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Accurate measurement of serum glycocholic acid (GCA) is crucial for evaluating the activity of chronic hepatitis. Moreover, GCA is a novel identified biomarker for hepatocellular carcinoma. Although some laboratories have used the liquid chromatography-tandem mass spectrometry (LC–MS/MS) method to measure GCA in recent years, the problem of potential interference of GCA analogues has not been solved well yet. Neither reference measurement procedures nor reference materials for GCA have been listed in the Joint Committee for Traceability in Laboratory Medicine (JCTLM) database. For standardization of GCA, it is urgent to establish a candidate measurement procedure for GCA. In this study, a candidate reference measurement procedure for the quantification of GCA in human serum based on isotope dilution liquid chromatography-tandem mass spectrometry (ID-LC–MS/MS) by a two-step sample pretreatment of protein precipitation and MAX solid-phase extraction was developed and validated. GCA can be completely separated from its structural analogues with gradient elution in 9 min compared with short time gradients published in previous literature by Huang's group. Method validation indicated perfect quantitation precision with intra-day and inter-day values that were ≤1.30% and ≤1.80%, respectively. The method showed excellent linearity with high regression coefficients (R2 > 0.999) over a range of 0.92 ng/g–38.38 μg/g and perfect recoveries at three spiked levels (99.87–100.43%). No interference, matrix effect, and carryover were observed. Moreover, the cRMP was successfully applied to measure GCA in serum samples and compared with two immunoassays in a clinical laboratory. As a candidate reference method, this method can promote a GCA standardization program. [ABSTRACT FROM AUTHOR]

Therapeutic drug monitoring is essential for ensuring the efficacy and safety of medications. This study introduces a streamlined approach that combines pipette-tip solid-phase extraction (PT-SPE) with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), facilitating rapid and high-throughput monitoring of drug concentrations. As a demonstration, this method was applied to the extraction and quantification of antidepressants in serum. Utilizing Zip-Tip C18, the method enabled the extraction of antidepressants from complex biological matrices in less than 2 min, with the subsequent MALDI-MS analysis yielding results in just 1 min. Optimal extraction recoveries were achieved using a sampling solution at pH 9.0 and a 10 μL ethanol desorption solution containing 0.1% phosphoric acid. For MALDI analysis, 2,5-dihydroxybenzoic acid was identified as the most effective matrix for producing the highest signal intensity. The quantification strategy exhibited robust linearities (R2 ≥ 0.997) and satisfactory limits of quantification, ranging from 0.05 to 0.5 μg/mL for a suite of antidepressants. The application for monitoring dynamic concentration changes of antidepressants in rat serum emphasized the method's efficacy. This strategy offers the advantages of high throughput, minimal sample usage, environmental sustainability, and simplicity, providing ideas and a reference basis for the subsequent development of methods for therapeutic drug monitoring. [ABSTRACT FROM AUTHOR]

A magnetic solid-phase extraction method with the dispersion of magnetic hypercrosslinked polystyrene (MHCPS) by carbon dioxide is proposed for the extraction and preconcentration of amphenicols (chloramphenicol, florfenicol, and thiamphenicol) from honey and milk before their determination by HPLC–MS/MS. Effervescent tablets, consisting of sodium bicarbonate, citric acid, and MHCPS in the case of honey and sodium bicarbonate and MHCPS in the case of milk, were used. The conditions for obtaining tablets were selected (the amount and ratio of the acid, base, and MHCPS in the composition of a tablet and its mass), ensuring the quantitative release of amphenicols. Procedures for the determination of amphenicols in honey and milk with the dispersion of the sorbent by carbon dioxide and the subsequent determination of the compounds by HPLC–MS/MS are developed. The limits of detection are 0.3–1 and 0.02–0.05 μg/kg for honey and milk, respectively. [ABSTRACT FROM AUTHOR]

The three-dimensional imprinted polymeric network was synthesized via a bulk polymerization reaction in the presence of a flavonoid as a template. In this reaction, methacrylic acid (MAA) and acrylic acid (AA), tetrahydrofuran and trimethylolpropanetrimethacrylate, were used as functional monomers, porogen, and cross-linker, respectively. In this study, two kinds of molecularly imprinted polymers (MIPs) with different ratios of 1:8:40 and 1:20:80 (template: functional monomer: cross-linker) were synthesized and compared together. The related binding capacities were calculated as equal to 392.08 mg/g and 609.00 mg/g, respectively, by UV-spectrometer. The synthesized polymers have been evaluated via field emission scan electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller techniques. High selectivity and the proper specific surface area as equal to 167.00 m2/g in MIPs-based methacrylic acid (MIPs-MAA) and 434 m2/g in MIPs-based acrylic acid (MIPs-AA) comparatively to non-imprinted molecular polymers are the privileged characteristics in this research. The MIPs provided are a good candidate for the separation of flavonoids with the solid phase extraction method. [ABSTRACT FROM AUTHOR]

This study introduces a miniaturised solid-phase extraction (µ-SPE) method coupled with ultra-high performance liquid chromatography and tandem mass spectrometry (UHPLC-MS/MS) for the simultaneous quantification of 23 compounds, including psychoactive drugs, narcotics and their metabolites, in urine samples. The µ-SPE method, using standard laboratory equipment such as a centrifuge, was developed and validated, offering a practical and economical alternative to more traditional SPE methods. The key extraction parameters: elution solvent composition, sample and elution volumes, and sorbent mass were optimized to enhance performance. The method demonstrated high sensitivity, with detection limits between 0.06 and 0.41 ng cm−3 and quantification limits from 0.19 to 1.24 ng cm−3. The precision was confirmed with an intra-day precision ranging from 0.2% to 7.5% and an inter-day precision from 1.2% to 13.4%. Recovery rates ranged from 84.2% to 109.4%, with minimal matrix effects observed for most analytes (|ME|< 10%). The relative error remained below 5%, indicating good accuracy. The method was also evaluated in terms of greenness, practical, and analytical aspects using the WAC model. Based on the validation results, it was concluded that the developed method could be a good confirmatory method for results obtained by immunochemical tests and could also be used in both clinical analyses and forensic toxicology. [ABSTRACT FROM AUTHOR]

This study investigates the presence of new psychoactive substances (NPS) and their metabolites in two wastewater treatment plants (WWTPs) situated in South Wales, UK (WWTP-1 and WWTP-2). Analysis was conducted for 35 NPS and metabolites, along with the inclusion of benzoylecgonine (main cocaine metabolite) and cannabis, the most detected illicit substances. Benzoylecgonine was identified as the predominant substance in both WWTPs. Epidemiological calculations revealed the average population consumption of cocaine to be 3.88 mg/d/1000 inhabitants around WWTP-1 and 1.97 mg/d/1000 inhabitants for WWTP-2. The removal efficiency of benzoylecgonine across both WWTPs was observed at an average of 73%. Subsequent qualitative analyses on randomly selected wastewater samples detected medicinal compounds including buprenorphine, methadone, and codeine in both WWTPs. An additional experiment employing enzymatic hydrolysis revealed the presence of morphine, an increased presence of codeine, and 11-Nor-9-Carboxy-THC (THC-COOH) post-hydrolysis. These findings underscore the significant presence of illicit substances and medicinal compounds in wastewater systems with the absence of NPS within the South Wales area, highlighting the necessity for enhanced monitoring and treatment strategies to address public health and environmental concerns. [ABSTRACT FROM AUTHOR]

Volatile organic compounds (VOCs) are continuously emitted into the atmosphere from natural and anthropogenic sources and rapidly spread from the atmosphere to different environments. A large group of VOCs has been included in the class of air pollutants; therefore, their determination and monitoring using reliable and sensitive analytical methods represents a key aspect of health risk assessment. In this work, an untargeted approach is proposed for the evaluation of the exposure to volatile organic compounds of workers in an engine manufacturing plant by GC–MS measurements, coupled with solid-phase microextraction (SPME). The analytical procedure was optimized in terms of SPME fiber, adsorption time, desorption time, and temperature gradient of the chromatographic run. For the microextraction of VOCs, the SPME fibers were exposed to the air in two different zones of the manufacturing factory, i.e., in the mixing painting chamber and the engine painting area. Moreover, the sampling was carried out with the painting system active and running (system on) and with the painting system switched off (system off). Overall, 212 compounds were identified, but only 17 were always present in both zones (mixing painting chamber and engine painting area), regardless of system conditions (on or off). Finally, a semi-quantitative evaluation was performed considering the peak area value of the potentially most toxic compounds by multivariate data analyses. [ABSTRACT FROM AUTHOR]

Bisphenols are widely used as monomers and additives in plastic production. Thus, bisphenol A (BPA) and its most prominent substitutes have been detected in many environmental and human samples. This study proposes an online solid-phase extraction analytical methodology coupled to liquid chromatography with tandem mass spectrometry for the determination of six bisphenols (BPA and bisphenols F (BPF), S (BPS), AF (BPAF), B (BPB), and E (BPE)) in urine samples as an efficient and automated methodology. The method was developed and validated for all bisphenols with good recoveries (92–112%) and repeatability (RSD ≤ 10%) despite the variable matrix effects, except BPAF (which would require a dedicated internal standard), achieving method quantification limits in the 0.05–2.2 ng mL−1 range. The methodology was subsequently applied to 435 urine samples from a non-occupational exposure population (civil servants for the regional government) from Santiago de Compostela (Galicia, Spain). Only BPA, BPF, and BPS were positively detected; the last two presented higher detection frequencies than BPA. When the urinary concentrations are extrapolated to human intake and compared to the European Food Safety Agency (EFSA) tolerable daily intake (TDI) of 2 × 10−4 µg kg−1 day−1 (TDI), all BPA positively identified samples would surpass this threshold. Although no TDI exists currently for the other two identified bisphenols, it is evident that human exposure to bisphenols should be limited. Finally, the results stratification by gender revealed higher levels of exposure to BPF in the women group. [ABSTRACT FROM AUTHOR]

In order to investigate the mechanism of plant growth promoting (PGP) effects of strain Bacillus velezensis WSW007, its PGP traits and production of volatile organic compounds (VOCs) were tested. The effects of VOCs produced by strain WSW007 on plant growth were observed by co-culturing this strain with tobacco seedlings in I-plates. Meanwhile, the effects of VOCs on tobacco gene expression were analysed by a transcriptome analysis and VOCs were identified by solid phase micro extraction coupled with gas chromatography-mass spectrometry (SPME-GC-MS) analysis. As results, strains WSW007 produced acetic acid and siderophore, and could solubilize phosphate; while it also significantly increased the fresh weight of tobacco seedlings via production of VOCs. In transcriptome analysis, plants co-cultured with strain WSW007 presented the highest up-regulated expression for the genes involved in plant growth and development processes, implying that the bacterial VOCs played a role as regulator of plant gene expression. Conclusively, the up-regulation in expression of growth- and development-related genes via VOCs production is an important PGP mechanism in strain B. velezensis WSW007. [ABSTRACT FROM AUTHOR]

An automated flow analysis-solid phase extraction (FA-SPE) system and methodology of ultra-high-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS) analysis were developed for the determination of selected antiviral drugs (acyclovir, amantadine, rimantadine, and oseltamivir) in water samples. The proposed FA-SPE approach enables the integration of various extraction stages and elimination of the sample evaporation step and offers individual customisation of SPE parameters, inter alia sample, and eluate flow rate and volume. Using the developed FA-SPE procedure, e.g. a 100-fold preconcentration of the target analytes in 1 h was achieved. A method for chromatographic analysis was also developed to determine the selected antiviral drugs in combination with the use of the FA-SPE system. The developed FA-SPE UHPLC-MS/MS method was validated including the determination of linearity of analytical graphs, limits of detection (5.5–99.9 pg mL−1) and quantification (18.3–329.8 pg mL−1), intra-day (1.8–8.3%) and inter-day (3.0–9.2%) precision, recovery (95.6–105.3%), and matrix effects (− 12.9 to 13.2%). The proposed method was successfully applied to analyse tap, drinking, and river water samples, revealing the presence of amantadine at a concentration of 40.1 pg mL−1 in one sample. The environmental impact of the developed FA-SPE sample preparation procedure was also assessed using the AGREEprep metric tool and compared with five other literature methods, achieving the most sustainable outcome. [ABSTRACT FROM AUTHOR]

A novel 3D magnetic nanocomposite material based on covalent organic polymers was successfully synthesized and utilized as an efficient sorbent for magnetic solid-phase extraction. It exhibited a regular core–shell structure, large specific surface area, superior stability, and paramagnetism. To evaluate its extraction efficiency, six flavonoids were tested, demonstrating maximum adsorption capacities ranging from 90 to 218 mg/g. Additionally, the material exhibited remarkable reusability and mechanical stability, maintaining its original state over eight cycles with consistent recovery. An analytical strategy combining magnetic solid-phase extraction with high performance liquid chromatography and tandem mass spectrometry was developed for the determination of flavonoids in orange, honey, soybean, and Dioscorea bulbifera L. samples. The low limits of detection (0.01–0.1 ng/mL) and limits of quantification (0.05–0.5 ng/mL), as well as satisfactory recovery (80.4–114.8%), were obtained. The linear range started from the limits of quantification to 500 ng/mL with R2 ≥ 0.9929. These results suggest that the prepared adsorbent possesses excellent adsorption capabilities for flavonoids, highlighting its significant potential for detecting these compounds in complex sample matrices. [ABSTRACT FROM AUTHOR]

A novel magnetic dispersive solid phase extraction (MDSPE) procedure based on the deep eutectic solvent (DES) modified magnetic graphene oxide/metal organic frameworks nanocomposites (MGO@ZIF-8@DES) was established and used for the efficient enrichment of estradiol, estrone, and diethylstilbestrol in cosmetics (toner, lotion, and cream) for the first time. Then, the three estrogens were separated and determined by UHPLC-UV analysis method. In order to study the features and morphology of the synthesized adsorbents, various techniques such as FT-IR, SEM, and VSM measurements were executed. The MGO@ZIF-8@DES nanocomposites combine the advantages of high adsorption capacity, adequate stability in aqueous solution, and convenient separation from the sample solution. To achieve high extraction recoveries, the Box-Behnken design and single factor experiment were applied in the experimental design. Under the optimum conditions, the method detection limits for three estrogens were 20–30 ng g−1. This approach showed a good correlation coefficient (r more than 0.9998) and reasonable linearity in the range 70–10000 ng g−1. The relative standard deviations for intra-day and inter-day were beneath 7.5% and 8.9%, respectively. The developed MDSPE-UHPLC-UV method was successfully used to determine three estrogens in cosmetics, and acceptable recoveries in the intervals of 83.5–95.9% were obtained. Finally, three estrogens were not detected in some cosmetic samples. In addition, the Complex GAPI tool was used to evaluate the greenness of the developed pretreatment method. The developed MDSPE-UHPLC-UV method is sensitive, accurate, rapid, and eco-friendly, which provides a promising strategy for determining hormones in different complex samples. [ABSTRACT FROM AUTHOR]

UV filters and benzotriazole UV stabilizers are considered emerging contaminants in the environment. LC–MS/MS and GC–MS methods, involving a single solid phase extraction protocol, were developed and validated to determine eight UV filters and seven UV stabilizers, respectively in wastewater from a wastewater treatment plant (WWTP) in Lüneburg, Germany. The LC–MS/MS method exhibited extraction recoveries of ≥ 71% at six different fortification levels with limits of detection (LODs) range of 0.02 ng mL−1 – 0.09 ng mL−1. Extraction recoveries of 47 to 119% at six different fortification levels were obtained for the GC–MS method with LODs range of 0.01 – 0.09 ng mL−1. Among the UV filters, the highest mean concentration was determined for octocrylene (OCR) in influent (3.49 ng mL−1) while the highest mean concentration was measured for 2-hydroxy-4-octyloxybenzophenone (UV 531) in influent (0.44 ng mL−1) among the UV stabilizers. Potential risk to aquatic organisms was assessed by the risk quotient approach. Only OCR presented a high risk to aquatic invertebrates whereas 2-ethylhexyl 4-methoxycinnamate (EHMC) and 2-ethylhexyl salicylate (EHS) posed high risks to algae. Benzotriazole UV stabilizers presented negligible risks to aquatic invertebrates and fish. This work reports the detection of rarely studied 4-aminobenzoic acid (PABA) and UV 531 in WWTP influent and effluent. The occurrence and risk assessment of target benzotriazole UV stabilizers in wastewater from a German WWTP was demonstrated for the first time. [ABSTRACT FROM AUTHOR]

Emerging contaminants (ECs) are substances that have no defined environmental quality standards or regulations, and have the potential to pose major adverse impacts on the environment and human health. The detection of contaminants in the natural environment is the key step for establishing precise environmental risk assessment approach for ECs. However, ECs come from different origins with various physicochemical properties, making their detection a complicated process. Moreover, their presence in the aquatic environment at trace concentration range (ng/L-µg/L), requires an accurate detection at low concentration levels. This study aims to develop an efficient analytical method for simultaneous determination of 5 different ECs in aqueous solution based on solid phase extraction technique (SPE) followed by liquid chromatography-mass spectrometry (LC–MS/MS). High recovery rates (72% to 114%) were achieved for all targeted compounds. Ciprofloxacin (CIP), diuron (DIU), terbutryn (TER) and diclofenac (DIC) had a limit of detection (LOD) of 5 µg/L and a limit of quantification (LOQ) of 10 ng/L, while LOD and LOQ for EE2 were 25 µg/L and 50 ng/L, respectively. These results confirm that the optimized method can be applied for extraction and analysis of ECs from different classes in the aquatic environment. [ABSTRACT FROM AUTHOR]

Magnetic solid-phase extraction (MSPE) is a highly effective method for separating metal ions from aquatic solutions, making it a popular choice for metal ion separation. This study investigated the behavior of Fe3O4@SiO2-SH core–shell composites for the adsorption and recovery of silver ions. The quality of the synthesized adsorbent was verified using XRD, FT-IR, EDS, FE-SEM, and EDAX-map analyses. Magnetic properties and surface charge changes were assessed using VSM and Zeta potential analyses. By implementing the classic OFAT method, the study evaluated the effect of various parameters on silver adsorption, such as pH, composite dosage, initial Ag+ concentration, temperature, and secondary metal ions. Results showed that the proposed composite had a high maximum adsorption capacity (112 mg/g) at pH = 6, ambient temperature, 0.1 g/L adsorbent dosage, and silver concentrations greater than 25 mg/L. The composite demonstrated good selectivity in Ag+ separation from a bimetallic solution containing silver and mercury ions. The results also showed that 1M HNO3 and 1M HCl solutions released over 78% and 70% of absorbed ions from the composite surface, respectively. However, the HCl solution enabled the precipitation of almost all desorbed Ag+, providing a selective recovery of silver ions. [ABSTRACT FROM AUTHOR]

Magnetised attapulgite (ATP-Fe3O4) adsorbent was synthesised using a sonochemistry approach for the solid phase extraction of As3+ from stimulated and unrefined crude oil samples. The average size of the Fe3O4 nanoparticles estimated from the Transmission Electron Microscopy (TEM) image was 10 nm. The TEM analysis also showed that Fe3O4 nanoparticles agglomerated in the ATP's tube and on its surface. The X-ray diffraction analysis (XRD) indicates that the crystallinity of the ATP reduced after the magnetisation process. The saturation magnetisation of the ATP-Fe3O4 was determined to be only 2.8 emu g-1. Under the optimum conditions (pH = 7, adsorbent dosage = 0.6 g, contact time = 90 min and sample volume = 50 mL), the As3+ removal was more than 98% for both types of oil. The limits of detection (LOD) and relative standard deviations (RSD%) were 2.88 ng mL-1 and 0.3423%, respectively. The adsorption process follows the pseudo-first-order kinetic model (R2 = 0.9696) and adheres to the Langmuir isotherm model (R2 = 0.9925). The reusability study showed that ATP-Fe3O4 is highly stable and can be reused five times with almost 100% removal efficiency. This research outcome aligns with the United Nations Sustainable Goal 7, Affordable and Clean Energy. [ABSTRACT FROM AUTHOR]

A new modified cellulose with diaminoguanidine (Cel-Gua) synthesized for specific recovery of Cu (II), Cd (II), and Hg (II) from the alum sample. Cellulose was silanized by 3-chloropropyltrimethoxysilane and then was modified with diaminoguanidine to obtain N-donor chelating fibers. Fourier transform-infrared spectroscopy, scanning electron microscopy, X-ray diffraction, zeta potential, electrons disperse X-ray analysis, elemental analyses (C, H and N), and thermogravimetric analysis were used for characterization. Factors influencing the adsorption were thoroughly examined. Under the optimal conditions, the Cel-Gua sorbent displayed maximum adsorption capacities of 94.33, 112.10 and 95.78 mg/g for Cu (II), Cd (II), and Hg (II), respectively. The sorption process of metal ions is equipped by kinetic model PSO and Langmuir adsorption isotherm. The calculated thermodynamic variables confirmed that the adsorption of Cu (II), Cd (II) and Hg (II) by Cel-Gua sorbent is a spontaneous and exothermic process. In our study, we used the molecular operating environment software to conduct molecular docking simulations on the Cel-Gua compound. The results of the docking simulations showed that the Cel-Gua compound displayed greater potency and a stronger affinity for the Avr2 effector protein derived from Fusarium oxysporum, a fungal plant pathogen (code 5OD4). The adsorbent was stable for 7 cycles, thus allowing its safe reutilization. [ABSTRACT FROM AUTHOR]

Background: The substantially operated analytical instruments dealing in the area of analytical chemistry are traditional methods like high-performance liquid chromatography (HPLC) and gas chromatography (GC). Since they use solvents, produce trash, and require energy, these methods seriously compromise the natural milieu. The excessive consumption of an enormous number of organic solvents, along with the trash created from it, can contaminate the environment. As a result, researchers are now creating novel Green Analytical Chemistry approaches to address these environmental problems and create an ecologically preferable replacement. Ecologically preferable replacement can be accomplished by using a green solvent, such as ethanol or water, in place of harmful solvents. Additionally, the need for solvent can be decreased by omitting the sample preparation stage wherever possible or by utilising alternate green extraction methods. Adoption of compact methods like ultra-high-performance liquid chromatography (UHPLC) may also result in a decrease in the amount of energy used and trash produced during analysis. Short conclusion: This review features information on using sustainable practises in analytical chemistry as well as details on using green solvents and sample preparation methods such as Solid Phase Extraction (SPE), Qucheers. It also provides information related of application of green analytical techniques such UHPLC, High-Performance Thin Layer Chromatography (HPTLC), and Thin Layer Chromatography (TLC). [ABSTRACT FROM AUTHOR]

The extraction of nandrolone as a steroid hormone using fast methods is of high importance. This was done by dispersive micro-solid phase extraction in the presence of two widely used organometallic frameworks (MIL-53(Al) and ZIF-8). The extraction steps were optimized by an extensive study on the main factors affecting the absorption/desorption efficiency. The optimum conditions were obtained by design of experiments for the extraction and determination of nandrolone in a blank human plasma matrix. Maximum extraction of nandrolone was achieved in 8.5 min by 2.5 mg of MIL-53(Al) in the solution with 0.89% (w/v) salt concentration, while the maximum extraction by ZIF-8 as another sorbent required 10 min, 4.5 mg of sorbent, and 0.60% (w/v) of salt concentration. Batch experiments were carried out to find appropriate kinetic and isotherm models. Finally, the analytical validation of the proposed method was investigated. The dynamic range of the method was from 0.05 to 1 µg/mL. The precision (expressed as the relative standard deviation, RSD) and accuracy (expressed as the percentage error) of extraction by MIL-53(Al) were found 3.90 and 3.39%, respectively, while those by ZIF-8 were calculated as 4.59 and 4.50%, respectively. The proposed method was successfully applied for the determination of nandrolone in spiked samples, achieving high recovery rates of approximately 96% and 94% using MIL-53(Al) and ZIF-8. [ABSTRACT FROM AUTHOR]

In the present study, the integration of magnetic dispersive micro-solid-phase extraction (MD-µSPE) with hollow fiber liquid-phase microextraction (HF-LPME) prior to gas chromatography–mass spectrometry (GC/MS) was developed to preconcentrate and determine trace amounts of chlorpyrifos pesticide. Azolla filiculoides fern biomass was loaded by magnetite nanoparticles to prepare magnetic adsorbent (azolla@Fe3O4). The structural characteristics of the produced magnetic nanocomposites (MNCs) were investigated by FESEM, TEM, VSM, FTIR, EDX, and XRD methods. In the proposed MD-µSPE/HF-LPME method, the adsorption/desorption variables in MD-µSPE step were optimized by Taguchi fractional factorial design. After chlorpyrifos adsorption in the optimized condition of MD-µSPE (Vsample = 50 mL, contact time = 15 min, solution pH = 3, adsorbent mass = 0.05 g, ionic strength = 0.01 mol L−1, and eluent type = ethanol), 2.0 mL of the desorbed ethanolic solution was added to 16 mL of 10% (w/v) NaCl aqueous solution for the next HF-LPME method and the final analysis was performed by GC/MS. The developed method showed a limit of detection of 0.05 μg L−1, a limit of quantification of 0.5 μg L−1, a dynamic linear range of 0.5–1000.0 μg L−1, preconcentration factors between 700 and 1050, and a repeatability (RSD%) of 6.9%. The suitability of the MD-µSPE/HF-LPME method was confirmed by measuring chlorpyrifos in real samples with relative recoveries in the range of 97.0–108.5%. The results showed good accuracy and precision of the developed MD-µSPE/HF-LPME method for the preconcentration and determination of trace amounts of chlorpyrifos in the aqueous samples. [ABSTRACT FROM AUTHOR]

The compound salidroside was synthesized through the glucosylation of p-tyrosol. This research prioritizes the purification of salidroside over process optimization due to insufficient product yield. High-performance centrifugal partition chromatography (HPCP) with biphasic solid-phase extraction on graphitic material is employed to achieve a final product purity of 95%. Salidroside authentication was conducted using ESIMS2 and NMR. The study integrates computational and experimental approaches, employing B3LYP with basis set 6-311++G (d, p) in density functional theory (DFT). Various characterizing instruments, including 1HNMR, IR, UV visible, and others, consistent with AIM theory (atoms in molecules) for ellipticity and experimental outcomes, are utilized. Donor–acceptor interactions are explored through NBO research. The calculated energy difference between the frontier molecular HOMO and LUMO orbitals indicates the stability of salidroside. Molecular docking studies and electrophilicity index evaluations reveal salidroside's interactions with binding proteins, ranging from 5.718 to 7.405 kcal/mol. Molecular dynamics simulations assess biomolecular stability. Drug-likeness tests suggest salidroside's antibiotic properties, exhibiting similarities with capsaicin, methylsalicylate, menthol, allantoin, lupeol, morphine, and mitragynine. This research contributes valuable scientific insights essential for innovative drug development. [ABSTRACT FROM AUTHOR]

Herein, a turn "Off/On" fluorescence probe based on ZnO quantum dots (ZnO-QDs) has been proposed and successfully utilized for the determination of Ara-C (cytarabine) using ceric ions (Ce4+) as quencher and ethylenediamine (ED) as a linker. The probe is based initially on the quenching effect of Ce4+ ions on the strong native fluorescence of ZnO-QDs forming the Turn Off system (Ce@ZnO-QDs) that believed to occur due to the aggregation-induced quenching (AIQ) mechanism. The second step is the addition of Ara-C in the presence of ethylenediamine (ED) that encourages the formation of Ara-C/ED/Ce4+ as well as the release of the free ZnO-QDs, leading to the recovery of the fluorescence intensity. The developed sensing platform shows a linear response towards Ara-C over the range of 10 to 1000 ng mL−1 giving a limit of detection (LOD) and limit of quantitation (LOQ) of 1.22 ng mL−1 and 3.70 ng mL−1, respectively. A dispersive magnetic solid phase micro-extraction (dMSPE) method was developed and optimized for the extraction of Ara-C in spiked human plasma using thiol-modified magnetite nanoparticles (S-MNPs). The proposed platform exhibits good sensitivity toward Ara-C in the presence of different interfering substances. Excellent recoveries are obtained after spiking different concentrations of Ara-C into rabbit plasma samples. The validated experimental parameters have been successfully applied to monitor the pharmacokinetic profile of Ara-C in rabbit plasma. A detailed adsorption kinetics study has been carried out to provide a deep insight into the adsorption behavior of Ara-C on the thiol-doped-magnetite nanoparticles. The greenness assessment of the proposed method was achieved and compared with other reported methods using two tools of greenness; the green analytical procedure index (GAPI) and the analytical greenness calculator AGREE. [ABSTRACT FROM AUTHOR]

Antibiotics are widely used as drugs to promote growth of livestock as well as to protect humans, fish, cattle, crops, and other living things from microbial infections. Significant amounts of antibiotic residues have been found in soil, edible parts of crops, manures made of animal excreta as well as in wastewater and this causes the rise of a serious problem of antibiotic resistance development. In this study, we have developed a GREEN extraction method for sulfamethoxypyridazine (SMXP), a sulfonamide veterinary antibiotic, from both soil and water for analysis using LC–MS/MS. An LC–MS/MS method has been optimized with a total run time of 5 min. For the extraction of SMXP from the soil a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe), technique was developed with an acceptable recovery of 102.91–111.26% with a method limit of Quantification (MLOQ) of 0.05 mg/kg and method limit of detection (MLOD) of 0.01 mg/kg. For the extraction of SMXP from water, solid-phase extraction (SPE) using a Hydrophilic Lipophilic Balance (HLB) cartridge was optimized with a recovery of 84–110%. The methods were repeatable as well as reproducible with a relative standard deviation (RSD) of ≤ 10%. The MLOQs were 0.01 and 0.05 mg/L(Kg) at 10:1 signal-to-noise ratio, respectively for water and soil. The developed methods were validated using other sulfonamide antibiotics for extraction from soil and water, and they were found to be acceptable. The sulfonamides exhibited soft matrix effects except for sulfadiazine in soil. To evaluate environmental and occupational hazards associated with the analytical method, an Analytical GREENness score was calculated and its values were 0.52 and 0.64 for the QuEChERS and HLB-SPE methods, respectively, indicating the greener nature of the SPE method. Further, the BAGI metric tool demonstrated values of 75 and 70 for soil and water extraction techniques indicating the applicability of the environmentally and occupationally safe methods. Hence, these methods can be safely used to extract and analyze SMXP and other sulfonamide antibiotics. [ABSTRACT FROM AUTHOR]

N-Acyl-homoserine lactones (AHL) play a major role in the communication of Gram-negative bacteria. They influence processes such as biofilm formation, swarming motility, and bioluminescence in the aquatic environment. A comprehensive analytical method was developed to elucidate the "chemical communication" in pure bacterial cultures as well as in the aquatic environment and engineered environments with biofilms. Due to the high diversity of AHLs and their low concentrations in water, a sensitive and selective LC-ESI-MS/MS method combined with solid-phase extraction was developed for 34 AHLs, optimized and validated to quantify AHLs in bacterial conditioned medium, river water, and treated wastewater. Furthermore, the developed method was optimized in terms of enrichment volume, internal standards, limits of detection, and limits of quantification in several matrices. An unanticipated variety of AHLs was detected in the culture media of Pseudomonas aeruginosa (in total 8 AHLs), Phaeobacter gallaeciensis (in total 6 AHLs), and Methylobacterium mesophilicum (in total 15 AHLs), which to our knowledge have not been described for these bacterial cultures so far. Furthermore, AHLs were detected in river water (in total 5 AHLs) and treated wastewater (in total 3 AHLs). Several detected AHLs were quantified (in total 24) using a standard addition method up to 7.3±1.0 µg/L 3-Oxo-C12-AHL (culture media of P. aeruginosa). [ABSTRACT FROM AUTHOR]

Stanozolol, a synthetic derivative of testosterone, is one of the common doping drugs among athletes and bodybuilders. It is metabolized to a large extent and metabolites are detected in urine for a longer duration than the parent compound. In this study, a novel dummy molecularly imprinted polymer (DMIP) is developed as a sorbent for solid-phase extraction of stanozolol metabolites from spiked human urine samples. The optimized DMIP is composed of stanozolol as the dummy template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker in a ratio of 1:10:80. The extracted analytes were quantitively determined using a newly developed and validated ultrahigh-performance liquid chromatography tandem mass spectrometry method, where the limits of detection and quantitation were 0.91 and 1.81 ng mL−1, respectively, fulfilling the minimum required performance limit decided on by the World Anti-Doping Agency. The mean percentage extraction recoveries for 3'-hydroxystanozolol, 4β-hydroxystanozolol, and 16β-hydroxystanozolol are 97.80% ± 13.80, 83.16% ± 7.50, and 69.98% ± 2.02, respectively. As such, the developed DMISPE can serve as an efficient cost-effective tool for doping and regulatory agencies for simultaneous clean-up of the stanozolol metabolites prior to their quantification. [ABSTRACT FROM AUTHOR]

A new detection platform based on a hydroxylated covalent organic framework (COF) integrated with liquid chromatography–tandem mass spectrometry (LC–MS/MS) was constructed and used for detecting adrenergic receptor agonists (ARAs) residues in milk. The hydroxylated COF was prepared by polymerization of tris(4-aminophenyl)amine and 1,3,5-tris(4-formyl-3-hydroxyphenyl)benzene and applied to solid-phase extraction (SPE) of ARAs. This hydroxylated COF was featured with hierarchical flower-like morphology, easy preparation, and copious active adsorption sites. The adsorption model fittings and molecular simulation were applied to explore the potential adsorption mechanism. This detection platform was suitable for detecting four α2- and five β2-ARAs residues in milk. The linear ranges of the ARAs were from 0.25 to 50 µg·kg−1; the intra-day and the inter-day repeatability were in the range 2.9–7.9% and 2.0–10.1%, respectively. This work demonstrates this hydroxylated COF has great potential as SPE cartridge packing, and provides a new way to determine ARAs residues in milk. [ABSTRACT FROM AUTHOR]

There is an imperative need to eliminate pharmaceutical residues from aquatic environments due to their hazardous properties, including toxicity, mutagenicity, and carcinogenicity, particularly when present in water sources. Conventional water treatment methods have proven insufficient in addressing nano-pollutants such as pharmaceutical residues. Consequently, the ongoing quest for economically viable, sustainable, and environmentally friendly removal mechanisms persists. In this particular study, we employed Giant Macroporous Silica (GMS) derived from marine sponges as a promising biosorbent. GMS exhibits commendable characteristics, including a high specific surface area, swift mass transfer capabilities, and non-discriminatory adsorption qualities. The efficacy of GMS in adsorbing carbamazepine (CBZ), a common drug residue, was scrutinized under diverse experimental conditions, including a sorbate/sorbent ratio ranging from 0.005 to 1.500 weight ratio, contact times spanning from 0 to 240 min, and initial pH values ranging from 5 to 9. Remarkably, at a concentration of 1000 µg L−1, GMS demonstrated an attractive adsorption rate (98.88%) of carbamazepine at pH 7.07, within 90 min. To enhance our understanding, we developed an ANFIS model utilizing the experimental parameters as inputs. The developed model exhibited a high correlation coefficient of 0.9944% and a root mean square error (RMSE) of 1.6693, indicating its dependability in accurately predicting the adsorption of CBZ on GMS. The results of our study highlight the efficacy of GMS in adsorbing CBZ, suggesting its considerable potential for adsorbing other pharmaceutical residues and nano-pollutants. Furthermore, we propose the possibility of developing a solid-phase extraction cartridge from GMS. [ABSTRACT FROM AUTHOR]

Ion mobility spectrometry with corona discharge ion source was used for the measurements of selected pesticides cybutryne, terbutryn, dichlorvos, and quinoxyfen in water. The analyses were carried out by (i) direct injection of the aqueous solution of the pesticides and (ii) extraction using solid phase microextraction by commercial SPME arrows. The instrumental and the experimental extraction parameters including the drift tube temperature, injection port temperature, and the SPME fiber type were studied and optimized to achieve the maximum signal intensity. The limit of detections obtained by the direct injection were about 0.1–1.0 mg L−1. Using the SPME arrow-ion mobility spectrometry method, the detection limits were improved 7–50 times and obtained as 0.01, 0.015, 0.05, and 0.1 mg L−1 for terbutryn, dichlorvos, cybutryne, and quinoxyfen, respectively. The recovery rate for analysis in surface water (real samples) was approximately 90–110% for both the direct injection and solid phase microextraction method. The capability of ion mobility spectrometry for the simultaneous detection of a mixture of the studied pesticides was assessed, and it was found that terbutryn, dichlorvos, and quinoxyfen can be detected simultaneously without peak overlapping. [ABSTRACT FROM AUTHOR]

The fouling phenomenon grabbed global attention and caused huge economic losses specifically in marine-related industries. Sessile behavior exposed the sponge to the risk of fouling. However, their bodies remained free from foulers, which were attributed to the chemical defense system. The objectives of this study were to determine the antibiofilm activity of the marine sponge, Stylissa carteri, and to characterize the isolated compound involved. The antibiofilm activity of S. carteri methanolic crude extract (MCE) and fractions was tested against biofilm-producing bacteria, Pseudomonas aeruginosa, using two different modes of crystal violet biofilm assays: preventive and detachment. Besides that, the disc-diffusion test was conducted to screen the antibacterial activity against gram-positive and gram-negative bacteria while a cytotoxicity assay was conducted on the HepG2 cell line. Bioassay-guided fractionation was carried out using vacuum liquid chromatography (VLC) and solid phase extraction using a C18 Sep-Pak Cartridge. The crystal compound was isolated and characterized through thin-layer chromatography (TLC), Fourier transform infrared (FTIR) spectroscopy, liquid chromatography-mass spectrometry (LCMS), and nuclear magnetic resonance (NMR) spectroscopy. The S. carteri MCE showed a promising result with a half-maximal inhibitory concentration (IC50) of 20.22 μg/mL in the preventive assay, while no IC50 was determined in the detachment assay since all inhibitions < 50%. The S. carteri MCE exhibited broad-spectrum antibacterial activity and displayed a non-cytotoxic effect. Fraction 4 from MCE of S. carteri (IC50 = 2.40 μg/mL) reduced the biofilm in the preventive assay at all concentrations and exhibited no antibacterial activity indicating the independence of antibiofilm from antibacterial properties. Based on the data obtained, an alkaloid named debromohymenialdisine (DBH) was identified from Fraction 4 of S. carteri MCE. In conclusion, S. carteri was able to reduce the establishment of the biofilm formed by P. aeruginosa and could serve as a prominent source of natural antifouling agents. [ABSTRACT FROM AUTHOR]

A novel approach employing activated nanodiamond combined with MIL-125 in micro solid-phase extraction has been successfully developed for the efficient extraction of cadmium and lead from food and water samples. Analytical parameters such as solution pH, adsorbent amount, sample volume, eluent concentration and volume, vortex time, and matrix effect to obtain the best recovery rates could be reached. The method's limits of detection were found to be 0.84 and 1.97 μg L−1 for Cd(II) and Pb(II). Its limits of quantification (LOQ) were found to be 2.81 and 6.57 μg L−1 for Cd(II) and Pb(II), respectively. Other performances that were found included preconcentration factors (PF) of 100 and 20 for Cd(II) and Pb(II), enhancement factors (EF) of 96 and 28 for Cd(II) and Pb(II), and relative standard deviation (RSD%) of 5.0 and 1.3 for Cd(II) and Pb(II), respectively. The method's validation was carried out using certified reference materials (SPS-WW2 wastewater and HR-1 Humber River sediment) ensuring its accuracy and reliability. The developed technique was successfully applied to determine the Cd(II) and Pb(II) contents in water and food samples. The optimized parameters and analytical characteristics demonstrate the method's efficiency in achieving low detection limits, high preconcentration factors, and reliable quantification. As a versatile tool for environmental and food safety analysis, this method contributes to the advancement of analytical techniques, ensuring accurate determination of trace metal concentrations in diverse sample matrices. [ABSTRACT FROM AUTHOR]

Triazine pesticides can easily remain in the environment and food, causing serious harm to organisms. Developing a pretreatment technology with strong purification and enrichment capabilities is of great significance for the detection of triazine. In this paper, magnetic dual-template nanomolecular imprinted polymers (MMIPs) were synthesized using silica-modified Fe3O4 magnetic shell nanoparticles as carriers, methacrylic acid (MAA) as a functional monomer, and cyromazine and melamine as template molecules. This material was characterized by transmission electron microscope (TEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The adsorption experiments were carried out and the results showed that the MMIPs had the chemical properties of surface molecular imprinting. The binding constants of MMIPs were 26.95 mg/L and 657.89 mg/L, and their maximum apparent binding capacity was 2.02 mg/g and 8.59 mg/g, respectively. The prepared MMIPs were used as adsorbents for dispersive solid phase extraction, and high-performance liquid chromatography analysis was coupled to determine triazine pesticides from three samples. The recovery of this method was between 84.8% and 109.5% and the limits of detection were between 0.01–0.03 µg/L. This method greatly shortens the sample pretreatment time and achieves the purpose of rapid pretreatment. [ABSTRACT FROM AUTHOR]

Nanocomposite microbeads (average diameter = 10–100 µm) were prepared by a microemulsion-solidification method and applied to the magnetic solid-phase extraction (m-SPE) of fourteen analytes, among pesticides, drugs, and hormones, from human urine samples. The microbeads, perfectly spherical in shape to maximize the surface contact with the analytes, were composed of magnetic nanoparticles dispersed in a polylactic acid (PLA) solid bulk, decorated with multi-walled carbon nanotubes (mPLA@MWCNTs). In particular, PLA was recovered from filters of smoked electronic cigarettes after an adequate cleaning protocol. A complete morphological characterization of the microbeads was performed via Fourier-transform infrared (FTIR) spectroscopy, UV–Vis spectroscopy, thermogravimetric and differential scanning calorimetry analysis (TGA and DSC), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The recovery study of the m-SPE procedure showed yields ≥ 64%, with the exception of 4-chloro-2-methylphenol (57%) at the lowest spike level (3 µg L−1). The method was validated according to the main FDA guidelines for the validation of bioanalytical methods. Using liquid chromatography-tandem mass spectrometry, precision and accuracy were below 11% and 15%, respectively, and detection limits of 0.1–1.8 µg L−1. Linearity was studied in the range of interest 1–15 µg L−1 with determination coefficients greater than 0.99. In light of the obtained results, the nanocomposite microbeads have proved to be a valid and sustainable alternative to traditional sorbents, offering good analytical standards and being synthetized from recycled plastic material. One of the main objectives of the current work is to provide an innovative and optimized procedure for the recycling of a plastic waste, to obtain a regular and reliable microstructure, whose application is here presented in the field of analytical chemistry. The simplicity and greenness of the method endows the procedure with a versatile applicability in different research and industrial fields. [ABSTRACT FROM AUTHOR]

The presence of human and veterinary pharmaceuticals (PhACs) in the environment poses potential risks. To comprehensively assess these risks, robust multiresidual analytical methods are essential for determining a broad spectrum of PhAC classes in various environmental compartments (soil, plants, and soil organisms). This study optimized extraction methods for analyzing over 40 PhACs from various matrices, including soil, lettuce, and earthworms. A four-step ultrasonic extraction method with varying extraction conditions and subsequent solid phase extraction was developed for soil samples. QuEChERS methods were optimized for extracting PhACs from lettuce and earthworm samples, addressing a literature gap in these less-studied matrices. The quantification of PhACs in soil, lettuce, and earthworm extracts was performed using a single LC–MS/MS method. Following thorough method validation, earthworms and lettuce were exposed to a mixture of 27 pharmaceuticals in a soil environment. The method validation results demonstrated the robustness of these methods for a broad spectrum of PhACs. Specifically, 29 out of 42 PhACs were extracted with an average efficiency > 50% and RSD < 30% from the soil; 40 out of 42 PhACs exhibited average efficiency > 50% and %RSD < 30% from the earthworms, while 39 out of 42 PhACs showed average efficiency > 50% and RSD < 30% from the lettuce. Exposure experiments confirmed the viability of these methods for quantifying a diverse range of PhACs in different environmental compartments. This study presents three thoroughly validated methods for determining more than 40 PhACs in diverse matrices, enabling a comprehensive assessment of PhAC dissemination in the environment. [ABSTRACT FROM AUTHOR]

Wastewater-based epidemiology (WBE) has become an objective and updated surveillance strategy for monitoring and estimating consumption trends of psychoactive substances (PSs) in the population. Firstly, magnetic shrimp shell biochar-based adsorbent (DZMBC) was synthesized and employed for extraction trace PSs from municipal wastewater. Proper pyrolysis temperature and increased KOH activator content favored the pore structure and surface area, thus facilitating extraction. DZMBC delivered exceptional extraction performance such as pH stability, anti-interference property, fast magnetic separation ability, reusability, and reproducibility. Then, a method based on magnetic solid-phase extraction (MSPE) followed by ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) was developed, validated, and utilized for the quantitative determination of five PSs in real wastewater samples. Methodological validation results indicated a favorable linearity, low method limits of detection (1.00–4.75 ng/L), and good precisions (intra-day and inter-day relative standard deviations < 4.8%). Finally, an objective snapshot of Chongqing drug use and consumption pattern was obtained. Methamphetamine (MAMP) and 3,4-methylenedioxymethamphetamine (MDMA) were the prevalent illegal drugs in local. Both concentrations and per capita consumption of MDMA displayed a change (P < 0.05) between July and September, while no statistical differences were observed for each week. [ABSTRACT FROM AUTHOR]

Background: 6-mercaptopurine (6-MP) is a chemotherapy drug mainly used to treat leukemia. It is a persistent organic pollutant and can remain in the environment for a long period of time. The presence of 6-MP in the environment poses a number of hazards and needs to be assessed to monitor its potential risk to human health and the environment. However, due to its trace amount in complicated matrices, a clean-up and preconcentration step before its determination is compulsory. Results: As a highly efficient adsorbent for the extrication of 6-mercaptopurine (6-MP), a novel carbon nanotube doped with camphor: decanoic acid deep eutectic solvent was synthesized and applied as a packing material for the pipette-tip micro solid phase extraction sorbent of 6-MP from tap, wastewater and seawater samples before its spectrophotometric determination. Characteristics and structure of this adsorbent was fully investigated. Factors affecting extraction, including type and volume of the eluent, ionic strength and pH of the sample solution, amount of adsorbent, and number of extraction and elution cycles were optimized using one-factor-at-a-time and response surface methodologies. The method was found to be linear in the range of 1 to 1000 µg/L with a limit of detection and quantification of 0.2 and 0.7 µg/L, respectively. Reproducibility as relative standard deviation was better than 4.6%. Conclusion: Application of deep eutectic solvent modified carbon nanotube indicated suitable microextraction results and good potential for rapid extraction of trace amounts of 6-MP from different aqueous samples. The amount of sample required for the analysis was less than 10 mL and only 1.5 mg of the adsorbent was used. The total analysis time, including extraction was less than 15 min and the adsorbent could be used for at least 10 times, without significantly losing its adsorption ability. Compared to using unmodified usual carbon nanotubes, deep eutectic solvent doped carbon nanotubes showed 19.8% higher extraction ability. [ABSTRACT FROM AUTHOR]

Bisphenol A (BPA), known for its endocrine-disrupting properties and potential to leach into food products, has led to significant food safety concerns. Therefore, the development of sensitive and selective BPA rapid detection methods is crucial. In this study, molecularly imprinted solid-phase extraction coupled to a colorimetric method was adopted for the smartphone-based determination of BPA. The molecularly imprinted polymer (MIP) was prepared via photopolymerization and used as a selective adsorbent material for SPE columns. The solid-phase extraction (SPE) columns with multiple cycles significantly reduced the extraction time to only 30 min. The developed method demonstrates useful sensitivity for BPA (LOD = 30 ppb). Furthermore, BPA migration from plastic packaging was evaluated under different storage conditions, revealing that microwave treatment for 5 min led to BPA release from polycarbonate packaging in juice and basic solutions. The MIP selective extraction/clean-up and smartphone-based optical sensor were successfully applied to BPA standard solutions and complex food samples (e.g., juice and tap water), resulting in reproducible and selective BPA determination (RSD ≤ 6%, n = 3). This rapid and cost-effective method of producing MIPs for BPA offers a promising solution for fast and low-cost sensing for on-site fresh food analysis. [ABSTRACT FROM AUTHOR]

Nucleic acid modifications have attracted increasing attention in recent years since they have been found to be related to a number of diseases including cancer. Previous studies have shown that the early development of endometrial cancer (EC) is often accompanied by changes in methylation levels of related genes, and the expression of related proteins that regulate reactive oxygen species (ROS) shows significant differences in EC cells and tissues. However, it has not been reported whether nucleic acid modifications related to methylation or ROS can serve as biomarkers for EC. Accurate quantification of these nucleic acid modifications still has challenges because their amounts in urine are very low and the interferences in urine are complicated. In this study, a novel dispersive solid-phase extraction (DSPE) method based on chitosan-carbon nanotube-Al2O3 (CS-CNT-Al2O3) has been established for the analysis of 5-hydroxymethyluracil (5 mU), 5-methyl-2′-deoxycytidine (5-mdC), 5-hydroxymethyl-2′-deoxycytidine (5-hmdC), 5-formyl-2′-deoxycytidine (5-fdC), and 8-hydroxy-2′-deoxyguanosine (8-OHdG) in EC patient urine samples coupled with UHPLC-QE-Orbitrap-MS/MS and HPLC–UV. Firstly, the synthesis of the CS-CNT-Al2O3 nanocomposite was conducted by a sono-coprecipitation method and was characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), and Fourier transform infrared (FTIR). Under the optimal extraction conditions of DSPE, we successfully quantified 5 mU, 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG in urine samples from 37 EC patients and 39 healthy controls. The results showed that there were significant differences in the levels of 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG in EC patients compared to the healthy control group. The receiver operator characteristic (ROC) curve analysis was carried out to evaluate the potential of 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG to distinguish EC patients from healthy volunteers. The area under the curve (AUC) for 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG was 0.7412, 0.667, 0.8438, and 0.7981, respectively. It indicated that 5-mdC, 5-hmdC, 5-fdC, and 8-OHdG had certain potential in distinguishing between EC patients and healthy volunteers and they could act as potential non-invasive biomarkers for early diagnosis of EC. Moreover, the present study would stimulate investigations of the effects of nucleic acid modifications on the initiation and progression of EC. [ABSTRACT FROM AUTHOR]

Globally, per- and polyfluoroalkyl substances (PFAS)–related research on paper products has focused on food packaging with less consideration on the presence of PFAS at different stages of the paper recycling chain. This study analysed the prevalence of PFAS in paper grades used for the manufacture of recycled paperboard. The presence of PFAS was attributed to the use of PFAS-containing additives, consumer usage, exposure to packed goods as well as contamination during mingling, sorting, collection, and recovery of paper recycling material. Q Orbitrap mass spectrometry was used to analyse the paper samples after accelerated solvent extraction and solid phase extraction. The distribution and possible propagation of 22 PFAS were determined in pre-consumer, retail and post-consumer paper products. Post-consumer samples had the highest combined average concentration (ΣPFAS) at 213 ng/g, while the ΣPFAS in retail (159 ng/g) and pre-consumer samples (121 ng/g) was detected at lower concentrations. This study showed that waste collection and recycling protocols may influence PFAS propagation and that measures must be developed to minimise and possibly eliminate exposure opportunities. [ABSTRACT FROM AUTHOR]

This study employed pre-synthesized multi-walled carbon nanotubes and their derivatives, which are used for solid phase extraction to remove the anionic dye Orange-G. The solid phases were examined and identified using several techniques, such as Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESE), zeta potential measurement, and X-ray diffraction (XRD). The solid phase amount for both systems was 0.01 g. The optimal initial concentration for Orange-G dye was 200–500 mg/L for MWCNTs derivatives and 600 mg/L for magnetic decorated systems. The ideal pH for MWCNT-tris was 5, while the pH for the other solid phases was found to be 3 in the first system. However, both systems used 25 mL of dye. The flow rate was 0.5–1.5 mL/min. The type and volume of elution were examined in this study, and it emerged that DMSO solvent was the optimal eluent with 2.5 mL for both systems. The study investigated two isotherm models, specifically Freundlich and Langmuir. The qmax was 990–1612 mg/g for the first system and 1724–1960 mg/g for the second one. [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]

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]

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]

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]

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 study, a carbon quantum dots composite was made from algal-cyanobacterial precursors using the oilothermal method. The performance of this composite as an adsorbent was evaluated in a model based on cadmium. The results showed that its optimal pH-dependent adsorption efficiency range is so broad that it covers pHs 5–10. The best correlations for adsorption isotherms and kinetics were observed with Langmuir and Elovich nonlinear models, respectively. The maximum cadmium adsorption capacity of 5.59882 ± 0.3276 mg/g and affinity constant of 2.66765 ± 0.56894 L/g were obtained in just 2 min of exposure time. The tolerance against ionic strength and co-existing cations was 5 ppm, and the recovery efficiency of cadmium from the natural sample was more than 95%. According to the findings of this research, it can be said that the algal-cyanobacterial origin carbon quantum dots composite, due to its unique properties, can be an efficient adsorbent for use in cadmium solid-phase extraction. [ABSTRACT FROM AUTHOR]

The existence of pesticides in water at ultra-trace levels necessitates the use of a suitable pre-concentration method for their detection. The objective of this study was to develop an ultra-synthetic adsorbent to extract chlorpyrifos (CPF) and imazalil (IMA) pesticides in water. X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy confirm that both oxidised and isophorone diamine multiwalled carbon nanotubes (IPD-MWCNTs) were successfully prepared with an intact structure; which was further confirmed by transmission electron microscopy (TEM) and energy-dispersive spectroscopy (EDS). The Brunauer–Emmet–Teller (BET) showed a high surface area of both oxidised and IPD-MWCNTs, which is linked to the formation of additional active sites. TGA further showed that the nanocomposites were highly stable within the pesticides quantification operating temperature. CPF and IMA were recovered using a low dosage of IPD-MWCNTs adsorbent (0.030 g) and eluted by a combined solvent (ethanol and chloroform (50:50, v/v)). The adsorbent was reusable over seven repeated cycles, with an acceptable percentage relative standard deviation (%RSD) ranging from 3 to 8%. The IPD-MWCNTs adsorption sites are highly stable and cannot be easily fouled, as compared to that of oxidised MWCNTs. Lower limits of detection (LOD) and quantification (LOQ) for CPF (0.026 and 0.078 µg.L−1) and IMA (0.033 and 0.100 µg.L−1) were achieved. Better recoveries for both analytes at low and high concentrations (as well as in real water samples) were obtained by IPD-MWCNTs whereas a conventional adsorbent (i.e. polymeric reverse phase) can only achieve better recoveries at high concentrations. [ABSTRACT FROM AUTHOR]

In this study, the influence of climatic season, molecular weight distribution, and spectroscopic properties on the formation of disinfection by-products and the biodegradability of dissolved organic matter from a tropical high-mountain reservoir was examined. Samples were collected during dry and rainy seasons and then concentrated using solid-phase extraction, with recoveries of 36.84 and 46.38%, respectively. The samples exhibited differences in their molecular weight distribution, with values of molecular weight equal to 1523.13 ± 30.41 Da for dry season samples and 2482.70 ± 13.45 Da for rainy season samples. Subsequently, the samples were fractionated using liquid preparative high-pressure size exclusion chromatography and analyzed for their biodegradability and their potential for the formation of trihalomethanes and haloacetic acids. It was observed that biodegradability was higher for the fractions with lower chromophore content (r = − 0.3571) and higher polydispersity (r = 0.5357), indicating that fractions that were more polydisperse and had a lower molecular weight were more susceptible to biological degradation. Among the haloacetic acids, bromochloroacetic acid was the major component, comprising 42.80% to 68.69% of the total haloacetic acids. Correlation analysis revealed a positive correlation between total haloacetic acids and total trihalomethanes with dissolved organic matter chromophoric character (r = 0.5357 and r = 0.4643, respectively), as well as with molecular weight (r = 0.1429 and 0.0714, respectively). [ABSTRACT FROM AUTHOR]