retention time was found to be 2.10 min. The developed method was validated for its specificity, linearity, accuracy, precision, the limit of detection, the limit of quantification, robustness, and solution stability based on International Council for Harmonisation (ICH) guidelines Q2 (R1). Our proposed method demonstrated superior performance compared to other reported methods. It exhibited a linearity range of 30 to 500 µg/mL and improved detectability with a limit of detection (LOD) of 4.65 µg/mL, highlighting its high sensitivity. Additionally, the separation was achieved in a remarkably short analysis time of just 2.1 min, which not only enhanced throughput but also significantly minimized waste and solvent consumption, thereby making it a more sustainable and effective alternative for β-sitosterol extraction. Moreover, in the light of green and white analytical chemistry, a comprehensive ecological and sustainable tri-color coded assessment protocol was established. The proposed method has been successfully applied to quantify β-sitosterol in commercial products (MEBO®, Avomeb® and BISTROl®) demonstrating its suitability for routine quality control analysis of β-sitosterol in pharmaceutical ointment dosage forms. Highlights: Quality control for evaluating MEBO anti-burn ointment is crucial The first study for the determination of β-sitosterol in MEBO A challenge in its extraction from the complex oily matrix of MEBO ointment Analytical Greenness, Blueness, and whiteness evaluation [ABSTRACT FROM AUTHOR]

The quest for sustainability, renewability, manufacturing cost efficiency and environmental friendliness in composite science and technology is ongoing, due to numerous benefits. In this research, mature stems of the Cayratia pedata (lam.) gagnep plant were harvested, and their long fibers were extracted through water retting and comprehensively characterized as a potential reinforcement for polymer matrix composites (PMCs). The results showed that Cayratia pedata (lam.) gagnep fibers (CPGF) with a lower density of 1158.00 ± 52 kg/m3 supported fabrication of PMCs with less weight and high strengths. Hemicellulose and cellulose of 16.47 ± 3.26 and 65.21 ± 5.31 wt% were obtained from CPGF via chemical analysis, respectively. Its crystallinity index of 67.84% confirmed comparatively higher crystalline material. Fourier transform infrared analysis identified the different functional groups in CPGF. The thermal degradation analysis of CPGF demonstrated its suitability as a reinforcing material in PMCs up to a fabrication temperature of 250 °C. The higher kinetic activation energy of CPGF at 97.40 kJ/mol also established its improved thermal stability. The outer shell of the CPGF had debris and non-cellulosic materials, as examined through a scanning electron microscope. Due to impurities, lignin and hemicellulose, untreated fibers were smoother than desired. The mean tensile strength of CPGF was 424.40 ± 24.45 MPa. Weibull distribution was employed to statistically investigate the single CPGF tensile properties. In summary, it can be concluded that CPGF is a better alternative, sustainable, renewable, low-cost and environmentally friendly reinforcing material when compared extensively with several similar plant fibers. [ABSTRACT FROM AUTHOR]

With recent evolution of cannabis legalization around the world and multiplication of cannabis derived products, identifying and qualifying cannabis consumption has a proven interest. Although blood, plasma, and urine are common matrices widely used in toxicology laboratories, oral fluid presents specific advantages. In the context of doping tests, addiction consultation or roadside checks, where other matrices are impractical to collect or can be adulterated, oral fluid is a promising matrix that allows a non-invasive, rapid, and monitored self-sampling. However, available devices required a consequent volume of oral fluid, more than 250 µL, sometimes difficult to collect. We present here a fully optimized quantitative method for seven cannabinoids, including four metabolites, in oral fluid, Δ9-tetrahydrocannabinol, 11-hydroxy-Δ9-tetrahydrocannabinol and 11-nor-9-carboxy-Δ9-tetrahydrocannabinol; cannabidiol, 7-hydroxy and 7-carboxycannabidiol; and cannabinol. After self-collection of 20 µL using an accurate and precise volumetric absorptive microsampling device (VAMS®), cannabinoids were derivatized with 2-fluoro-1-methylpyridinium p-toluenesulfonate to increase sensitivity. The successive steps of the proposed method, including biosampling, 1 h sample preparation with derivatization, and acquisition by ultrahigh-performance liquid chromatography coupled to high-resolution mass spectrometry, were fully optimized. A limit of quantification of 0.5 ng/mL (≈10 pg per sampling) was thus targeted, adapted to the legal threshold required by the authorities and to clinical monitoring. Applied to six cannabis consumers, the proposed method made it possible to quantify in 20 µL oral fluid samples, Δ9-tetrahydrocannabinol ranging from 0.5 to 6236 ng/mL, cannabidiol from 0.6 to 190 ng/mL and cannabinol from 0.5 to 118 ng/mL. [ABSTRACT FROM AUTHOR]

There is growing interest in road pollution that enters surface waters. Additive chemicals used in the manufacture of plastics, including tyre rubber, are mobile pollutants that pose a threat to aquatic life. Therefore, an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was developed to measure 25 plastic additive chemicals in road runoff and water of retention ponds used to manage road runoff. A straightforward direct injection methodology was adopted to minimise sample handling and risk of contamination. Using this approach, the method quantitation limits (MQLs) ranged from 4.3 × 10−3 to 13 µg/L. These were adequate to determine most chemicals at or below their freshwater predicted no-effect concentration (PNEC). Method trueness ranged from 18 to 148% with most chemicals being within 80–120%. The method was applied to water from four retention ponds in series to measure additive chemicals entering the ponds (i.e., in road runoff) and passing through each pond. Greatest concentrations were observed in road runoff during heavy rainfall following dry weather. Here, 1,3-diphenylguanidine (DPG) exceeded its current PNEC of 1.05 µg/L. Notably, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine-quinone (6PPD-quinone) was determined at 0.13 µg/L which is greater than its lowest acute toxicity threshold (0.095 µg/L). Similarity in additive chemical concentrations throughout the retention ponds during steady flow suggests little or no removal occurs. However, further studies are needed to assess the fate and removal of plastic additive chemicals in retention ponds and the risk posed to aquatic environments. Such research can be facilitated by this newly developed UHPLC-MS/MS method. [ABSTRACT FROM AUTHOR]

The analysis of serum for biomarkers is a standard method in clinical diagnosis and health assessment. The application of Raman spectroscopy to probe biomarkers in serum is increasingly investigated due to its time- and cost-efficiency. However, time-consuming sample preparation is often required to analyze the serum samples. Additionally, hemolyzed samples are commonly discarded due to interference in the measurements. This study focuses on the application of the online coupling of size exclusion chromatography (SEC) to diode array detector (DAD) and capillary-enhanced Raman spectroscopy (CERS) for direct analysis of hemolyzed serum samples. We demonstrate that different protein classes such as serum albumin and immunoglobulin G (IgG) can be identified in hemolyzed serum according to a calculated hit quality index (HQI). Additionally, different oxidation and binding states of the heme prosthetic group are investigated at 532-nm excitation. The online coupling of SEC-DAD-CERS enables the detailed characterization of blood serum proteins, including the differentiation of IgG, serum albumin, and hemoglobin. [ABSTRACT FROM AUTHOR]

The analysis of polar analytes with the help of hydrophilic interaction liquid chromatography (HILIC) using classic methods of high-performance liquid chromatography is not without its downsides. In these applications, acetonitrile is prevalent as main eluent and sample diluent. This results not only in slow diffusion processes during the separation, but also in often unstable sample solutions where polar analytes are concerned. Furthermore, there are ecological concerns. With the use of supercritical fluid chromatography (SFC) which uses supercritical carbon dioxide as eluent, and other green solvents as alternative for the sample preparation, the separation of polar analytes could be vastly improved with this technique. Fast diffusion within carbon dioxide led to shorter analysis times and higher plate numbers. Regarding sample diluents, small alcohols such as ethanol and 2-propanol, as well as acetone, yielded promising results while analytes showed higher solubility and stability within these solvents compared to acetonitrile. Other green solvents such as dihydrolevoglucosenone (Cyrene) and dimethyl carbonate were found to be unsuitable sample diluents for applications in SFC. [ABSTRACT FROM AUTHOR]

Quality control (QC) samples are commonly used in metabolomics approaches for three main reasons: (i) the initial conditioning of the column; (ii) the correction of analytical drift especially between batches; and (iii) the evaluation of measurement precision. In practice, there are several ways to prepare and conserve QC samples. The most common in untargeted metabolomics is to pool samples after or before extraction, in order to obtain pooled QC samples accounting, respectively, for analytical variance or for both analytical and sample preparation variances. In this study, focusing on untargeted analysis of tea (Camellia sinensis) leaves, we compared three ways of preparing pooled QC samples (two usual and one unusual QC sample preparations) and their efficiency to improve data quality in terms of inter-batch correction, measurement precision, and VIP candidates selection on datasets obtained using two mass spectrometry (MS) technologies (Orbitrap and time of flight (QToF)). We also investigated the effect of data processing modalities, based on the different QC preparations, on data loss and on the global structure of the datasets. Generally, our results show that usual QC sample preparation leads to comparable datasets quality in terms of precision and dispersion on both MS instruments. They also show that QC preparation is crucial for VIP selection; in fact, up to 54% of biomarkers candidates were specific of the QC preparation type used for data processing. [ABSTRACT FROM AUTHOR]

The development of a newly fabricated ion-selective electrode (ISE) solid-contacted type for the determination of prucalopride succinate represents a significant advancement in analytical chemistry, particularly in the context of green chemistry principles. The optimization process involved numerous trials to ensure the selection of a cation exchanger and ionophore that offer high sensitivity and selectivity for prucalopride succinate. Through these optimization trials, sodium tetrakis was identified as the most suitable cation exchanger, while calix [8] arene demonstrated the highest affinity towards prucalopride succinate as the ionophore. This careful selection of components ensures accurate and specific detection of prucalopride succinate. To enhance the electroanalytical performance of the ISE, a graphene nanocomposite layer was developed as an ion-electron transducer between the carbon and synthetic polymeric membrane. This graphene-nanocomposite layer improves the overall performance of the ISE, providing a Nernstian slope of 57.249 mV per decade, which aligns with the recommendations of the International Union of Pure and Applied Chemistry (IUPAC). The integration of these components and the utilization of green chemistry principles in the design of the fabricated ISE enable rapid and accurate determination of prucalopride succinate. This innovative approach holds great potential for applications in pharmaceutical analysis and quality control, providing a more sustainable and efficient method for the analysis of prucalopride succinate. [ABSTRACT FROM AUTHOR]

1,4-Azaborine-based arenes are promising electroluminescent emitters with thermally activated delayed fluorescence (TADF), offering narrow emission spectra and high quantum yields due to a multi-resonance (MR) effect. However, their practical application is constrained by their limited operational stability. This study investigates the degradation mechanism of MR-TADF molecules. Electroluminescent devices incorporating these compounds display varied operational lifetimes, uncorrelated with excitonic stability or external quantum efficiency roll-off. Bulk electrolysis reveals significant instability in the radical cationic forms of MR-TADF compounds, with device lifetime linked to the Faradaic yield of oxidation. Comprehensive chemical analyses corroborate that the degradation byproducts originated from intramolecular cyclization of radical cation, followed by hydrogen atom transfer. The mechanism is further supported by enhanced stability observed in a deuterated MR-TADF emitter, attributed to a secondary kinetic isotope effect. These findings provide insights into the stabilizing effects of deuteration and mechanism-driven strategies for designing MR-TADF compounds with improved operational longevity. The limited operational stability of multi-resonance thermally activated delayed fluorescence emitters often constrains their practical application. Here, the authors report a direct correlation between device lifetime and Faradaic yield for oxidative degradation of emitter molecules. [ABSTRACT FROM AUTHOR]

A practical, rapid, and reliable method for the ultra-trace determination of 90Sr by triple quadruple collision/reaction cell inductively coupled plasma mass spectrometry (CRC–ICP–MS/MS) has been developed. Suitable sample preparation was investigated, and the chemical separation has been achieved with the decontamination factor over 1 × 105 for interfering nuclide 90Zr. The concentrations of 90Sr in two kinds of samples were determined successfully, with the average values of 7.2 ± 0.7 fg·g−1, 5.0 ± 0.5 fg·g−1, respectively. The ratios of 90Sr to 88Sr were 5.2 × 10–8, 2.2 × 10–9, respectively, and the instrumental detection limit of 90Sr was 0.09 pg·g−1. [ABSTRACT FROM AUTHOR]

The pH optical sensors work on the principle of pH-related changes in the absorption or emission of a probe. They have generated much interest during the past decades due to their wide applications in fields such as analytical chemistry, biochemistry, clinical medical diagnosis, and environmental monitoring. Two ruthenium(II) polypyridine complexes, [Ru(bpy)2(hipp)]2+ (Ru1) and [Ru(bpy)2(dcipp)]2+ (Ru2), were chosen as pH probes. Here, bpy denotes 2,2-bipyridine, hipp denotes 2-(1H-imidazo [4,5-f][1,10]phenanthrolin-2-yl)phenol, and dcipp denotes 2,4-dichloro-6-(1H-imidazo[4,5-f] [1,10]phenthrolin-2-yl)phenol, respectively. The pH effects on the absorption and emission spectra of Ru1 and Ru2 were investigated by pH titrations. Ru1 and Ru2 were found to be pH-sensitive and revealed different ionization constants, suggesting their potential use as optical pH sensors and applications in environmental monitoring. [ABSTRACT FROM AUTHOR]

Tin sulfide (SnS) semiconductors have become emerging sensor materials for the electrochemical sensing of heavy metals in trace amounts due to their supportive electrochemical properties. This study reports the synthesis, characterization of SnS/rGO composites and sensing of mercury and lead ions in an aqueous solution. SnS/rGO composites with the proper loading of rGO concentration were synthesized using simple solvothermal method and applied for sensing the heavy metals of mercury and lead ions. The synthesized samples were characterized by XRD, FE-SEM, TEM, FTIR and Raman spectroscopy to study the structure and morphology of the samples. Cyclic voltammetry and AC impedance were used to characterize the samples for electrochemical detection of toxic metals Hg and Pb ions. The XRD analysis reveals that the average crystallite of SnS/rGO nanoplates is in the range of 56–67 nm and was confirmed by TEM. FE-SEM analysis reveals the formation of nanoplates on rGO sheets. Raman spectroscopy and FTIR analysis confirm the presence of rGO and the composition of the prepared sample. The electrochemical sensing of SnS and SnS/rGO nanoplates with graphite powder in 0.1 M KOH solution showed good reversibility and was applied for sensing of HgCl2 and PbCl2 with a quick response time of 2 s. The LOD for Hg and Pb ions was found to be 47.3–65.3 ppm, respectively. All the prepared electrodes of SnS and SnS/rGO composites could be effectively supported by the electrochemical sensing response to HM ions in alkali medium. [ABSTRACT FROM AUTHOR]

The synthesis of new functionalized silica gel with immobilized thiosemicarbazone fragments by the reaction of aldehyde silica gels with thiosemicarbazide in an ethanol medium in the presence of a catalytic amount of hydrochloric acid is described. The material was characterized by thermogravimetric analysis and infrared spectroscopy data. Effective solid-phase extraction of Sn(II) and Hg(II) using synthesis organomineral material—silica with immobilized thiosemicarbazone fragment has been demonstrated. Determination of Sn(II) and Hg(II) in samples whose matrix excludes the possibility of direct ETAAS (electrothermal atomic absorption spectrometry) determination, for example in sea waters, an approach has been proposed to replace the matrix of the analyzed sample with a sorbent matrix based on modified silica. ETAAS conditions for the determination and preconcentration of Sn(II) and Hg(II) in the sorbent used with slurry sampling have been described. The proposed methodology for determination Sn(II) and Hg(II) was tested on the example of sea water of the Black Sea, fresh tap water and mineral drinking water "Esentuki." The error of determination was no more than 10% rel. The detection limit for mercury was 50 ng/L, tin 7 ng/L. The concentration factor is 100 for both elements. The advantage of the developed ETAAS approach for the determination of mercury and tin in comparison with other spectroscopic methods (ICP-AES, ICP-MS) is shown. [ABSTRACT FROM AUTHOR]

Remote analysis of the chemical composition of various substances in real time is a pressing problem. Current development of the fiber based evanescent wave spectroscopy (FEWS) in the mid-infrared range meets modern industrial, environmental, safety and medical needs. This paper presents a sensitivity analysis of the fiber probes for FEWS based on bent chalcogenide fibers as sensing elements. A previously developed methodology is applied to study the sensitivity of bent fiber tapers and bent fibers of constant diameter immersed in a liquid analyte. The wave optics based approach is used in calculations of the attenuation coefficients of the bend modes in the COMSOL Multiphysics solver. For evaluation of the bent fiber taper transmittance, the method of local modes is applied. The sensitivity analysis is carried out for the probes made of chalcogenide fibers of Ge20Se80 composition immersed in an aqueous solution of isopropyl alcohol with concentrations of 0 to 50 vol.%. The results of FEWS measurements with the U-shaped fiber taper of a certain geometry are used for assessment of the analysis outcomes. The role of light launching conditions in the operation of a fiber probe is discussed. [ABSTRACT FROM AUTHOR]

The Vaccinium genus, with over 200 species, is prized for its fruits and traditional medicinal uses. Introduced to South America in the 1980s, it has become a significant crop, particularly in Tucumán, Argentina. Southern highbush blueberries are the most cultivated. Recent research suggests that the leaves and stems of these species contain higher levels of beneficial compounds compared to fruits. This study explores the potential of V. myrtillus L. leaves and stems, typically discarded as agricultural waste, as sources of bioactive compounds. It provides the first detailed analysis of their anatomy and chemical composition, revealing high levels of phenolic compounds with antioxidant properties. Leaf extracts show stronger antioxidant activity compared to stems. Toxicity tests on Artemia salina indicate their safety for further exploration. These findings suggest that V. myrtillus L. waste by-products could be valuable as sources of bioactive compounds, promoting their application in pharmaceuticals, food, or cosmetics industries. [ABSTRACT FROM AUTHOR]

Chemical genetics is a multidisciplinary research method. In this study, it is used to screen compounds that promote aluminum-induced malate secretion in Arabidopsis thaliana. Inhibition of p38 mitogen-activated protein kinase (p38 MAPK; LY2228820) significantly increased the transcription of Arabidopsis thaliana aluminum-activated malate transporter 1 (AtALMT1) and sensitive to proton rhizotoxicity 1 (STOP1)-regulated genes, multidrug and toxic compound extrusion and aluminum sensitive 3, but not AtSTOP1 and the Al-biomarker genes At3g28510, At5g13320, suggesting that LY2228820 increased the early expression of STOP1-regulated genes without affecting AtSTOP1 expression. Inhibition of p38 MAPK (LY2228820) and Aurora A (MLN8237) increased aluminum-activated malate transport via AtALMT1, suggesting that both MLN8237 and LY2228820 interfere with AtALMT1 activity. An increase in root elongation was also observed in Arabidopsis after applying compounds LY2228820 and MLN8237. Thus, both LY2228820 and MLN8237 may play important roles in alleviating the inhibitory effects of aluminum on roots. [ABSTRACT FROM AUTHOR]