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The fishy odor of fish oil, a popular nutritional supplement, affects its quality as well as consumer acceptance and eating experience. An objective or scientific method for analyzing fish oil's olfactory characteristics is still lacking. This study examined anchovy oil to develop qualitative and quantitative approaches for identifying fishy odor components. Multiple fish oil refining samples were analyzed using gas chromatography-ion mobility spectrometry (GC-IMS). Due to their significant alterations during fish oil refining, low threshold values, and distinct olfactory properties, the unsaturated aldehydes (E)-2-pentenal and (E,E)-2,4-heptadienal and the unsaturated ketone 1-penten-3-one may contribute to the fishy odor. Among the chemicals, (E,E)-2,4-heptadienal was chosen as the marker for developing a method to quantify fishy odor and analyze deodorization samples using headspace solid-phase micro-extraction gas chromatography-mass spectrometry (HS-SPME-GC-MS). The quantitative study of fishy odor in fish oil is a pioneering approach that can help improve quality assurance and refining process. [ABSTRACT FROM AUTHOR]

Per- and polyfluorinated alkyl substances (PFASs) are a group of anthropogenic chemicals used in a range of industrial processes and consumer products. Recently, their ubiquitous presence in the environment as well as their toxicological effects in humans have gained relevant attention. Although the occurrence of PFASs is widely investigated in scientific community, the standardization of analytical method for all matrices still remains an important issue. In this review, we discussed extraction and detection methods in depth to evaluate the best procedures of PFAS identification in terms of analytical parameters (e.g., limits of detection (LODs), limits of quantification (LOQs), recoveries). Extraction approaches based on liquid–liquid extraction (LLE), alkaline digestion, and solid phase extraction (SPE), followed by liquid chromatography–mass spectrometry (LC-MS) and gas chromatography–mass spectrometry (GC-MS) analysis are the main analytical methods applied in the literature. The results showed detectable recoveries of PFOA and PFOS in meat, milk, vegetables, eggs products (90.6–101.2% and of 89.2–98.4%), and fish (96–108%). Furthermore, the low LOD and LOQ values obtained for meat (0.00592–0.01907 ng g−1; 0.050 ng g−1), milk (0.003–0.009 ng g−1; 0.010–0.027 ng g−1), fruit (0.002–0.009 ng g−1; 0.006–0.024 ng g−1), and fish (0.00369–0.017.33 ng g−1; 0.05 ng g−1) also confirmed the effectiveness of the recent quick, easy, cheap, effective, rugged, and safe method (QuEChERS) for simple, speedy, and sensitive ultra-trace PFAS analysis. [ABSTRACT FROM AUTHOR]

Alkaloids are major dietary components well known for their pharmacological activities. Herbal matrices require extensive processing due to their high level of complexity in order to isolate their alkaloidal contents. Molecularly imprinted polymers (MIPs) are tailored receptors with a highly specific molecular recognition, which is the most important function of receptors. They can hence be utilized in applications wherein selective binding activities are of significance, such as solid phase extraction (SPE), chromatographic separation and chemical sensors. This review presents on recent applications of MIPs to analyze alkaloids in plants and bio-fluid samples as well as herbal formulations. We discuss the development of nano-sized MIPs for various applications, particularly in biomimetic sensors for electrochemical detection of various alkaloids. Due to its easier phase separation compared to common MISPEs, magnetic MISPEs were also discussed in order to explore the potential benefits of this approach for further phytochemical applications. [ABSTRACT FROM AUTHOR]

Antimicrobial resistance (AMR) has emerged and spread globally. Recent studies have also reported the presence of antimicrobials in a wide variety of aquatic environments. Conducting a nationwide monitoring survey of AMR in the environment to elucidate its status and to assess its impact on ecosystems and human health is of social importance. In this study, we developed a novel high-throughput analysis (HTA) system based on a 96-well plate solid-phase extraction (SPE), using automated pipetting and an SPE pre-treatment system. The effectiveness of the system as an HTA for antimicrobials in environmental water was verified by comparing it with a conventional manual analytical system in a domestic hospital over a period of two years and four months. The results of the manual analysis and HTA using a combination of automated pipetting and SPE systems were generally consistent, and no statistically significant difference was observed (p > 0.05) between the two systems. The agreement ratios between the measured concentrations based on the conventional and HTA methods were positively correlated with a correlation coefficient of r = 0.99. These results indicate that HTA, which combines automated pipetting and an SPE pre-treatment system for rapid, high-volume analysis, can be used as an effective approach for understanding the environmental contamination of antimicrobials at multiple sites. To the best of our knowledge, this is the first report to present the accuracy and agreement between concentrations based on a manual analysis and those measured using HTA in hospital wastewater. These findings contribute to a comprehensive understanding of antimicrobials in aquatic environments and assess the ecological and human health risks associated with antimicrobials and antimicrobial-resistant bacteria to maintain the safety of aquatic environments. [ABSTRACT FROM AUTHOR]

Urinary proteins have been studied quite exhaustively in the past, however, the small sized peptides have remained neglected for a long time in dairy cattle. These peptides are the products of systemic protein turnover, which are excreted out of the body and hence can serve as an important biomarker for various pathophysiologies. These peptides in other species of bovine have been reported to possess several bioactive properties. To investigate the urinary peptides in buffalo and simultaneously their bioactivities, we generated a peptidome profile from the urine of Murrah Buffaloes (n = 10). Urine samples were processed using <10 kDa MWCO filter and filtrate obtained was used for peptide extraction using Solid Phase Extraction (SPE). The nLC-MS/MS of the aqueous phase from ten animals resulted in the identification of 8165 peptides originating from 6041 parent proteins. We further analyzed these peptide sequences to identify bioactive peptides and classify them into anti-cancerous, anti-hypertensive, anti-microbial, and anti-inflammatory groups with a special emphasis on antimicrobial properties. With this in mind, we simultaneously conducted experiments to evaluate the antimicrobial properties of urinary aqueous extract on three pathogenic bacterial strains: S. aureus, E. coli, and S. agalactiae. The urinary peptides observed in the study are the result of the activity of possibly 76 proteases. The GO of these proteases showed the significant enrichment of the antibacterial peptide production. The total urinary peptide showed antimicrobial activity against the aforementioned pathogenic bacterial strains with no significant inhibitory effects against a buffalo mammary epithelial cell line. Just like our previous study in cows, the present study suggests the prime role of the antimicrobial peptides in the maintenance of the sterility of the urinary tract in buffalo by virtue of their amino acid composition. [ABSTRACT FROM AUTHOR]

Advancing our understanding of dissolved organic matter (DOM) chemistry in aquatic systems necessitates the integration of data streams from multiple analytical platforms. Some measurements require pretreatment with solid phase extraction (SPE), while others are performed directly on whole water samples. Evidence has suggested that SPE will be biased against select DOM fractions, leading to concerns over the ability to establish data linkages across platforms with variable needs for SPE pretreatment, such as those from optical measurements and those that provide high‐resolution molecular information. Here, we directly addressed this concern by assessing the impact of SPE on DOM optical properties through excitation–emission matrices with parallel factor analysis (PARAFAC) for 47 samples across a stream network within a single watershed reflective of variable DOM sources. PARAFAC data was further paired with molecular information obtained by Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). A comparison of PARAFAC models first revealed no systematic qualitative differences in major components between whole water DOM and DOM isolated by SPE (SPE‐DOM); however, quantitative biases against select components were observed. Further linkages with FTICR‐MS data revealed that the molecular fingerprint associated with each PARAFAC component was consistent between the whole water DOM and SPE‐DOM. Our results suggest that bulk scale linkages across these analytical platforms could be inferred irrespective of the observed quantitative biases resulting from SPE for samples within this example watershed. This work represents a key step toward the systematic evaluation of linkages between optical and high‐resolution mass spectrometry datasets in freshwater lotic environments. [ABSTRACT FROM AUTHOR]

Since hop secondary metabolites have a direct correlation with the quality of beer and other hop-based beverages, and the volatile fraction of hop has a complex composition, requiring effective separation, here we explore the application of headspace solid-phase microextraction as a sample preparation method, coupled with comprehensive two-dimensional gas chromatography–mass spectrometry (GC×GC–MS) analysis. The methodology involved the use of a DVB/PDMS fibre with 500 mg of hop cone powder, extracted for 40 min at 50 °C, for both GC–MS and GC×GC–MS. The varieties Azacca, Cascade, Enigma, Loral, and Zappa were studied comprehensively. The results demonstrate that GC×GC–MS increases the number of peaks by over 300% compared to classical GC–MS. Overall, 137 compounds were identified or tentatively identified and categorised into 10 classes, representing between 87.6% and 96.9% of the total peak area. The composition revealed the highest concentration of sesquiterpene hydrocarbons for Enigma, whilst Zappa showed a relatively significant concentration of monoterpene hydrocarbons. Principal component analysis for all compounds and classes, along with hierarchical cluster analysis, indicated similarities between Zappa and Cascade, and Azacca and Loral. In conclusion, this method presents an optimistic advancement in hop metabolite studies with a simple and established sample preparation procedure in combination with an effective separation technique. [ABSTRACT FROM AUTHOR]

The time-consuming nature of many sample treatment protocols continues to be recognized as the main bottleneck of analytical procedures, which, in most cases, use long analysis times, excessive amounts of solvents and reagents, and energy. However, the increased awareness of the need for environmental protection and the development of Green Analytical Chemistry (GAC) has led to significant advancements in the field of sample treatment. Today, advances in the miniaturization of sample treatment techniques, the development of sorbents with tunable properties, and greener alternatives (for example from waste valorization) are gaining interest in the analysis of psychoactive compounds. Indeed, techniques offering rapid sample preparation, minimal use of solvents, reagents, and energy, and a significant reduction of waste generation are chosen by the scientific community. In recent years, non-toxic extraction media, such as ionic liquids, and deep eutectic solvents have emerged as alternatives to petroleum-based solvent extractions. Similarly, sorbent-based techniques have benefited from engineered materials and nanotechnology, incorporating novel sorbents with optimized physicochemical properties to enhance extraction efficiency and selectivity. To meet sustainability standards, GAC provides a wealth of information in the field of green awareness, and the application of green metrics has been extended into the literature in the past decade. These tools serve as guides and encourage scientists to develop the most appropriate methodologies that focus on both analytical performance and sustainability, using different concepts and criteria. This article collects and discusses examples of different sample preparation techniques applied to drug analysis, highlighting their strategies for greening the processes and their evaluation using tools such as HEXAGON, Analytical greenness metric for sample preparation (AGREEprep), and Sample preparation metric of sustainability (SPMS) tools.

Introduction: The presence of pharmaceuticals and personal care products in environmental matrices is considered one of the major scientific concerns. Most of these substances are disposed of unchanged through wastewater treatment plants and sewage systems. Consequently, they are continuously introduced into the water systems and progressively contaminate surface, ground and drinking water. During the COVID-19 pandemic, a large number of emerging contaminants including parabens were released to the environment through various routes. In this study, the occurrence of parabens (methylparaben (MePB), ethylparaben (EtPB), propylparaben (PrPB), and butylparaben (BuPB) was investigated in wastewater samples from various wastewater treatment plants (WWTPs) and the receiving surface waters in KwaZulu Natal and Gauteng Provinces (South Africa).Methods: The samples were collected between October 2020 and December 2021, covering the 2nd, 3rd and 4th waves of the COVID-19 pandemic. A solid phase extraction protocol with high-performance liquid chromatography was used to extract and enrich parabens before analysis.Results and Discussion: Methylparaben (2.02–84.7 μg/L), EtPB (

Clofazimine (CLF) is a riminophenazine derivative and a new therapeutic option with high efficacy for patients with rifampicin-resistant tuberculosis (TB). The blood levels of CLF are low and suboptimal, so therapeutic drug monitoring is required. Prior to this study, there were no molecular imprinting–based solid phase extraction (SPE) sorbents that could be used to determine the blood CLF levels. Hence, we prepared a magnetic molecularly imprinted polymer (MMIPs) to capture CLF. We employed computational selection of a functional monomer and crosslinker and confirmed these selections based on the association constant (Ka) and a Job plot. We synthesised MMIPs with two surface modifiers and characterized the polymers. Our computational analysis based on the bond energy revealed that methyl methacrylate (MMA) was the most suitable functional monomer at a CLF-to-MMA molar ratio of 1:4. Based on the bond energy, the most suitable crosslinker was trimethylolpropane trimethacrylate (TRIM) at a CLF-to-TRIM molar ratio of 1:1. We determined the Ka of MMA and TRIM in different solvents. Isopropanol produced the highest Ka. The Job plot showed that a template-to-MMA-to-TRIM molar ratio of 1:4:20 was optimal to synthesize imprinted polymer in isopropanol. We prepared MMIPs using two different modifiers, namely aminopropyltrimethoxysilane (APTES) and oleic acid (OA), using the ratio determined from the Job plot. Physical characteristic tests carried out using FT-IR, SEM-EDS, PSA, BET and VSM, showed that the synthesis was success with a spherical and uniform agglomeration of particles, also a flat surface with many holes with a particle size of MMIP-APTES and MMIP-OA respectively 0.14 μm and 0.28 μm, showed a surface area for MMIP-APTES is 2874.51 m2/g and MMIP-OA 2913.07 m2/g, exhibiting superparamagnetic properties with a saturation magnetization value of MMIP-APTES 21.1 emu/g−1 and MMIP-OA 49.9 emu/g−1. Adsorption capacity result showed that MMIP-OA fits well with the Langmuir model, while MMIP-APTES fits better with the Freundlich. Application of MMIP-SPE (Magnetic Molecular Imprinted Polymer-Solid Phase Extraction) APTES resulted 92.3 ± 6.1 % and MMIP-SPE-OA 51.5 ± 8.1 % for recovering CLF in blood. The result of selectivity test also showed that MMIP-SPE-APTES is better than MMIP-SPE-OA and selectively recover CLF from human blood plasma existed together with other TB-Drugs. The study result shows that MMIPs with APTES modification can be used for CLF determination in human blood plasma.

Objective To establish a rapid screening method for 34 emerging contaminants in surface water by ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry （UHPLC-Q-TOF-MS）. Methods The pretreatment conditions of solid phase extraction （SPE） were optimized by orthogonal experimental design and the surface water samples were concentrated and extracted by Oasis® HLB and Oasis® MCX SPE columns in series. The extracts were separated by Kinetex® EVO C18 column， with gradient elution of 0.1% formic acid aqueous solution and 0.1% formic acid methanol solution. Q-TOF-MS ‘fullscan’ and ‘targeted MS/MS’ modes were used to detect 34 emerging contaminants and to establish a database with 34 emerging contaminants precursor ion， product ion and retention times. Results The 34 emerging contaminants exhibited good linearity in the concentration range respectively and the correlation coefficients （r） were higher than 0.97. The limit of detection was 0.2-10 ng/L and the recoveries were 81.2%-119.2%. The intra-day precision was 0.78%-18.70%. The method was applied to analyze multiple surface water samples and 6 emerging contaminants were detected， with a concentration range of 1.93-157.71 ng/L. Conclusion The method is simple and rapid for screening various emerging contaminants at the trace level in surface water.

Rationale: Secondary hypertension is often caused by activation of complex multi‐organ endocrine systems, while renin activity indicated by angiotensins (Angs), aldosterone (ALD) and cortisol (COR) in such systems are generally accepted as its diagnostic markers. As antibody‐based methods cannot offer comparable quantification for these biomarkers, a liquid chromatography (LC)–tandem mass spectrometry (MS/MS)‐based approach was developed to quantify them simultaneously and accurately. Methods: Five different beads for magnetic solid‐phase extraction (MSPE) were evaluated towards their enrichment efficiency for these biomarkers. An LC system with optimized elution gradient and a triple‐quadrupole MS with tuned parameters were coupled to quantitatively monitor the extracted analytes. The method performance was further examined such as linearity, precision, stability, recovery rate and matrix effect. Based on the developed method, the abundance of Ang II, ALD and COR in plasma was measured and the quantification was compared with that derived from commercial ELISA kits. Results: As compared with other MSPEs, Angs, ALD and COR were highly enriched by the HLB magnetic beads with satisfactory recoveries. These analytes were simultaneously quantified by LC/MS/MS and all the method parameters for quantification were well matched with the requirements of clinical testing. Comparison of the quantitative results derived from ELISA and LC/MS/MS exhibited that the two methods offered basically comparable values with Pearson r values at 0.896, 0.895 and 0.835, respectively. The stability test for plasma Angs at room temperature indicated that the abundance of Ang II was relatively stable within 3 h, whereas that of Ang I and Ang 1–7 was time‐dependently changed. Conclusions: Coupling of HLB beads and LC/MS/MS thus enables simultaneous quantification of a set of biomarkers related to secondary hypertension. [ABSTRACT FROM AUTHOR]

Rationale: The volatile organic compounds (VOCs) of Lonicerae Japonicae flos (LJF) and Lonicera flos (LF) play a pivotal role in determining their sensory characteristics, medicinal properties, and subsequent impact on market pricing and consumer preferences. However, the differences and specificity of these VOCs remain obscure. Hence, it is crucial to conduct a comprehensive characterization of the VOCs in LJF and LF and pinpoint their potential differential VOCs. Methods: In this study, headspace gas chromatography–ion mobility spectrometry (HS‐GC/IMS) and headspace solid‐phase microextraction gas chromatography–mass spectrometry (HS‐SPME‐GC/MS) were employed to comprehensively investigate the compositional characteristics and distinctions in VOCs between LJF and LF. Multivariate statistical analysis was used to identify candidate differential VOCs of LJF and LF samples. Results: A total of 54 and 88 VOCs were identified using HS‐GC/IMS and HS‐SPME‐GC/MS analysis, respectively. Primary VOCs detected in LJF include leaf alcohol, (E)‐2‐hexen‐1‐ol dimer, 2‐octyn‐1‐ol, and (E)‐3‐hexen‐1‐ol. Key VOCs prevalent in LF encompass farnesol, heptanoic acid, octanoic acid, and valeric acid. Multivariate statistical analysis indicates that compounds such as phenethyl alcohol and leaf alcohol were selected as potential VOCs for distinguishing between LJF and LF. Conclusion: This research conducted a comprehensive analysis of the fundamental volatile components in both LJF and LF. It subsequently elucidated the distinctions and specificities within their respective VOC profiles. And this study enables differentiation between LJF and LF through the analysis of VOCs, offering valuable insights for enhancing the quality control of both LJF and LF. [ABSTRACT FROM AUTHOR]

In this research, a novel magnetic zirconium-based metal-organic framework (Fe3O4@SiO2@MIP-202, MMOF), was fabricated, fully characterized, and applied for the batch-mode solid phase extraction of trace amounts of Pd2+ ions from water and wastewater samples before its spectrophotometric detection. Pd2+ ions were desorbed from MMOF by nitric acid and were complexed by treating with KI solution to have a maximum absorbance at 410 nm. The synthesized MMOF composite showed a very large surface area (65 m2.g− 1), good magnetization (1.7 emu.g− 1) and a large pore volume (0.059 cm3.g− 1) with adsorption capacity of 194.5 mg of Pd2+ ions/g of the adsorbent. This nanosorbent boasts chemo-mechanical stability, high adsorption capacity due to its vast active sites, and facile recovery facilitated by its magnetic properties. Parameters affecting the extraction efficiency of the method were optimized as pH of the sample 7.4, volume of the sample 25 mL, 15 mg adsorbent, 1 mL of 0.1 M HNO3 eluent, with 10 and 15 min as the extraction and desorption times, respectively. The calibration curve was found to be linear across the 10.0–1500.0 µg.L− 1 range with a limit of detection of 1.05 µg.L− 1. The obtained extraction efficiency and enrichment were 98% and 245, respectively. The total analysis time was less than 30 min. This MMOF has never been used for the extraction of Pd2+ ions before. [ABSTRACT FROM AUTHOR]

The sample preparation step is pivotal in glycoproteomic analysis. An effective approach in glycoprotein sample preparation involves enriching glycopeptides by solid-phase extraction (SPE) using polar stationary phases in hydrophilic interaction liquid chromatography (HILIC) mode. The aim of this work is to show how different experimental conditions influence the enrichment efficiency of glycopeptides from human immunoglobulin G (IgG) on an aminopropyl-modified SPE column. Different compositions of the elution solvent (acetonitrile, methanol, and isopropanol), along with varying concentrations of elution solvent acidifiers (formic and acetic acid), and different concentrations of acetonitrile for the conditioning and washing solvents (65%, 75%, and 85% acetonitrile) were tested to observe their effects on the glycopeptide enrichment process. Isopropanol proved less effective in enriching glycopeptides, while acetonitrile was the most efficient, with methanol in between. Higher formic acid concentrations in the elution solvent weakened the ionic interactions, particularly with sialylated glycopeptides. Substituting formic acid with acetic acid led to earlier elution of more glycopeptides. The acetonitrile concentration in conditioning and washing solutions played a key role; at 65% acetonitrile, glycopeptides were not retained on the SPE column and were detected in the flow-through fraction. Ultimately, it was proven that the enrichment method was applicable to human plasma samples, resulting in a significant decrease in the abundances of non-glycosylated peptides. To the best of our knowledge, this study represents the first systematic investigation into the impact of the mobile phase on glycopeptide enrichment using an aminopropyl-modified SPE column in HILIC mode. This study demonstrates the substantial impact of even minor variations in experimental conditions, which have not yet been considered in the literature, on SPE-HILIC glycopeptide enrichment. Consequently, meticulous optimization of these conditions is imperative to enhance the specificity and selectivity of glycoproteomic analysis, ensuring accurate and reliable quantification. [ABSTRACT FROM AUTHOR]

Background: Both in clinical routine and in preclinical research, the established standard procedure for the final purification of radiometal-labeled peptide radiopharmaceuticals is cartridge-based reversed-phase (RP) solid phase extraction (SPE). It allows the rapid and quantitative separation of the radiolabeled peptide from hydrophilic impurities and easy integration into automated synthesis procedures. However, product elution from RP cartridges necessitates the use of organic solvents and product recovery is sometimes limited. Thus, an alternative purification method based on commercially available size exclusion cartridges was investigated. Results: Since most peptide radiopharmaceuticals have a molecular weight > 1 kDa, Sephadex G10 cartridges with a molecular size cut-off of 700 Da were used for the final purification of a broad palette of 68Ga-, 64Cu- and 99mTc-labeled experimental peptide radiotracers as well as the clinically relevant ligand PSMA-617. Results (radiochemical purity (RCP, determined by ITLC), recovery from the solid support) were compared to the respective standard RP-SPE method. Generally, retention of unreacted 68Ga, 64Cu and 99mTc salts on the G10 cartridges was quantitative up to the specified elution volume (1.2 mL) for 68Ga and 99mTc and 99.6% for 64Cu. Even at increased elution volumes of 1.5-2 mL, RCPs of the eluted 68Ga- and 99mTc -radiopeptides were > 99%. For all peptides with a molecular weight ≥ 2 kDa, product recovery from the G10 cartridges was consistently > 85% upon respective adjustment of the elution volume. Product recovery was lowest for [68Ga]Ga-PSMA-617 (67%, 1.2 mL to 84%, 2 mL). The pH of the final product solution was found to be volume-dependent (1.2 mL: pH 6.3; 1.5 mL: pH 5.9; 2 mL: pH 5.5). Notably, the G10 cartridges were reused up to 20 times without compromising performance, and implementation of the method in an automated radiosynthesis procedure was successful. Conclusions: Overall, size exclusion purification yielded all peptide radiopharmaceuticals in excellent radiochemical purities (> 99%) in saline within 10–12 min. Although product recovery is marginally inferior to classical SPE purifications, this method has the advantage of completely avoiding organic solvents and representing a cost-effective, easy-to-implement purification approach for automated radiotracer synthesis. [ABSTRACT FROM AUTHOR]

Background: Brassinosteroids (BRs) are a class of naturally occurring steroidal phytohormones mediating a wide range of pivotal developmental and physiological functions throughout the plant’s life cycle. Therefore, it is of great significance to determine the content and the distribution of BRs in plants.Regretfully, although a large number of quantitative methods for BRs by liquid chromatography-tandem mass spectrometry (LC-MS/MS) have been reported, the in planta distribution of BRs is still unclear because of their lower contents in plant tissues and the lack of effective ionizable groups in their chemical structures. Methods: We stablished a novel analytical method of BRs based on C18 cartridge solid-phase extraction (SPE) purification, 4-(dimethylamino)-phenylboronic acid (DMAPBA) derivatization, and online valve-switching system coupled with ultrahigh performance liquid chromatography-electro spray ionization-triple quadrupole mass spectrometry (UHPLC-ESI-MS/MS). This method has been used to quantify three structural types of BRs (epibrassinolide, epicastasterone, and 6-deoxo-24-epicastaster one) in different organs of Brassica napus L. (rapeseed). Results: We obtained the contents of three structural types of BRs in various organ tissues of rapeseed. The contents of three BRs in rapeseed flowers were the highest, followed by tender pods. The levels of three BRs all decreased during the maturation of the organs. We outlined the spatial distribution maps of three BRs in rapeseed based on these results, so as to understand the spatial distribution of BRs at the visual level. Conclusions: Our results provided useful information for the precise in situ localization of BRs in plants and the metabolomic research of BRs in future work. The in planta spatial distribution of BRs at the visual level has been studied for the first time. [ABSTRACT FROM AUTHOR]

Due to an outbreak of coronavirus spreading in recent years, there is an urgent need for effective, rapid, and non‐invasive diagnostics to detect and differentiate among patients who are infected and uninfected with SARS‐CoV‐2 for controlling the virus propagation. This study developed an alternative method for COVID‐19 screening from volatile analysis of metabolites mainly studied in sweat samples obtained from the populations in Bangkok, Thailand, during December 2020 to April 2022. A total of 140 collected samples; 70 positive confirmed COVID‐19 cases and another 70 negatives confirmed COVID‐19 cases were applied to be separated, detected, and identified as volatile organic compounds (VOCs)/odor occurring from SARS‐CoV‐2 infection body by the technique of Headspace solid‐phase microextraction gas chromatography‐mass spectrometry (HS‐SPME‐GC‐MS) together with principle component analysis (PCA), which allowed potential volatile markers of COVID‐19 such as pentadecane, nonanal, styrene, xylene, ethylbenzene, and 2‐ethylhexyl acrylate (up to 94 % accuracy, 93 % sensitivity, 96 % selectivity, and 94 % specificity), respectively, along with limit of detection in a range of 0.26–125 μg. The result was validated by comparison with the RT‐PCR results. [ABSTRACT FROM AUTHOR]

The antiretroviral drugs (ARVDs) have been reported to be among the emerging water pollutants as a results attention is being paid on their analysis. This work therefore explored for the first time the multi-template MIP for the selective removal of selected ARVDs (abacavir, efavirenz and nevirapine) in wastewater, river water and tap water. The adsorption studies of a multi-template MIP were conducted by determining the effect of an increase in ARVDs concentration in solution and the effect of an increase in contact time between the sorbent and the ARVDs. High adsorption efficiencies were observed for abacavir, efavirenz and nevirapine analytes within 5 min and the maximum adsorption efficiency was observed at 60 min ranging from 94.76 to 96.93%. Adsorption kinetics showed that pseudo-second rate order was the best fitting model, while adsorption isotherms indicated that the Freundlich isotherm (R2 = 0.94–0.98) best described the adsorption mechanism of ARVDs onto the MIPs. These results indicated that the electrostatic attractions influenced the multilayer coverage and chemisorption process. Selectivity studies conducted in the presence of competitors gave the recoveries between 92 and 98% for the target analytes, while they were 63–79% for competitors indicating good selectivity and strong affinity of the polymer towards the target analytes. Reusability studies showed that the MIP can be reused for up to 8 cycles with recoveries above 92% for all target ARVDs. The application of the MIP-DSPE method to wastewater, river and tap water samples gave concentrations of 28.75–178.02, 1.95–13.15 and 2.17–6.27 µg L−1, respectively. These results indicate the potential unplanned consumption of ARVDs upon drinking contaminated water which could result to their resistance by the human body. Therefore, their continuous monitoring as well as investigation of their removal strategies is of paramount importance. [ABSTRACT FROM AUTHOR]

Rationale: Osilodrostat is an inhibitor of 11‐beta‐hydroxylase (CYP11B) and is used for the treatment of Cushing's disease but also categorized as an anabolic agent. The use of osilodrostat is prohibited in horseracing and equestrian sports. To the best of our knowledge, this is the first metabolic study of osilodrostat in equine plasma. Methods: Potential metabolites of osilodrostat were identified by differential analysis using data acquired from pre‐ and post‐administration plasma samples after protein precipitation with liquid chromatography electrospray ionization high‐resolution mass spectrometry (LC/ESI–HRMS). [Correction added on 27 January 2023, after first online publication: In the preceding sentence, "C–HRMS" was changed to "LC/ESI–HRMS" in this version.] For quantification of osilodrostat, a strong cation exchange solid‐phase extraction was employed, and the extracts were analyzed using LC/ESI–triple quadrupole tandem mass spectrometry (LC/ESI–QqQ‐MS/MS) to establish its elimination profile. Such extracts were further analyzed using LC/ESI–HRMS to investigate the detectability of osilodrostat and its identified mono‐hydroxylated metabolite over a 2‐week sampling period. Results: Mono‐hydroxylated osilodrostat was identified based on the differential analysis and mass spectrometric interpretations, and it was found to be the most abundant metabolite in plasma. Elimination profile of osilodrostat in plasma was successfully established over the 24‐h post‐administration period. Both osilodrostat and its mono‐hydroxylated metabolite were detected up to the last sampling point at 2 weeks using HRMS, and osilodrostat could be confirmed up to 8‐day post‐administration with its reference material using HRMS as well. Conclusions: For doping control, screening of both the parent drug osilodrostat and its mono‐hydroxylated metabolite in equine plasma would be recommended due to their extended detection windows of up to 2 weeks. Given the availability of reference material for potential confirmation in forensic samples, osilodrostat is considered the most appropriate monitoring target. [ABSTRACT FROM AUTHOR]

This document is a summary of a special issue of the journal Molecules titled "Mass Spectrometry for Biomedical and Food Analysis." The special issue includes twelve articles that cover the latest advances in mass spectrometry for biomedical and food analysis. The articles discuss topics such as the molecular mechanisms of asthma treatment, biomarker discovery for breast cancer, amino acid metabolic profiling for brain tumor diagnosis, analysis of cyclic tetrapyrroles in biological samples, progress in major depressive disorder research, development of certified reference materials for vinyl acetate and dinotefuran, certification of selenium-enriched yeast reference material, pesticide residue analysis, fragmentation pathways of organophosphorus flame retardants, ginsenoside profiling in steamed Panax quinquefolius, and the determination of A1 and A2 β-casein in milk. The special issue aims to provide valuable information to readers and advance knowledge in the field of mass spectrometry for biomedical and food analysis. [Extracted from the article]

In recent years, there has been a growing interest in plant pigments as readily available nutraceuticals. Photosynthetic pigments, specifically chlorophylls and carotenoids, renowned for their non-toxic antioxidant properties, are increasingly finding applications beyond their health-promoting attributes. Consequently, there is an ongoing need for cost-effective methods of isolation. This study employs a co-precipitation method to synthesize magnetic iron oxide nanoparticles. Scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) confirms that an aqueous environment and oxidizing conditions yield nanosized iron oxide with particle sizes ranging from 80 to 140 nm. X-ray photoelectron spectroscopy (XPS) spectra indicate the presence of hydrous iron oxide FeO(OH) on the surface of the nanosized iron oxide. The Brunauer–Emmett–Teller (BET) surface area of obtained nanomaterial was 151.4 m2 g−1, with total pore volumes of pores 0.25 cm3 g−1 STP. The material, designated as iron oxide nanoparticles (IONPs), serves as an adsorbent for magnetic solid phase extraction (MSPE) and isolation of photosynthetic pigments (chlorophyll a, lutein) from extracts of higher green plants (Mentha piperita L., Urtica dioica L.). Sorption of chlorophyll a onto the nanoparticles is confirmed using UV–vis spectroscopy, Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS), and high-performance liquid chromatography (HPLC). Selective sorption of chlorophyll a requires a minimum of 3 g of IONPs per 12 mg of chlorophyll a, with acetone as the solvent, and is dependent on a storage time of 48 h. Extended contact time of IONPs with the acetone extract, i.e., 72 h, ensures the elimination of remaining components except lutein, with a spectral purity of 98%, recovered with over 90% efficiency. The mechanism of chlorophyll removal using IONPs relies on the interaction of the pigment's carbonyl (C=O) groups with the adsorbent surface hydroxyl (–OH) groups. Based on molecular dynamics (MD) simulations, it has been proven that the selective adsorption of pigments is also influenced by more favorable dispersion interactions between acetone and chlorophyll in comparison with other solutes. An aqueous environment significantly promotes the removal of pigments; however, it results in a complete loss of selectivity. [ABSTRACT FROM AUTHOR]

There is a strong interest in monitoring copper in environmental waters, but its direct analysis suffers from strong matrix interferences. This is why, a sample pretreatment based on solid‐phase extraction (SPE) is often used but conventional sorbents usually lack specificity. It is overcome with ion‐imprinted polymers (IIPs). This work evaluates for the first time the use of the dummy approach for the synthesis of Cu(II)‐targeting IIPs. Two analog ions Ni(II) and Zn(II) were tested as templates and the resulting IIPs were packed in SPE cartridges. The SPE procedure was designed by optimizing a washing step following the sample percolation, to eliminate the interfering ions retained on the IIP by non‐specific interactions. To optimize the washing step, solutions at different pH or containing tris(hydroxymethyl)aminomethane as a complexing agent at different concentrations were tested and combined. Zn‐IIP appeared more promising than Ni‐IIP, showing excellent specificity and a high selectivity. Its retention capacity was determined to be 100 µg/g, and different isotherm models were evaluated to fit with the adsorption data. Finally, applications to mineral and sea waters were successfully completed and led to high and repeatable extraction recoveries for Cu(II) (88 ± 1% and 83 ± 3%, respectively). [ABSTRACT FROM AUTHOR]

The fruits of Sapindus saponaria L., popularly known as 'saboeiro', have been used in medicine. This study evaluated the antioxidant and antitumor activities of the hydroethanolic extract (HAE) and fractions obtained from the fruit pericarp of S. saponaria. The HAE was obtained from the S. saponaria fruit pericarp by maceration; this was followed by fractionation using reversed-phase solid-phase extraction, resulting in fractions enriched with acyclic sesquiterpenic oligoglycosides (ASOG) and saponins (SAP1, and SAP2), confirmed by mass spectrometry with electrospray ionization (ESI-QTOF-MS). The greatest citotoxic activity was observed with the SAP1 fraction against the CaCo2 cell line with a GI50 of 8.1 µg mL−1, while the SAP2 fraction had a GI50 of 13.6 µg mL−1 against CaCo2. The HAE demonstrated the greatest antioxidant activity. S. saponaria has potential therapeutic use in the pharmaceutical industry as a natural anti-oxidant or antitumor product. [ABSTRACT FROM AUTHOR]

Introduction: Skin sensitization, which leads to allergic contact dermatitis, is a key toxicological endpoint with high occupational and consumer prevalence. This study optimized several in vitro assays listed in OECD skin sensitization test guidelines for use on a quantitative high-throughput screening (qHTS) platform and performed in silico model predictions to assess the skin sensitization potential of prioritized compounds from the Tox21 10K compound library. Methods: First, we screened the entire Tox21 10K compound library using a qHTS KeratinoSensTM (KS) assay and built a quantitative structure--activity relationship (QSAR) model based on the KS results. From the qHTS KS screening results, we prioritized 288 compounds to cover a wide range of structural chemotypes and tested them in the solid phase extraction--tandem mass spectrometry (SPE--MS/ MS) direct peptide reactivity assay (DPRA), IL-8 homogeneous time-resolved fluorescence (HTRF) assay, CD86 and CD54 surface expression in THP1 cells, and predicted in silico sensitization potential using the OECD QSAR Toolbox (v4.5). Results: Interpreting tiered qHTS datasets using a defined approach showed the effectiveness and efficiency of in vitro methods. We selected structural chemotypes to present this diverse chemical collection and to explore previously unidentified structural contributions to sensitization potential. Discussion: Here, we provide a skin sensitization dataset of unprecedented size, along with associated tools, and analysis designed to support chemical assessments. [ABSTRACT FROM AUTHOR]

Five carbapenemase enzymes, coined the 'big five', have been identified as the biggest threat to worldwide antibiotic resistance based on their broad substrate affinity and global prevalence. Here we show the development of a molecular detection method for the gene sequences from the five carbapenemases utilising the isothermal amplification method of recombinase polymerase amplification (RPA). We demonstrate the successful detection of each of the big five carbapenemase genes with femtomolar detection limits using a spatially separated multiplex amplification strategy. The approach uses tailed oligonucleotides for hybridisation, reducing the complexity and cost of the assay compared to classical RPA detection strategies. The reporter probe, horseradish peroxidase, generates the measureable output on a benchtop microplate reader, but more notably, our study leverages the power of a portable Raman spectrometer, enabling up to a 19-fold enhancement in the limit of detection. Significantly, the development approach employed a solid-phase RPA format, wherein the forward primers targeting each of the five carbapenemase genes are immobilised to a streptavidin-coated microplate. The adoption of this solid-phase methodology is pivotal for achieving a successful developmental pathway when employing this streamlined approach. The assay takes 2 hours until result, including a 40 minutes RPA amplification step at 37 °C. This is the first example of using solid-phase RPA for the detection of the big five and represents a milestone towards the developments of an automated point-of-care diagnostic for the big five using RPA. [ABSTRACT FROM AUTHOR]

The practice of incorporating animal manure into soil is supported within the European Circular economy as a possible substitute for mineral fertilizers and will become crucial for the sustainability of agriculture. However, this practice may indirectly contribute to the dissemination of antibiotics, resistance bacteria, and resistance genes. In this study, medicated drinking water and poultry litter samples were obtained from a broiler-chick farm. The obtained poultry litter was incorporated into the soil at the experimental field site. The objectives of this research project were first to develop analytical methods able to quantify fluoroquinolones (FQs) in medicated drinking water, poultry litter, and soil samples by LC–MS; second to study the fate of these FQs in the soil environment after incorporation of poultry litter from flock medicated by enrofloxacin (ENR); and third to screen the occurrence of selected fluoroquinolone resistance encoding genes in poultry litter and soil samples (PCR analysis). FQs were quantified in the broiler farm's medicated drinking water (41.0 ± 0.3 mg∙L−1 of ENR) and poultry litter (up to 70 mg∙kg−1 of FQs). The persistence of FQs in the soil environment over 112 days was monitored and evaluated (ENR concentrations ranged from 36 μg∙kg−1 to 9 μg∙kg−1 after 100 days). The presence of resistance genes was confirmed in both poultry litter and soil samples, in agreement with the risk assessment for the selection of AMR in soil based on ENR concentrations. This work provides a new, comprehensive perspective on the entry and long-term fate of antimicrobials in the terrestrial environment and their consequences after the incorporation of poultry litter into agricultural fields. [ABSTRACT FROM AUTHOR]

Here, a simple/efficient analytical strategy based on dispersive solid phase extraction was developed using CoSn(OH)6 nanocubes for lead ions from environmental water samples by FAAS (flame atomic absorption spectrometry). CoSn(OH)6 was synthesized as an adsorbent using the co‐precipitation method and characterized. The characterization studies proved the cube‐shaped morphology and uniform size distribution. The optimal experimental conditions were found by optimization studies and, the limit of quantification (LOQ), limit of detection (LOD), linear dynamic range were recorded as 37.6 μg/L, 11.3 μg/L, and 40–600 μg/L, respectively. The enhancement factor of the presented method was calculated as 158.7‐folds compared to the LOD of the conventional FAAS system. Recovery experiments were performed to check the method's applicability/accuracy and the percent recovery results varied from 89.0 % to 112.9 %. According to these findings, the developed method was successfully applied for the quantitative determination of the target analyte in a seawater sample matrix. [ABSTRACT FROM AUTHOR]

Solvent‐assisted dispersive solid‐phase extraction (SA‐DSPE) approach was developed to measure triazole fungicides (TFs). In the SA‐DSPE technique, the addition of 1000 μL of ethanol as a disperser solvent, along with a small quantity of benzil as a sorbent to the sample solution, led to a cloudy solution. After completion of the extraction, the mixture was subjected to centrifugation to isolate benzil. Next, benzil was dissolved in ethanol, and the resulting solution was subsequently analyzed by a gas chromatography‐flame ionization detector. This method demonstrated high linearity (R2 > 0.9963) and repeatability (relative standard deviation % < 4.3) for the quantification of TFs under the optimal conditions (sorbent: benzil, amount of benzil: 2% w/v, pH of solution: 7.0, disperser solvent: ethanol, volumes of ethanol: 1000 μL, centrifuge time: 3 min, extraction temperature: 25°C, and ionic strength: without salt addition). The proposed SA‐DSPE yielded detection limits, quantification limits, and preconcentration factors within the ranges of 0.3–0.9 ng/mL, 1.0–3.0 ng/mL, and 419–426, respectively. Finally, the validated method was employed to determine TFs in a diverse range of real samples, encompassing waters, fruits, vegetables, and agricultural soils, with relative recoveries ranging from 93.0% to 104%. [ABSTRACT FROM AUTHOR]

A hybrid material, consisting of commercially available nitrocellulose (NC) membrane non-covalently modified with amino-polyethylene glycol functionalized reduced graphene oxide (NH2-PEG-rGO) nanoparticles, was successfully synthesized for oligonucleotide extraction. Fourier Transform Infrared Spectroscopy (FTIR) confirmed the modification of the NC membrane, revealing characteristic peaks of both compounds, i.e., NC and NH2-PEG-rGO. Scanning Electron Microscopy (SEM) exhibited morphological changes in the NC/NH2-PEG-rGO hybrid membrane, marked by the introduction of NH2-PEG-rGO particles, resulting in a distinctly smothered surface compared to the porous surface of the NC control membrane. Wettability assays revealed hydrophobic behavior for the NC/NH2-PEG-rGO hybrid membrane, with a water contact angle exceeding 90°, contrasting with the hydrophilic behavior characterized by a 16.7° contact angle in the NC membrane. The performance of the NC/NH2-PEG-rGO hybrid membrane was evaluated for the extraction of ssDNA with fewer than 50 nucleotides from solutions containing various ionic species (MnCl2, MgCl2, and MnCl2/MgCl2). The NC/NH2-PEG-rGO hybrid membrane exhibited optimal performance when incubated in MgCl2, presenting the highest fluorescence emission at 525 relative fluorescence units (r.f.u.). This corresponds to the extraction of approximately 610 pg (≈13%) of the total oligo-DNA, underscoring the efficacy of the pristine material, which extracts 286 pg (≈6%) of oligo-DNA in complex solutions. [ABSTRACT FROM AUTHOR]

• A series of novel fluorinated plant biomass adsorbents have been facilely synthesized. • The developed fluorinated cedar slag (FCS) exhibits excellent adsorption efficiency of PFCs. • The modified biomass material is suitable for the adsorption of PFCs from environmental water. • The FCS-SPE-HPLC-MS/MS approach can be applied for highly sensitive detection of PFCs. Perfluorinated compounds (PFCs) are toxic and widely present in the environment, and therefore effective adsorbents are required to remove PFCs from environmental water. In the present study, a new type of fluorinated biomass materials was synthesized via an ingenious fluorosilanization reaction. These adsorbents were applied for the adsorption of 13 typical PFCs, including perfluorocarboxylic acids (PFCAs) and perfluorosulfonic acids (PFSAs). By comparing their adsorption performance, Fluorinated cedar slag (FCS) was discovered to have the best absorption efficiency and enabled highly efficient enrichment of PFCs. The adsorption recovery of FCS with the investigated PFCs is greater than 90% under the optimal adsorption condition. Ascribed to the high affinity of F-F sorbent-sorbate interaction, FCS had good adsorption capacities of PFCs from aqueous solution, with the maximum adsorption capacity of 15.80 mg/g for PFOS and 10.71 mg/g for PFOA, respectively. Moreover, the adsorption time could be achieved in a short time (8 min). Using the FCS absorbent, an innovative FCS-solid phase extraction assisted with high performance liquid chromatography-electrospray-tandem mass spectrometry (FCS-SPE-HPLC-ESI-MS/MS) method was first developed to sensitively detect PFCs in the environmental water samples. The intra-day and inter-day recovery rates of the 13 compounds ranged from 90.7%-104.3%, with the RSD of 2.1%-4.7% (intra-day) and 2.5%-8.5% (inter-day), respectively. This research demonstrates the potential of the newly fluoro-functionalized plant biomass to adsorb PFCs from environmental water, with the advantages of high adsorption efficiencies, high anti-interference, easy operation and low economic cost. [Display omitted] [ABSTRACT FROM AUTHOR]

Anchoring an imidazole‐di‐tert‐butyl‐arylsilane possessing an azido group to a polystyrene resin provided a heterogeneous precursor that was radiolabeled easily using aqueous [18F]fluoride. After optimizing the conditions (i.e., using DMSO as solvent and heating at 160°C for 15 min), the desired [18F]fluorosilane was obtained in 24% radiochemical yield (RCY) and 78% radiochemical purity (RCP) using solid‐phase extraction as sole purification. Then, this compound was conjugated by strain‐promoted alkyne–azide cycloaddition to a model single‐variable domain possessing a cyclooctyne tag, yielding to the desired 18F‐labeled bioconjugate in 2% RCY and >95% RCP after purification by a size exclusion chromatography. [ABSTRACT FROM AUTHOR]

Liposomes have emerged as a drug delivery system for various chemotherapeutics providing enhanced bioavailability and reduced toxicity. In vitro drug release profiling of liposomal formulations is one of the essential tests for the premarket approval and post market quality control. We developed an automated electroanalytical method for drug release profiling of liposomal doxorubicin formulation. In this electroanalytical method, square wave voltammetry mode was selected to determine the released drug, the only redox-active analyte, by measuring the current at the pulsed potential ranges. Therefore, no separation from liposomal encapsulated doxorubicin is needed. This electroanalytical method provided a continuous drug release measurement for 24 h. The drug release increased as the release media pH and temperature increased. At 37 °C, the drug release increased from 7 % to 40 % when the pH increased from 5.5 to 7.4, In addition, at pH 6.5, as the temperature increased from 37 °C to 52 °C, total drug release increased by more than two-fold. Complete drug release (more than 80 %) was obtained at pH 6.5 and 52 °C in less than 3 h. The brand name and the two generic formulations showed similar drug release profile in all experimental conditions. This method is an alternative to traditional methods which require separation steps such as dialysis or solid phase extraction to quantitate released doxorubicin. This method may be further applied in the in vitro release testing of other liposomal formulations containing redox-active drug substances, e.g., liposomes encapsulating daunorubicin. [Display omitted] • Automated electro analytical method was developed for in vitro drug release profiling of liposomal doxorubicin. • Square wave voltammetry signal associated with redox reaction of doxorubicin was used for the quantitation of released doxorubicin. • Effect of pH, temperature and ammonium ion concentration was evaluated. • Drug release profiling of three formulations were compared. [ABSTRACT FROM AUTHOR]

This work is devoted to the preparation and characterization of silver sulfide (Ag2S) nanoparticles and used as an adsorbent for the separation and purification of Zr(IV), Y(III), and Sr(II) as a simulation mode for the purification of 89Zr from its parents (Y or Sr) and separation of 90Y from its parent Sr using batch and dynamic conditions. N2 adsorption-desorption isotherm for Ag2S is of type IV with a specific surface area (222 ± 0.4 m2/g). The surface is homogeneous texture in which connected channels of diameter 8.3 µm with embedded lamellar structures and the average nanoparticle sizes of 42 ± 3 nm. Ag2S nanoparticles sorbent material shows high selectivity for Zr(IV) from 0.01 M HCl with fast kinetics while 67.2% of Y(III) was removed at pH 4.5 and Sr(II) ions are nil. The adsorption process is exothermic and the intra-particle diffusion and film diffusion were involved in the adsorption mechanism. Also, the separation process was achieved using the column technique with a purity of 100% using different concentrations of HNO3 as eluent. Silver sulfide as an adsorbent material shows a promising potential with high sensitivity for separation and purification trace of Zr, Y, and Sr ions. [ABSTRACT FROM AUTHOR]

In this study, a novel adsorbent was prepared by modification of graphite with deep eutectic solvent based on camphor–thymol (by the mole ratio of 1:1) and was utilized as a separation phase for pipette tip micro-solid phase extraction of mitoxantrone from seawater, drug, urine and blood samples. After extraction, mitoxantrone content of samples was determined by spectrophotometry at 260 nm wavelength. Various variables which could affect the extraction, including pH, amount of extracting phase, volumes of sample and eluent, type of eluent, and number of the extraction/ejection cycles of solution and eluent, were evaluated and optimized by both one-variable-at-a-time and response surface methodology methods. Observations indicated that the highest extraction achieved when 200 mg of the adsorbent was employed for 100 µL of sample solution with 7 extraction cycles at pH 7.0. Analyte was desorbed from the adsorbent by 200 µL of methanol (as eluent) after 3 ejection cycles. The linear dynamic range of the technique was between 1 and 1000 µg L−1, and the limit of detection and quantification were 0.2 µg L−1 and 0.7 µg L−1, respectively. Finally, the proposed extraction was successfully employed for the determination of mitoxantrone in various real samples with complicated matrices. [ABSTRACT FROM AUTHOR]

Aquantitative determination method for polysorbate 80 in biological medicinal preparations using size-exclusion chromatography with UV detection was developed. OASIS HLB solid-phase extraction cartridges were used to extract polysorbate 80 from formulations with high protein concentrations. The HPLC separation was performed using a TSKgel G2000SWX column in isocratic mode. The mobile phase was phosphate buffer (0.1 M) containing sodium sulfate (0.1 M) and sodium dodecyl sulfate (0.1%). The developed method could be used for quantitative determination of polysorbate 80 in biological medicinal products. [ABSTRACT FROM AUTHOR]

In this research, a molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using oxazepam (OZ) as a template molecule and was subsequently applied as a selective sorbent for the extraction of diazepam (DZP) and its metabolites in urine samples using an SPE cartridge. OZ, temazepam (TZ), nordiazepam (NZ) and DZP were analyzed in the final extracts by high-performance liquid chromatography with diode array detection (HPLC-DAD). The SPE extraction steps were optimized, and the evaluation of an imprinting factor was carried out. The selectivity of the method for OZ versus structurally related benzodiazepines (BZDs), such as bromazepam (BRZ), tetrazepam (TTZ) and halazepam (HZ), was investigated. Under the optimum conditions, the proposed methodology provided good linearity in the range of 10–1500 ng/mL, with limit of detection values between 13.5 and 21.1 ng/mL and recovery levels for DZP and its metabolites from 89.0 to 93.9% (RSD ≤ 8%) at a concentration level of 1000 ng/mL. The proposed method exhibited good selectivity, precision and accuracy and was applied to the analysis of urine samples from a real case of DZP intake. [ABSTRACT FROM AUTHOR]

Cytokinins (CKs) are small signaling molecules present in all kingdoms of life; however, their biological relevance outside of plants is poorly characterized. CK detection across kingdoms has been shown to be inconsistent and is often organism or cell line dependent. To ensure optimal detection in epithelioma papulosum cyprini (EPC), a cold-blooded vertebrate cell line, a range of biomasses were evaluated. CKs were extracted by solid-phase extraction and then detected using high-performance liquid chromatography and tandem mass spectrometry. The objectives were to establish endogenous CK profiles and characterize their biosynthesis in EPC cells. Among the 14 CKs that were scanned for, only 4 forms were detected overall within the samples analyzed, including, N6-(Δ2-isopentenyl) adenine-9-riboside (iPR), N6-(Δ2-isopentenyl) adenine-9-riboside-5′ (mono/di/tri)phosphate (iPNT), and cis-zeatin-9-riboside-5′ (mono/di/tri)phosphate (cZNT) and 2‐methylthio‐zeatin (2MeSZ). The total CK concentrations ranged from 0.03 pmol/g to 681.025 pmol/gfwt. The results from this study provided evidence that EPC cells can produce and process CKs. [ABSTRACT FROM AUTHOR]

In this work, monodisperse and nano‐porous poly(bismaleimide‐co‐divinylbenzene) microspheres with large specific surface area (427.6 m2/g) and rich pore structure were prepared by one‐pot self‐stable precipitation polymerization of 2,2′‐bis[4‐(4‐maleimidophenoxy) phenyl] propane and divinylbenzene. The prepared poly(bismaleimide‐co‐divinylbenzene) microspheres were employed as dispersive solid‐phase extraction (DSPE) adsorbent for the extraction of triazine herbicides. Under optimized conditions, good linearities were obtained between the peak area and the concentration of triazine herbicides in the range of 1–400 µg/L (R2 ≥ 0.9987) with the limits of detection of 0.12–0.31 µg/L. Triazine herbicides were detected using the described approach in vegetable samples (i.e., cucumber, tomato, and maize) with recoveries of 93.6%–117.3% and relative standard deviations of 0.4%–3.5%. In addition, the recoveries of triazine herbicides remained above 80.7% after being used for nine DSPE cycles, showing excellent reusability of poly(bismaleimide‐co‐divinylbenzene) microspheres. The adsorption of poly(bismaleimide‐co‐divinylbenzene) microspheres toward triazine herbicides was a monolayer and chemical adsorption. The adsorption mechanism between triazine herbicides and adsorbents might be a combination of hydrogen bonding, electrostatic interaction, and π‐π conjugation. The results confirmed the potential use of the poly(bismaleimide‐co‐divinylbenzene) microspheres‐based DSPE coupled to the high‐performance liquid chromatography method for the detection of triazine herbicide residues in vegetable samples. [ABSTRACT FROM AUTHOR]

Mycotoxin contamination is widespread in plants and herbs, posing serious threats to the consumer and human health. Of them, alternariol (AOH) has attracted great attention as an "emerging" mycotoxin in medicinal herbs. However, a specific and high‐throughput extraction method for AOH is currently lacking. Thus, developing an efficient pre‐treatment technique for AOH detection is extremely vital. Here, a novel automated magnetic solid‐phase extraction method was proposed for the highly efficient extraction of AOH. Combining the aptamer‐functionalized magnetic nanoparticles (AMNPs) and the automatic purification instrument, AOH could be extracted in medicinal herbs in high throughput (20 samples) and a short time (30 min). The main parameters affecting extraction were optimized, and the method was finally carried out by incubation AMNPs with 3 mL of sample solution for 10 min, and then desorption in 75% methanol for liquid‐phase detection. Under optimal conditions, good reproducibility, stability, and selectivity were realized with an adsorption capacity of 550.84 ng/mg. AOH extraction in three edible herbs showed good resistance to matrix interference with recovery rates from 86% to 111%. In combination with AMNPs and the automatic purification instrument, high‐throughput and labor‐free extraction of AOH in different complex matrices was achieved, which could be extended in other complex matrices. [ABSTRACT FROM AUTHOR]

A 30 year old man was found with no signs of life in front of the house. The cyanide concentration in blood and urine was determined five years after the man's death. What is more, a stability study was conducted for 730 days in an authentic casework blood sample. Sample preparation procedure included precipitation with methanol:water mixture, solid phase extraction (SPE) and derivatization with the use of PFB-Br (pentafluorobenzyl bromide). The sample was analyzed using GC-QqQ-MS/MS (gas chromatopraphy coupled with tandem mass spectrometry) isotope dilution method. Separation was done using a SH-RXI-5MS column (30 m x 0.25 mm, 0.25 µm). Detection of PFB-CN and PFB-13CN was achieved using a triple-quadrupole mass spectrometer with an electron ionization (EI) ion source in multiple reaction monitoring (MRM) mode. After 5 years from the man's death, cyanide concentration was: 1900 ng/mL in blood and 500 ng/mL in urine. Stability study performed in an authentic blood sample 6 and 7 years after the man's death revealed cyanide concentrations of 1898.2 ng/mL and 1618.7 ng/mL, respectively. While spectrophotometric and colorimetric methods recorded both decrease and increase in cyanide concentration over time, newer chromatographic methods mainly indicate a decrease. The studies presented in this paper seem to confirm this trend. However, in order to interpretate the results of cyanide concentration in biological material reliably, more research is still necessary. [ABSTRACT FROM AUTHOR]

Background The consumption of foods containing amphenicols, a type of antibiotic, is a major concern for human health. A stable and accurate detection method can provide technical support for food-safety monitoring. Objective An effective and efficient method was established for determining amphenicols in animal-derived foods through the simultaneous use of solid-phase extraction (SPE) cleanup and ultrahigh-performance liquid chromatography/mass spectrometry (UPLC-MS/MS). Method Samples were extracted using 1.0% ammoniated ethyl acetate solution, degreased with n -hexane, and then concentrated and cleaned using a C18 SPE column. Next, gradient elution was performed using methanol and 0.05% aqueous ammonia as the mobile phase, followed by separation using a C18 column. The target compound was detected using electrospray ionization, both in positive and negative modes, through multiple reaction monitoring, and quantified using an internal-standard method. Results The content of chloramphenicol (CAP), florfenicol (FF), and florfenicol amine (FFA) (content range: 0.2–8.0 µg/kg) as well as that of thiamphenicol (TAP; content range: 1.0–40.0 µg/kg) show a good linear relationship, with a correlation coefficient of r  >   0.999. Furthermore, recoveries of 86.7–111.9% and relative standard deviations of <9.0% were achieved. The limits of detection and quantification are obtained as 0.03–0.33 and 0.1–1.0 μg/kg, respectively. Conclusions The proposed method has excellent stability and accuracy, and can be successfully used for the qualitative and quantitative determination of amphenicols, i.e. CAP, TAP, FF, and FFA residues in 210 animal-derived food samples, of which FF and FFA were detected in four samples. Highlights A stable and accurate method was successfully established for the simultaneous determination of CAP, TAP, FF, and FFA in animal-derived foods using UPLC-MS/MS. Effective sample pretreatment was established, lipids were removed using n -hexane, concentration and cleanup were achieved with the C18 SPE column, and matrix effects were effectively reduced, thus improving the method's accuracy and stability. The method was validated for eight common animal-source foods, including beef, lamb, pork, chicken, egg, milk, fish, and honey. This method has good applicability for CAP, TAP, FF, and FFA in animal-derived foods. [ABSTRACT FROM AUTHOR]