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Organochlorine pesticides (OCPs) are used globally to control pests in the food industry. However, some have been banned due to their toxicity. Although they have been banned, OCPs are still discharged into the environment and persist for long periods of time. Therefore, this review focused on the occurrence, toxicity, and chromatographic determination of OCPs in vegetable oils over the last 22 years (2000–2022) (111 references). Literature search shows that OCPs kill pests by destroying endocrine, teratogenic, neuroendocrine, immune, and reproductive systems. However, only five studies investigated the fate of OCPs in vegetable oils and the outcome revealed that some of the steps involved during oil processing introduce more OCPs. Moreover, direct chromatographic determination of OCPs was mostly performed using online LC-GC methods fitted with oven transfer adsorption desorption interface. While indirect chromatographic determination was favored by QuEChERS extraction technique, gas chromatography frequently coupled to electron capture detection (ECD), gas chromatography in selective ion monitoring mode (SIM), and gas chromatography tandem mass spectrometry (GC-MS/MS) were the most common techniques used for detection. However, the greatest challenge still faced by analytical chemists is to obtain clean extracts with acceptable extraction recoveries (70–120%). Hence, more research is still required to develop greener and selective extraction methods toward OCPs, thus improving extraction recoveries. Moreover, advanced techniques like gas chromatography high resolution mass spectrometry (GC-HRMS) must also be explored. OCPs prevalence in vegetable oils varied greatly in various countries, and concentrations of up to 1500 µg/kg were reported. Additionally, the percentage of positive samples ranged from 1.1 to 97.5% for endosulfan sulfate. [ABSTRACT FROM AUTHOR]

Chlorination of seawater forms a range of secondary oxidative species, collectively termed "chlorine-produced oxidants" (CPOs). These compounds do not have the same biocidal efficacy, the same fate and behavior in the marine environment, the same potential formation of chlorination by-products (CBPs), nor the same effects on marine organisms. Their chemical speciation is an important step toward an accurate assessment of the effectiveness of chlorination and the potential impacts of its releases, among others. The aim of this paper - which is the second of a trilogy dedicated to the chemical speciation of CPOs in seawater - is to cover all aspects related to CPOs analysis in seawater, from sampling to instrumental determination. First, it discusses the procedures involved in synthesis, storage, and standardization of analytical standards. Second, it deals with sampling and sample preparation, addressing all relevant issues related to these two key steps. Third, it provides a comprehensive and up-to-date overview of the colorimetric, titrimetric, and electrochemical methods used for CPOs determination and thoroughly discusses their advantages and limitations. Finally, this review ends with some recommendations for progress in the field of CPO analysis with the three aforementioned approaches. Chromatographic and mass spectrometric-based methods will be covered in the third and final article (Part III). [ABSTRACT FROM AUTHOR]

Curcumol, a significant bioactive molecule, requires accurate detection methods due to its extensive pharmacological properties. This study develops high‐performance liquid chromatography (HPLC) methods to detect curcumol and constructs sample pretreatment techniques using salt‐assisted liquid‐liquid microextraction (SALLME). The optimization process focuses on conditions for acetonitrile (ACN) anhydrous sodium sulfate‐assisted liquid‐liquid microextraction. By adding excess anhydrous sodium sulfate to an ACN aqueous solution, ACN precipitates, forming a saturated saline solution and resulting in a two‐phase system. Curcumol, being highly soluble in ACN, separates into and enriches within the ACN phase, achieving effective matrix separation. SALLME demonstrated an enrichment factor of up to 12.4 for curcumol. The extracted ACN is then injected into an HPLC instrument for quantitative detection and analysis. The method exhibited a good linear range (0.5–10.0 µg/mL) and a low detection limit (0.05 µg/mL). The results indicate that curcumol can be effectively separated from complex matrices using this technique. By optimizing salt concentration and temperature, the HPLC method for determining curcumol in biological samples was successfully established, achieving recoveries between 86.2% and 137.6% in spiked urine and blood samples. Furthermore, this method offers rapid, efficient, and environmentally friendly sample preparation, promising significant applications in pharmacological and clinical settings. [ABSTRACT FROM AUTHOR]

An easy, safe, simple, and efficient pH‐switchable hydrophobic deep eutectic solvent (DES)‐based liquid‐phase microextraction was developed for the extraction of chlorobenzenes (CBs) from water samples followed by a gas chromatography–electron capture detector (GC–ECD). The switchability of the synthesized DESs was tested by changing the pH. The DES synthesized from thymol:octanoic acid (OA) in a molar ratio of 2:1 had the highest efficiency in extracting CBs from water samples. 1,4‐Dibromobenzene was used as internal standard (IS). The optimal conditions were established to be 20.0 µL of thymol:OA (2:1), 100 µL of 5 mol L−1 KOH, 100 µL of 5 mol L−1 HCl, 60 s of extraction time, and without salt addition. Under the optimum conditions, the calibration graphs were linear in the range of 0.005–150 µg L−1, and limits of detection were in the range of 0.001–0.03 µg L−1. The relative standard deviations, including intraday and inter‐day for 5.0 µg L−1 of dichlorobenzene isomers, 2.0 µg L−1 of trichlorobenzene and tetrachlorobenzene isomers, and 0.50 µg L−1 of pentachlorobenzene and hexachlorobenzene isomers in water with using IS, were in the range of 0.6%–3.2% (n = 7) and 3.8%–6.7% (n = 7), respectively. The accuracies, including inter‐day and intraday, were in the range of 93.5%–106.3% and 91.7%–109.4%, respectively. [ABSTRACT FROM AUTHOR]

AbstractStatins are the most prescribed drug for regulating the high cholesterol level in the blood, which can lead to severe complications, such as cardiovascular diseases and other health complications. A wide range of analytical techniques have been employed for the quantification of statins from various origins, including fermentation derived (lovastatin, pravastatin, and compactin), semi-synthetic (simvastatin), and synthetic (atorvastatin, rosuvastatin, and fluvastatin) routes. The presence of more than one structural form and structural analogue generated in the biosynthesis pathway, as well as reaction intermediates and macromolecules in the clinical sample, complicates the quantification of statins. Furthermore, significant concentrations of statins in environmental samples pose serious health and ecology hazards, and estimating statins in those diluted samples is extremely difficult. On the other hand, the: cost, accurate estimation of the desired one from other structural forms, sample complexity, time, limits of detection and quantification, were major criteria distinguishing the usability of each technique. As a result, the current manuscript focuses on analytical techniques such as molecular spectroscopy (normal and derivatives UV-Visible spectrophotometer), chromatography (TLC, HP-TLC, HPLC, GC, swing column, micellar, and supercritical fluid), mass spectroscopy (HPLC-MS/MS and GC-MS/MS), sequential flow injection, capillary electrophoresis, and cyclic voltammetry, as well as their: optimal operating conditions, limits of detection and quantification, advancements, and limitations. Furthermore, various online and offline sample preparations (precipitation, solid phase extraction, liquid-liquid extraction, and micellar extraction) have been highlighted as an essential pretreatment technique to avoid the interference caused by structural analogues and other macromolecules. The greener and more sustainable concepts used in analytical approaches for the quantification statins are also highlighted with current advancements. [ABSTRACT FROM AUTHOR]

A technology is developed for manufacturing planar microfluidic chips (MFCs) based on Silgard 8040, encompassing template fabrication, mold production, sealing, and adsorbent filling. These MFCs, filled with a Porapak-Q adsorbent, facilitate sample preparation and calibration under uniform conditions, integrating both sample collection and preconcentration stages. Experimental investigations have identified optimal conditions for acetone preconcentration using Silgard 8040-based MFCs, achieving a maximum concentration factor of 43 at adsorption temperature (Tads) of 0°C, desorption temperature (Tdes) of 70°C, adsorption volume (Vads) of 45 mL, and desorption time (tdes) of 1 s. The feasibility of using MFCs for sample collection and preparation, taking into account sample storage time, has been evaluated. The procedure maintains accuracy within 6–10% over 8 h without a necessity for additional drying of the collected samples from exhaled air. [ABSTRACT FROM AUTHOR]

Super‐resolution (SR) microscopy is a cutting‐edge method that can provide detailed structural information with high resolution. However, the thickness of the specimen has been a major limitation for SR methods, and large biological structures have posed a challenge. To overcome this, the key step is to optimise sample preparation to ensure optical homogeneity and clarity, which can enhance the capabilities of SR methods for the acquisition of thicker structures.Oocytes are the largest cells in the mammalian body and are crucial objects in reproductive biology. They are especially useful for studying membrane proteins. However, oocytes are extremely fragile and sensitive to mechanical manipulation and osmotic shocks, making sample preparation a critical and challenging step.We present an innovative, simple and sensitive approach to oocyte sample preparation for 3D STED acquisition. This involves alcohol dehydration and mounting into a high refractive index medium. This extended preparation procedure allowed us to successfully obtain a unique two‐channel 3D STED SR image of an entire mouse oocyte. By optimising sample preparation, it is possible to overcome current limitations of SR methods and obtain high‐resolution images of large biological structures, such as oocytes, in order to study fundamental biological processes.Lay Abstract: Super‐resolution (SR) microscopy is a cutting‐edge tool that allows scientists to view incredibly fine details in biological samples. However, it struggles with larger, thicker specimens, as they need to be optically clear and uniform for the best imaging results. In this study, we refined the sample preparation process to make it more suitable for SR microscopy. Our method includes carefully dehydrating biological samples with alcohol and then transferring them into a mounting medium that enhances optical clarity. This improved protocol enables high‐resolution imaging of thick biological structures, which was previously challenging. By optimizing this preparation method, we hope to expand the use of SR microscopy for studying large biological samples, helping scientists better understand complex biological structures. [ABSTRACT FROM AUTHOR]

Gold nanoparticles (AuNPs) have emerged as promising agents in biomedical applications due to their unique physicochemical properties. This study investigates the cellular interactions of AuNPs with A549 (non-small cell lung adenocarcinoma) and BEAS-2B (normal bronchial epithelial) cell lines. AuNPs were synthesized via the citrate reduction method, resulting in 20, 50, and 70 nm particles. Cells were incubated with AuNPs for increasing durations (30 minutes, 4 hours, and 24 hours). Post-incubation, cells were washed with PBS, air-fixed, and subsequently analyzed using Atomic Force Microscopy (AFM) to obtain detailed topographical maps. AFM imaging revealed distinct interactions between AuNPs and the two cell lines. A549 cells displayed darker regions on the cell surface, indicative of topographical depressions likely resulting from nanoparticle-induced membrane collapse. In contrast, BEAS-2B cells did not exhibit such depressions, which is consistent with the literature that suggests cancer cells are mechanically softer than normal cells. The surface roughness analysis results indicated that the preservation of surface integrity post-fixation validates the air-fixation methodology for obtaining reliable mechanical data from AFM analyses. [ABSTRACT FROM AUTHOR]

Although not expected to be used due to restrictions raised on their usage, Persisted Organic Pollutants (POP) such as organochlorinated pesticides (OCPs) can be found in several matrices, even nowadays. The lack of biodegradation and, furthermore, their persistence in the environment result in the possible occurrence of these lipophilic toxins in several matrices, from environmental samples and foods to human milk. The current review focuses on the usage of hyphenated techniques for the determination and monitoring of OCPs in several matrices, such as milk—both animal and human milk. The lipid matrix of milk and dairy products favors the possible bioaccumulation of the above pollutants, and the complex matrix of the dairy products is a challenge for method development. Additionally, spectroscopic methods—mainly Nuclear Magnetic Resonance (NMR)-based metabolomics—for biomonitoring of OCPs persistence, bioaccumulation, and effect of possible exposure, along with NMR usage in several methods developed, are also presented and discussed. Finally, we introduce and present the metabolomic approach for OCPs and other POPs in lipid matrices. [ABSTRACT FROM AUTHOR]

Summary: Sphingolipids (SL) are bioactive compounds in milk, dairy products, and infant formula. SL has been found to have different health benefits, such as anti‐inflammatory, antimicrobial, anticancer, and cholesterol‐lowering characteristics. SL requires careful extraction, separation, and identification due to their unique characteristics. This review discusses the importance of extracting, purifying, and analysing SL from milk and dairy products. OE (Organic extraction), SPE (solid‐phase extraction), and SFE (supercritical CO2) techniques, as well as dispersive OE and SPE, are the most common methods. In addition, this review discussed various analytical techniques that can be used to determine and quantify SL classes, including TLC (thin‐layer chromatography), HPLC (high‐performance liquid chromatography), nuclear magnetic resonance spectroscopy, and mass spectrometry. These techniques are crucial for understanding the amounts of SL dairy products and infant formula. The paper also focuses on the different types of SL present in milk, dairy products, and infant formula and their concentrations. SL has the potential to be applied to the development of functional foods, and further research in this area is needed. This article sheds light on the extract, purification, and analysis of SL dairy products and infant formula, as well as their potential health benefits. [ABSTRACT FROM AUTHOR]

Food allergens in processed foods are affected by heating, processing, and the food matrix. To conduct highly reliable tests, extracting allergens into test solutions is necessary for appropriate detection. In addition to the commonly used enzyme-linked immunosorbent assay (ELISA), liquid chromatography-mass spectrometry (LC–MS), which has the advantage of simultaneously detecting multiple allergens in foods, is being increasingly used. When managing food allergens at food manufacturing sites, obtaining the same measured values is desirable, regardless of the analytical method used. Therefore, in this study, we focused on the importance of pretreatment steps for LC–MS when examining food allergens in processed foods, which can be difficult to analyze. The ELISA method uses food extracts optimized for analyzing allergens in processed foods. We developed a high-resolution accurate mass spectrometry (HRAM)-LC–MS/MS method using the same food extract used in the ELISA method and an MS sample preparation kit. Multiple food allergen analysis was performed using 1, 5, 10, and 20 ppm of allergen-incurred processed foods. Overall, a strong correlation was observed between the measured values of HRAM-LC–MS/MS and ELISA, demonstrating the applicability of multi-allergen analysis using LC–MS. [ABSTRACT FROM AUTHOR]

Ricin is a toxic protein regarded as a potential chemical weapon for bioterrorism or criminal use. In the event of a ricin incident, rapid analytical methods are essential for ricin confirmation in a diversity of matrices, from environmental to human or food samples. Mass spectrometry–based methods provide specific toxin identification but require prior enrichment by antibodies to reach trace-level detection in matrices. Here, we describe a novel assay using the glycoprotein asialofetuin as an alternative to antibodies for ricin enrichment, combined with the specific detection of signature peptides by high-resolution mass spectrometry. Additionally, optimizations made to the assay reduced the sample preparation time from 5 h to 80 min only. Method evaluation confirmed the detection of ricin at trace levels over a wide range of pH and in protein-rich samples, illustrating challenging matrices. This new method constitutes a relevant antibody-free solution for the fast and specific mass spectrometry detection of ricin in the situation of a suspected toxin incident, complementary to active ricin determination by adenine release assays. [ABSTRACT FROM AUTHOR]

Antimicrobial residues in milk pose a significant risk to human health, prompting regulatory bodies to establish safety limits to protect consumers. While traditional screening methods have primarily targeted single analytes or classes, recent advancements in multiclass screening techniques offer more comprehensive and efficient monitoring. This review highlights these advancements and focuses on methods developed since 2010, such as microbial inhibition tests, immunoassays, biosensors and LC–MS‐based approaches. It also discusses the strengths and limitations of these techniques, as well as the challenges associated with analysing milk's complex matrix, emphasising the ongoing need for innovation in food safety practices. [ABSTRACT FROM AUTHOR]

Despite advancements in the sensitivity and performance of analytical instruments, sample preparation remains a bottleneck in the analytical process. Currently, solid-phase extraction is more widely used than traditional organic solvent extraction due to its ease of use and lower solvent requirements. Moreover, various microextraction techniques such as micro solid-phase extraction, dispersive micro solid-phase extraction, solid-phase microextraction, stir bar sorptive extraction, liquid-phase microextraction, and magnetic bead extraction have been developed to minimize sample size, reduce solvent usage, and enable automation. Among these, in-tube solid-phase microextraction (IT-SPME) using capillaries as extraction devices has gained attention as an advanced "green extraction technique" that combines miniaturization, on-line automation, and reduced solvent consumption. Capillary tubes in IT-SPME are categorized into configurations: inner-wall-coated, particle-packed, fiber-packed, and rod monolith, operating either in a draw/eject system or a flow-through system. Additionally, the developments of novel adsorbents such as monoliths, ionic liquids, restricted-access materials, molecularly imprinted polymers (MIPs), graphene, carbon nanotubes, inorganic nanoparticles, and organometallic frameworks have improved extraction efficiency and selectivity. MIPs, in particular, are stable, custom-made polymers with molecular recognition capabilities formed during synthesis, making them exceptional "smart adsorbents" for selective sample preparation. The MIP fabrication process involves three main stages: pre-arrangement for recognition capability, polymerization, and template removal. After forming the template-monomer complex, polymerization creates a polymer network where the template molecules are anchored, and the final step involves removing the template to produce an MIP with cavities complementary to the template molecules. This review is the first paper to focus on advanced MIP-based IT-SPME, which integrates the selectivity of MIPs into efficient IT-SPME, and summarizes its recent developments and applications. [ABSTRACT FROM AUTHOR]

Due to technological advances in mass spectrometry, significant progress has been achieved recently in plant hormone research. Nowadays, plant hormonomics is well established as a fully integrated scientific field focused on the analysis of phytohormones, mainly on their isolation, identification, and spatiotemporal quantification in plants. This review represents a comprehensive meta-study of the advances in the phytohormone analysis by mass spectrometry over the past decade. To address current trends and future perspectives, Web of Science data were systematically collected and key features such as mass spectrometry-based analyses were evaluated using multivariate data analysis methods. Our findings showed that plant hormonomics is currently divided into targeted and untargeted approaches. Both aim to miniaturize the sample, allowing high-resolution quantification to be covered in plant organs as well as subcellular compartments. Therefore, we can study plant hormone biosynthesis, metabolism, and signalling at a spatio-temporal resolution. Moreover, this trend has recently been accelerated by technological advances such as fluorescence-activated cell sorting or mass spectrometry imaging. [ABSTRACT FROM AUTHOR]

A robust microextraction device in the form of a glass vial internally coated with metal–organic frameworks (MOFs) is designed, fabricated by in situ growth of different Zr‐based MOFs, and fully characterized for its novel use as an analytical platform. This device, uniformly coated by the MOF, ensures high simplicity and short times when used as an analytical microextraction tool, as the device acts as both the sample container and the extraction device, being tested for monitoring the presence of a group of endocrine‐disrupting chemicals in pool waters. The thin film format and MOF nature allow for high extraction efficiency and preconcentration of these target contaminants. Adsorption and desorption of the analytes are studied through kinetic experiments, with uptakes up to 90% for propylparaben in the UiO‐66‐abdc vial, and an extremely fast desorption in just seconds. The UiO‐66‐abdc vial does not require more than 15 min to perform a complete extraction‐desorption cycle, with limits of detection down to 0.10 µg L−1 in pool waters. The MOF‐coated vials are demonstrated to be easily (and highly) reusable by simple washing for a few min followed by drying. The simplicity of the method can be pushed further working in static mode or by a simple manual shaking. [ABSTRACT FROM AUTHOR]

pH is one of the key parameters in chemistry and impacts almost all chemical and biological processes. Also, within analytical chemistry and sensing, pH plays a critical role. This review underscores the critical role of pH manipulation in overcoming analytical challenges posed by complex sample matrices and dynamic environmental conditions. It explores the available tools to control pH at a local scale and how those are or can be applied to improve sensor performance. We focus on four key areas where pH modulation has been or could be leveraged to advance chemical sensing capabilities: i) sensing alkalinity and buffer capacity, ii) sample pretreatment, iii) sensing pH dependent analytes and iv) reducing biofouling. We analyze existing strategies, but also try to identify unexplored possibilities which may have potential and can be exploited for sensing. [ABSTRACT FROM AUTHOR]

Introduction: Chlorine gas can be toxic when inhaled or absorbed at high concentrations through the skin. It can cause pulmonary edema, pulmonary inflammation, respiratory failure, and potentially death. Monitoring chlorine exposure helps in determining treatment regimens and may inform safeguards, such as personal protective equipment and ventilation systems. Therefore, verification of chlorine exposure is crucial to protecting human health. This has led to identification of multiple biomarkers of Cl2 exposure with associated innovations in methods of analysis to monitor these markers. Materials and methods: In this review of the last 30 years of literature, biomarkers and associated methods of detection for the determination of chlorine exposure from biological samples are detailed and critically evaluated. Results and discussion: From the 36 included studies, the most useful biomarkers for Cl2 exposure include tyrosine adducts, chlorohydrin, chloro-fatty-acids, chloro-fatty-aldehydes, and chloro-fatty-alcohols. The most common sample preparation methods for these markers are hydrolysis and extraction and the most common analysis techniques are chromatographic separation with mass spectrometric detection. Conclusion: The findings of this review emphasize the need for continued research into biomarkers and stronger evaluation of proposed analytical methods, including validation, to allow more appropriate comparison, which will ultimately improve patient outcomes. [ABSTRACT FROM AUTHOR]

In this work, an easy, safe, simple, and efficient pH‐switchable deep eutectic solvents (DESs)‐based liquid phase microextraction followed by high‐performance liquid chromatography‐diode array detector analysis was developed for the determination of 1,3‐dimethylamylamine (DMAA). The switchability of the obtained DESs was investigated by changing the pH. Then the best‐selected DES was characterized and the application of the selected DES in the extraction of DMAA from sports nutrition and bodybuilding supplements was investigated. The DES synthesized from l‐menthol: oleic acid in a molar ratio of 1:2 had the highest efficiency in the extraction of the target compound. Under the optimum conditions, (50 µL of DES, 100 µL of 4 mol/L KOH, 100 µL of 4 mol/L HCl, extraction time of 40 s and without salt addition) the calibration graph was linear in the range of 0.05–100 µg/kg and limit of detection was 0.02 µg/kg. The relative standard deviations including intra‐day and inter‐day for 10.0 µg/kg of DMAA in real samples were 2.7% (n = 7) and 5.3% (n = 7), respectively. The enrichment factor and percentage extraction recovery of the method were 283 and 85%, respectively. The relative recoveries for DMAA in different samples were in the range of 90%–109%. [ABSTRACT FROM AUTHOR]

Vitamin K is one of the many health-promoting substances whose impact on the human body has been underestimated until recently. However, recently published research results have changed this situation, prompting some researchers to consider it a new panacea for diseases of old age. The result is a significant increase in interest in the accurate analysis of vitamin K in various types of samples, ranging from food, through dietary supplements, to biological matrices and clinical trials, both observational and interventional. This review summarizes the current state of knowledge about the proven and speculated biological activity of vitamin K and its importance for the world's aging societies, including the methods used for its isolation and analysis in various matrices types. Of all the analytical methods, the currently preferred methods of choice for the direct analysis of vitamin K are chromatographic methods, in particular liquid chromatography-tandem mass spectrometry. This technique, despite its sensitivity and selectivity, requires an appropriate stage of sample preparation. As there is still room for improvement in the efficiency of these methods, especially at the sample preparation stage, this review shows the directions that need to be taken to make these methods faster, more efficient and more environmentally friendly. [ABSTRACT FROM AUTHOR]

We present a comparison of common electron microscopy sample preparation methods for studying crystallisation processes from solution using both scanning and transmission electron microscopy (SEM and TEM). We focus on two widely studied inorganic systems: calcium sulphate, gypsum (CaSO4·2H2O) and calcium carbonate (CaCO3). We find significant differences in crystallisation kinetics and polymorph selection between the different sample preparation methods, which indicate that drying and chemical quenching can induce severe artefacts that are capable of masking the true native state of the crystallising solution. Overall, these results highlight the importance of cryogenic (cryo)‐quenching crystallising solutions and the use of full cryo‐TEM as the most reliable method for studying the early stages of crystallisation. [ABSTRACT FROM AUTHOR]

Among the various compounds regarded as emerging contaminants (ECs), pharmaceuticals and personal care products (PPCPs) are of particular concern. Their continuous release into the environment has a negative global impact on human life. This review summarizes the sources, occurrence, persistence, consequences of exposure, and toxicity of PPCPs, and evaluates the various analytical methods used in the identification and quantification of PPCPs in a variety of solid and liquid environmental matrices. The current techniques of choice for the analysis of PPCPs are state-of-the-art liquid chromatography coupled to mass spectrometry (LC-MS) or tandem mass spectrometry (LC-MS2). However, the complexity of the environmental matrices and the trace levels of micropollutants necessitate the use of advanced sample treatments before these instrumental analyses. Solid-phase extraction (SPE) with different sorbents is now the predominant method used for the extraction of PPCPs from environmental samples. This review also addresses the ongoing analytical method challenges, including sample clean-up and matrix effects, focusing on the occurrence, sample preparation, and analytical methods presently available for the determination of environmental residues of PPCPs. Continuous development of innovative analytical methods is essential for overcoming existing limitations and ensuring the consistency and diversity of analytical methods used in investigations of environmental multi-class compounds. [ABSTRACT FROM AUTHOR]

UV spectrophotometric determination of salicylic acid in several multicomponent drugs using an ethylcellulose-based sorbent for solid-phase extraction (SPE) for sample preparation was shown to be selective. Selective binding of the analyte to sorbent active sites and stepwise elution successively with purified water and NaOH solution (0.1 M) during SPE eliminated interference of other active pharmaceutical ingredients of multicomponent drugs during identification and quantitation of salicylic acid by UV spectrophotometry. Use of the ethylcellulose sorbent made it possible to improve the metrological parameters and decrease systematic error of the quantitative procedure by an average of 47%. [ABSTRACT FROM AUTHOR]

Here, we provide an overview of the key factors to consider when using fluorescence nanoscopy (FN), including biological questions that can be addressed and aspects that might improve the reliability and effectiveness of FN experiments. We cover the main aspects related to sample preparation, including the selection of appropriate fixation, affinity-based labels, and fluorescent dyes. We discuss current limitations and possible future developments in the field that would facilitate a broader application of FN. We discuss multiplexing possibilities (allowing the simultaneous detection of multiple targets in a single experiment), live cell imaging for the study of cellular and molecular dynamic processes, and quantitative workflows. Recently, biologists have gained access to several far-field fluorescence nanoscopy (FN) technologies that allow the observation of cellular components with ~20 nm resolution. FN is revolutionizing cell biology by enabling the visualization of previously inaccessible subcellular details. While technological advances in microscopy are critical to the field, optimal sample preparation and labeling are equally important and often overlooked in FN experiments. In this review, we provide an overview of the methodological and experimental factors that must be considered when performing FN. We present key concepts related to the selection of affinity-based labels, dyes, multiplexing, live cell imaging approaches, and quantitative microscopy. Consideration of these factors greatly enhances the effectiveness of FN, making it an exquisite tool for numerous biological applications. [ABSTRACT FROM AUTHOR]

Preparation of biomacromolecules for structural biology studies is a complex and time‐consuming process. The goal is to produce a highly concentrated, highly pure product that is often shipped to large facilities with tools to prepare the samples for crystallization trials or for measurements at synchrotrons and cryoEM centers. The aim of this article is to provide guidance and to discuss general considerations for shipping biomacromolecular samples. Details are also provided about shipping samples for specific experiment types, including solution‐ and cryogenic‐based techniques. These guidelines are provided with the hope that the time and energy invested in sample preparation is not lost due to shipping logistics. [ABSTRACT FROM AUTHOR]

Psychological disorders and dramatic social problems are serious concerns regarding the abuse of amphetamine and its stimulant derivatives worldwide. Consumers of such drugs experience great euphoria along with serious health problems. Determination and quantification of amphetamine-type stimulants are indispensable skills for clinical and forensic laboratories. Analysis of low drug doses in bio-matrices necessitates applications of simple and also effective preparation steps. The preparation procedures not only eliminate adverse matrix effects, but also provide reasonable clean-up and pre-concentration benefits. The current review presents different methods used for sample preparation of amphetamines from urine as the most frequently used biological matrix. The advantages and limitations of various sample preparation methods were discussed focusing on the miniaturized methods. [ABSTRACT FROM AUTHOR]

This study investigated the capability of electromembrane extraction (EME) as a general technique for peptides, by extracting complex pools of peptides comprising in total of 5953 different substances, varying in size from seven to 16 amino acids. Electromembrane extraction was conducted from a sample adjusted to pH 3.0 and utilized a liquid membrane consisting of 2‐nitrophenyl octyl ether and carvacrol (1:1 w/w), containing 2% (w/w) di(2‐ethylhexyl) phosphate. The acceptor phase was 50 mM phosphoric acid (pH 1.8), the extraction time was 45 min, and 10 V was used. High extraction efficiency, defined as a higher peptide signal in the acceptor than the sample after extraction, was achieved for 3706 different peptides. Extraction efficiencies were predominantly influenced by the hydrophobicity of the peptides and their net charge in the sample. Hydrophobic peptides were extracted with a net charge of +1, while hydrophilic peptides were extracted when the net charge was +2 or higher. A computational model based on machine learning was developed to predict the extractability of peptides based on peptide descriptors, including the grand average of hydropathy index and net charge at pH 3.0 (sample pH). This research shows that EME has general applicability for peptides and represents the first steps toward in silico prediction of extraction efficiency. [ABSTRACT FROM AUTHOR]

Porous cage materials with certain dimensions, sizes, shapes, and functions have been regarded as promising materials for sample preparation, chromatographic separation, and detection process. In contrast to infinite frameworks such as metal‐organic frameworks or covalent organic frameworks, porous cage materials are constructed from discrete molecules containing at least one internal cavity. The well‐defined cavities in porous cage materials provide opportunities for non‐covalent interactions. These interactions can be programmed into the ligand design or supramolecular cage constructing using the cages as building blocks, offering various host‐guest recognition with great selectivity. In this review, we desire to elucidate the fundamental principles governing the design and fabrication of porous cage materials with well‐defined cavities, good solvent processability, and modifiable groups, the applications of these porous cage materials in sample preparation, chromatographic separation, and detection were discussed. The recent advantages of porous cage materials for the analysis process were summarized. We state the potential of these materials and provide an outlook for further application strategies. We expect that this review can inspire interest in the porous cage materials research area for analysis. [ABSTRACT FROM AUTHOR]

Mass spectrometry has revolutionized cell signaling research by vastly simplifying the analysis of many thousands of phosphorylation sites in the human proteome. Defining the cellular response to perturbations is crucial for further illuminating the functionality of the phosphoproteome. Here we describe µPhos ('microPhos'), an accessible phosphoproteomics platform that permits phosphopeptide enrichment from 96-well cell culture and small tissue amounts in <8 h total processing time. By greatly minimizing transfer steps and liquid volumes, we demonstrate increased sensitivity, >90% selectivity, and excellent quantitative reproducibility. Employing highly sensitive trapped ion mobility mass spectrometry, we quantify ~17,000 Class I phosphosites in a human cancer cell line using 20 µg starting material, and confidently localize ~6200 phosphosites from 1 µg. This depth covers key signaling pathways, rendering sample-limited applications and perturbation experiments with hundreds of samples viable. We employ µPhos to study drug- and time-dependent response signatures in a leukemia cell line, and by quantifying 30,000 Class I phosphosites in the mouse brain we reveal distinct spatial kinase activities in subregions of the hippocampal formation. Synopsis: The study introduces µPhos, an accessible, plate-based workflow for low-input mass spectrometry-based phosphoproteomics. µPhos greatly facilitates high-dimensional experimental designs, as demonstrated by a 96-well drug response screen and analysis of small anatomical regions in the mouse brain. Systematic optimization results in sensitive and selective enrichment of phosphopeptides in <100 µL, allowing direct processing of 96-well plates within one working day. µPhos combined with dia-PASEF reproducibly quantifies 6000 to 17,000 confidently localized phosphosites from 1 to 20 µg protein starting material. Sub-region resolved analysis of the mouse brain phosphoproteome infers spatially distinct kinase activity. Time-course analysis of chronic myeloid leukemia cells treated with tyrosine kinase inhibitors reveals drug-specific responses. The study introduces µPhos, an accessible, plate-based workflow for low-input mass spectrometry-based phosphoproteomics. µPhos greatly facilitates high-dimensional experimental designs, as demonstrated by a 96-well drug response screen and analysis of small anatomical regions in the mouse brain. [ABSTRACT FROM AUTHOR]

This study was conducted to optimize the calcimetry method (CM) and back titration method (BTM) for determination of calcium carbonate equivalent (CCE) in calcareous soils. For this purpose, 12 soil samples with wide CCE ranges and various physiochemical properties were selected to investigate the effect of contact time, sample preparation, soil-to-HCl ratio, heating, and HCl concentration on CCE measured by CM and BTM. Afterward, the optimized methods were compared by analysis of 100 calcareous soil samples. Results showed that the sample preparation is a key parameter affecting CCE determination, and the complete crushing of the sample without sieving led to the best results. Improper soil-to-hydrochloric acid (HCl) ratio led to overestimation of CCE. The kinetic experiment results revealed that the CCE dissolution in HCl was fast, and equilibrium was established in less than 5 minutes. The optimized BTM involved weighing 1–10 g of ground soil (depending on CCE content), adding 20 mL of 1 N HCl, heating for 5 minutes on a hotplate, and titrating by 1 N NaOH in the presence of phenolphthalein. The optimized CM involved weighing 1–5 g ground soil and adding 7 mL of 4 N HCl with a contact time of 5 minutes. The BTM and CM were highly correlated (r = 0.991) in the determination of CCE in a wide range of calcareous soils (100 soil samples), and the relevant regression equation can be employed as a transfer function to convert the BTM to CM results. [ABSTRACT FROM AUTHOR]

Aroma determination in alcoholic beverages has become a hot research topic due to the ongoing effort to obtain quality products, especially in a globalized market. Consumer satisfaction is mainly achieved by balancing several aroma compounds, which are mixtures of numerous volatile molecules enclosed in challenging matrices. Thus, sample preparation strategies for quality control and product development are required. They involve several steps including copious amounts of hazardous solvents or time‐consuming procedures. This is bucking the trend of the ever‐increasing pressure to reduce the environmental impact of analytical chemistry processes. Hence, the evolution of sample preparation procedures has directed towards miniaturized techniques to decrease or avoid the use of hazardous solvents and integrating sampling, extraction, and enrichment of the targeted analytes in fewer steps. Mass spectrometry coupled to gas or liquid chromatography is particularly well suited to address the complexity of these matrices. This review surveys advancements of green miniaturized techniques coupled to mass spectrometry applied on all categories of odor‐active molecules in the most consumed alcoholic beverages: beer, wine, and spirits. The targeted literature consider progresses over the past 20 years. [ABSTRACT FROM AUTHOR]

In this study, a new method was developed for extraction and determination of polycyclic aromatic hydrocarbons (PAHs) in biota samples. The biota samples were packed inside a porous membrane bag and subjected to ultrasonication-assisted solvent extraction. This method showed good applicability to both low and high sample weights. The effect of various parameters such as type and volume of extraction solvent, ultrasonication time, sample weight, and dimensions of extraction device on extraction performance was evaluated. The developed method showed a good linear range from 12.5 to 100 ng/g for all the selected analytes with correlation coefficients ranging from 0.9907 to 0.9999. The limits of detection ranged from 0.97 to 3.47 ng/g. The method's precision was assessed based on relative standard deviations, which were below 13.5% indicating an acceptable precision. The developed procedure used for determination of PAHs in biota samples is characterized by many positive features. The packing of dried biota samples inside the membrane bag is advantageous because it eliminates several steps such as filtration or centrifugation and further extract purification. As the samples are protected inside the membrane bag, they can be easily separated from the solvent extract after the completion of the extraction process by simply removing the membrane bag. Moreover, the membrane may hinder the transportation of macromolecules to the extract, thus resulting in a relatively cleaner extract. Due to its simplicity and excellent figures of merit, this method presents a better potential for routine analysis of polycyclic aromatic hydrocarbons in biota samples. [ABSTRACT FROM AUTHOR]

The measurement uncertainty (MU) in environmental analyses is usually considered as a combination of the additive contributions from sampling, sample preparation and analytical measurement (usually instrumental). The target MU for such studies is usually relatively high due to the natural sample heterogeneity and/or the complicated pretreatment procedure required. In the analytical practice, the contribution of the sample preparation to MU is rarely evaluated. Thus, it remains a hidden part of the one related to the analysis. However, the knowledge for the contribution of sample preparation might provide important information and further possibility for optimization of the entire analytical procedure and reduction of the expanded MU of the analytical result. From statistical point of view, the separation of uncertainty contributions from the different steps is, generally, not a trivial task. Selection of the proper statistical approach depends on the data structure and quality, variables distribution, etc. In the present study, three different statistical methods for evaluation of the uncertainty contribution of the sample preparation were applied, compared, and discussed. The considered approaches are based on, both, classical and robust analysis of variances (ANOVA) applied to data from instrumental analysis of marine algae and bee honey samples, undergoing microwave digestion. Some general recommendations on the statistical approach selection are revealed based on real experimental data set. [ABSTRACT FROM AUTHOR]

Soil is one of the main destinations for pesticides and veterinary drugs used in agriculture and animal production. The negative consequences of the accumulation of these compounds in the environment make it important to monitor these compounds in the soil. In this study, we compared different extraction procedures using solvent shaking, ultrasound, or QuEChERS, and their combinations, for the simultaneous determination of 75 pesticide and seven veterinary drug residues in agricultural soil by ultra-high performance liquid chromatography coupled to serial mass spectrometry (UHPLC–MS/MS). The method using QuEChERS combined with shaking showed the best results for soil using the addition of water, followed by extraction with acetonitrile acidified with acetic acid and shaking in a shaker. For partitioning, anhydrous magnesium sulfate and anhydrous sodium acetate were used. The extract was centrifuged, filtered, and diluted (1:4, v/v) in water for determination by UHPLC–MS/MS. Method validation showed adequate accuracy and precision results, with recoveries between 70 and 120% and RSD ≤ 20% for the vast majority of the compounds evaluated at the spike levels of 10, 25, 50, and 100 μg kg−1. The method limits of detection (LOD) and quantification (LOQ) ranged from 3.0 to 7.5 μg kg−1 and from 10 to 25 μg kg−1, respectively. The method was applied to different agricultural soil samples and proved to be efficient for routine analysis. [ABSTRACT FROM AUTHOR]

Sample preparation, including extraction, separation, and purification, is a vital process for natural product analysis. As an attractive sample pretreatment method, magnetic solid‐phase extraction (MSPE) has gained plenty of attention, mainly due to its simpler operation, less consumption of organic solvents, and shorter processing time than traditional SPE. This updated review is devoted to summarizing the applications of MSPE based on different magnetic nanomaterials in the analysis of various natural products in complex matrixes, such as biological samples, plants, and Chinese herbal preparations in the past four years (2020–2023). The preparation and fabrication of different materials are briefly introduced. Furthermore, the extraction mechanism and interaction forces between adsorbent and analytes are elaborated, and the advantages and disadvantages of different adsorbents coupled with various analytical methods for MSPE of different natural products are summarized. Moreover, the future trends and opportunities for MSPE in the natural product analysis are discussed. It is expected that this work can provide updated information for future research on the applications of MSPE in such fields. [ABSTRACT FROM AUTHOR]

Accurate measurement of steroid hormones is crucial to elucidate new mechanisms of action and diagnose steroid metabolism-related diseases. This study presents a simple, sensitive, and automated analytical method for nine representative steroid hormones. The method involves on-line coupling of in-tube solid-phase microextraction (IT-SPME) with liquid chromatography–tandem mass spectrometry (LC–MS/MS). The steroid hormones were extracted and enriched on a Supel-Q PLOT capillary column using IT-SPME. Subsequently, they were separated and detected within 6 min using a Discovery HS F5-3 column and positive ion mode multiple reaction monitoring system via LC–MS/MS. Calibration curves of these compounds using each stable isotope-labeled internal standard (IS) showed linearity with correlation coefficients greater than 0.9990 in the range of 0.01–40 ng/mL, with limits of detection (S/N = 3) of 0.7–21 pg/mL. Moreover, intra- and inter-day variations were lower than 8.1 and 15% (n = 6), respectively. The recoveries of these compounds from saliva samples were in the range of 82–114%. The developed IT-SPME/LC–MS/MS method of steroid hormones is a highly sensitive, specific, and non-invasive analytical method that allows extraction and enrichment with no organic solvents, and enables direct automated online analysis by simply ultrafiltrating a small sample of saliva. [ABSTRACT FROM AUTHOR]

Infrared microscopy has become a significant analytical technique with a transformative impact on various scientific disciplines. This review examines its applications in biomedical research, materials science, environmental monitoring, and art conservation. The non-invasive and label-free technique has revolutionized disease diagnostics, drug discovery, and tissue engineering by providing comprehensive molecular and cellular insights. In materials science, it has significantly advanced understanding of microstructure and material properties, facilitating the development of novel materials. In environmental monitoring, infrared microscopy plays a crucial role in assessing microplastics and atmospheric pollutants, supporting environmental protection efforts. In art preservation, the technique offers valuable insights into the composition and deterioration of historical artworks. Recent advancements in sensor technology, particularly InGaAs and graphene-based detectors, coupled with artificial intelligence and machine learning, have greatly enhanced image analysis capabilities. The review identifies key challenges such as surpassing the diffraction limit and interpreting complex data. Ethical concerns, including data privacy and equitable access to technology, are also emphasized. Infrared microscopy remains a vital tool for advancing scientific knowledge and practical applications. Its impact is poised to expand with future technological developments, contingent upon addressing both technological challenges and ethical considerations. [ABSTRACT FROM AUTHOR]

Microwave-induced combustion (MIC) was proposed in this study for honey decomposition aiming for As, Cd, Hg, and Pb determination by inductively coupled plasma mass spectrometry (ICP-MS). Sample mass (up to 1.0 g), absorbing solution (0.5 to 14.4 mol L−1 HNO3, and H2O), heating program, and combustion aids were evaluated. The Eurachem guidelines were used for method validation. The proposed method enabled combustion of a high sample mass (0.8 g of honey, with 0.4 g of microcrystalline cellulose and 100 µL of 6 mol L−1 NH4NO3) using 6 mL of an absorbing solution consisting of 1 mol L−1 HNO3, which resulted in low residual carbon in solution (< 25 mg L−1). Honey samples from different geographical origins were analyzed. Results showed no significant difference in comparison to other two microwave decomposition methods, based on microwave-assisted wet digestion with single reaction chamber (MAWD-SRC) and microwave-assisted wet digestion (MAWD). Standard addition experiments resulted in recoveries higher than 98%. The limits of detection ranged from 1.10 (As) to 4.60 ng g−1 (Pb). In addition to using only diluted reagents and resulting in digests virtually free of interferences, the proposed method was faster (< 30 min) than most of those presented in the literature. [ABSTRACT FROM AUTHOR]

This work discusses ceramic filter materials used as substrates to study biological objects by electron microscopy. The composition, structure, pore sizes, and morphology of ceramic substrates made of foamed silicate prior to and following the application of inverse silicon oxide opals were evaluated by x-ray diffraction analysis and SEM method. Adescription of the use of the obtained filtering substrates in an experiment with biological objects is given. The substrates seem promising for electron microscopy, since they can be used for sample preparation of biological objects with the use of metal spraying or ionic liquid. This technique, together with the filtering porous material and the technical capabilities of the microscope, preserves the physical characteristics of biological objects. [ABSTRACT FROM AUTHOR]

Abstract: Point‐of‐care testing (POCT) has played important role in clinical diagnostics, environmental assessment, chemical and biological analyses, and food and chemical processing due to its faster turnaround compared to laboratory testing. Dedicated manipulations of solutions or particles are generally required to develop POCT technologies that achieve a "sample‐in‐answer‐out" operation. With the development of micro‐ and nanotechnology, many tools have been developed for sample preparation, on‐site analysis and solution manipulations (mixing, pumping, valving, etc.). Among these approaches, the use of acoustic waves to manipulate fluids and particles (named acoustofluidics) has been applied in many researches. This review focuses on the recent developments in acoustofluidics for POCT. It starts with the fundamentals of different acoustic manipulation techniques and then lists some of representative examples to highlight each method in practical POC applications. Looking toward the future, a compact, portable, highly integrated, low power, and biocompatible technique is anticipated to simultaneously achieve precise manipulation of small targets and multimodal manipulation in POC applications. [ABSTRACT FROM AUTHOR]

Sample preparation is of utmost importance for any microscopy and microstructural analysis. Correct preparation will allow accurate interpretation of microstructural features. A well‐polished section is essential when scanning electron microscopy (SEM) is used in backscattering electron (BSE) mode and characteristic X‐rays are to be quantified using an energy‐dispersive spectroscopy (EDS) detector. However, obtaining a well‐polished section, especially for cementitious materials containing aggregates, is considered to be challenging and requires experience. A sample preparation procedure consists of cutting, grinding and polishing. Undercutting of soft and brittle paste between harder aggregates can be overcome by vacuum epoxy impregnation offering mechanical support in the matrix. Furthermore, most of the attention during the sample preparation is given to the polishing of the sample. There is a wide range of suggestions on polishing steps, ranging from grain sizes, time and applied force; however, the final assessment of a polish surface is often subjective and qualitative. Therefore, a quantitative, reproducible guidance on the grinding steps, effect of experimental parameters and the influence of different grinding steps on the surface quality are required. In this paper, the influence of grinding was quantitatively evaluated by a digital microscope equipped with optical profilometry tools, through a step‐wise procedure, including sample orientation, grinding time and the difference between cement paste and concrete. Throughout the grinding procedure, the surface profiles were determined after each grinding step. This showed the step‐wise change in surface roughness and quality during the grinding procedure. Finally, the surface qualities were evaluated using optical and electron microscopy, which show the importance of the grinding/prepolishing steps during sample preparation. [ABSTRACT FROM AUTHOR]

Aquatic ecosystems serve as the primary reservoir for microplastics entering the environment. The assessment of the microplastics content in natural waters and sediments is a pressing task, the resolution of which is essential for evaluating the degree of pollution of water bodies, identifying sources of contamination, and assessing potential risks to aquatic inhabitants. Currently, there is no universal analytical approach to separating microplastics from natural waters and sediments for subsequent identification. This review summarizes information on the methods for sampling microplastics from natural waters and sediments and sample preparation techniques, including size- and density-based particle separation methods, as well as digestion-based methods relying on the digestion of samples to remove natural organic matter. Additionally, it outlines the classification of microplastics and provides general insights into their prevalence in aquatic ecosystems and potential toxicity. [ABSTRACT FROM AUTHOR]

To conduct a food safety survey by analysing the pesticide content of various commercial beverages, a dispersive micro-solid-phase extraction procedure was performed using MIL-68 (Al) (a metal-organic framework based on aluminium and 1,4-benzenedicarboxylic acid) as an efficient adsorbent following a preconcentration step by dispersive liquid–liquid microextraction. In the extraction process, the adsorbent was added to an aqueous solution containing the mentioned pesticides and vortexed well. After centrifugation, the analytes loaded on the adsorbent were eluted using 2-propanol. Then, µL-level of 1,1,2-trichloroethane, as the extraction solvent, was mixed with the obtained 2-propanol phase and injected into deionised water containing dissolved Na2SO4 in which a cloudy solution appeared. One microlitre of the sedimented phase after centrifugation of the cloudy solution was injected into a gas chromatograph equipped with a flame ionisation detector. Satisfactory outcomes such as wide linear ranges (5.95–1000 μg L−1), acceptable relative standard deviations (4.6–6.9% for intra- (n = 6) and 5.6–7.4% for inter-day (n = 3) precisions), high enrichment factors (228–350), reasonable extraction recoveries (45–70%), satisfactory relative recoveries (82–108%), and low limits of detection (1.15–1.80 µg L−1) and quantification (3.80–5.95 µg L−1) were obtained. This research demonstrates the successful application of MIL-68 (Al) for the analysis of some pesticides in fruit beverages. Also, using mg amount of the sorbent and µL volume of the extraction solvent makes the method precious. Moreover, using a green metal, aluminium, as the central ion of the synthesised metal-organic framework is another beneficial aspect of the research. [ABSTRACT FROM AUTHOR]

Vacuum‐assisted headspace solid‐phase microextraction (Vac‐HS‐SPME) is a technique used to enhance SPME sampling of semi‐volatile organic compounds. Here, it was combined with a high‐capacity SPME Arrow, which features a larger volume of extraction phase and a more rugged configuration than traditional extraction fibers. An in‐depth assessment of the critical parameters was conducted to achieve optimal extraction of representative compounds from a model solid sample matrix (Ottawa sand). Operational fundamentals investigated included the types of seals needed to create a leak‐free environment under vacuum conditions; the magnitude of the vacuum applied and time needed to activate the Vac kinetics; order of sample vial preparation methods (VPMs); and other standard variables associated with extract analysis by gas chromatography‐mass spectrometry. When exploring the limits of sample VPMs, results indicated an ideal workflow requires the solid sample to be spiked before sealing the vial, allow the sample to rest overnight, then apply vacuum at a pressure of ‐677 mbar (out of ‐789 mbar maximum possible vacuum with pump and compressor used), exerted on the vial for 90 s. This work provides the necessary workflow for the optimization of Vac‐HS‐SPME sampling of analytes from solid matrices. [ABSTRACT FROM AUTHOR]

Establishing the influence of sample preparation method on shear wave velocity or associated small-strain shear modulus (G0) of silty sands is a subject of considerable interest. This paper presents an attempt to address this topic through a comprehensive experimental programme covering four sample preparation methods. The experiments were conducted on clean Toyoura sand and its mixtures with two types of fines of different sizes. For each sample preparation method, a range of void ratio and confining stress was investigated to obtain a comprehensive view of the influence of sample preparation and its interplay with other factors. One of the notable findings is that, compared with clean sand, the difference of G0 induced by different sample reconstitution methods can be much enlarged for silty sand, and the influence is coupled with the size disparity ratio of the mixtures. The reduction of G0 due to the presence of fines also depends on sample preparation method and for smaller fines the reduction is more significant. A careful examination of the X-ray images of the specimens made by different methods suggests that the observed effects are mainly associated with the different contact conditions of coarse and fine grains. [ABSTRACT FROM AUTHOR]

Introduction: Changes in the categories and concentrations of salivary metabolites may be closely related to oral, intestinal or systemic diseases. To study salivary metabolites, the first analytical step is to extract them from saliva samples as much as possible, while reducing interferences to a minimum. Frequently used extraction methods are protein precipitation (PPT), liquid-liquid extraction (LLE) and solid-phase extraction (SPE), with various organic solvents. The types and quantities of metabolites extracted with different methods may vary greatly, but few studies have systematically evaluated them. Objectives: This study aimed to select the most suitable methods and solvents for the extraction of saliva according to different analytical targets. Methods: An untargeted metabolomics approach based on liquid chromatography-mass spectrometry was applied to obtain the raw data. The numbers of metabolites, repeatability of the data and intensities of mass spectrometry signals were used as evaluation criteria. Results: PPT resulted in the highest coverage. Among the PPT solvents, acetonitrile displayed the best repeatability and the highest coverage, while acetone resulted in the best signal intensities for the extracted compounds. LLE with the mixture of chloroform and methanol was the most suitable for the extraction of small hydrophobic compounds. Conclusion: PPT with acetonitrile or acetone was recommended for untargeted analysis, while LLE with the mixture of chloroform and methanol was recommended for small hydrophobic compounds. [ABSTRACT FROM AUTHOR]

Organophosphate flame retardants (OPFRs) are high-production volume chemicals widely present in environmental compartments. The presence of water-soluble OPFRs (tri-n-butyl phosphate (TnBP), tris(2-butoxyethyl) phosphate (TBEP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCPP), and triethyl phosphate (TEP)) in water compartments evidences the struggle of conventional wastewater treatment plants (WWTPs) to effectively eliminate these toxic compounds. This study reports for the first time the use of white-rot fungi as a promising alternative for the removal of these OPFRs. To accomplish this, a simple and cost-efficient quantification method for rapid monitoring of these contaminants' concentrations by GC–MS while accounting for matrix effects was developed. The method proved to be valid and reliable for all the tested parameters. Sample stability was examined under various storage conditions, showing the original samples to be stable after 60 days of freezing, while post-extraction storage techniques were also effective. Finally, a screening of fungal degraders while assessing the influence of the glucose regime on OPFR removal was performed. Longer chain organophosphate flame retardants, TBP and TBEP, could be easily and completely removed by the fungus Ganoderma lucidum after only 4 days. This fungus also stood out as the sole organism capable of partially degrading TCEP (35% removal). The other chlorinated compound, TCPP, was more easily degraded and 70% of its main isomer was removed by T. versicolor. However, chlorinated compounds were only partially degraded under nutrient-limiting conditions. TEP was either not degraded or poorly degraded, and it is likely that it is a transformation product from another OPFR's degradation. These results suggest that degradation of chlorinated compounds is dependent on the concentration of the main carbon source and that more polar OPFRs are less susceptible to degradation, given that they are less accessible to radical removal by fungi. Overall, the findings of the present study pave the way for further planned research and a potential application for the degradation of these contaminants in real wastewaters. [ABSTRACT FROM AUTHOR]

Nowadays, molecularly imprinted polymers (MIPs) are well established and are considered excellent materials for performing selective extractions. However, with the progressive implementation of the principles of green chemistry, it is necessary to find greener alternatives for both the synthesis and further use of MIPs in sample preparation. Accordingly, in the present work, different deep eutectic solvents (DES, both hydrophilic and hydrophobic), as an alternative to conventional organic solvents (i.e., toluene), were evaluated as porogens for the synthesis of imprinted fibers (monoliths), using fused silica capillaries as molds, for solid-phase microextraction (SPME). From this study, the polymer prepared with propazine (dummy template), methacrylic acid (monomer), ethylene glycol dimethacrylate (cross-linker), and a formic acid:L-menthol (1:1) DES (porogen) showed the best performance for selective rebinding of triazines. After optimization of the different variables involved in SPME, the new imprinted fibers were successfully applied to the extraction of target analytes (desisopropylatrazine, desethylatrazine, simazine, and atrazine) from soil sample extracts, providing relative recoveries ranging from 75.7 to 120.1%, reaching limits of detection within the range of 6.2–15.7 ng g−1, depending upon the analyte. [ABSTRACT FROM AUTHOR]

Although in situ transmission electron microscopy (TEM) of nanomaterials has been gaining importance in recent years, difficulties in sample preparation have limited the number of studies on electrical properties. Here, a support‐based preparation method of individual 1D and 2D materials is presented, which yields a reproducible sample transfer for electrical investigation by in situ TEM. A mechanically rigid support grid facilitates the transfer and contacting to in situ chips by focused ion beam with minimum damage and contamination. The transfer quality is assessed by exemplary specimens of different nanomaterials, including a monolayer of WS2. Possible studies concern the interplay between structural properties and electrical characteristics on the individual nanomaterial level as well as failure analysis under electrical current or studies of electromigration, Joule heating, and related effects. The TEM measurements can be enriched by additional correlative microscopy and spectroscopy carried out on the identical object with techniques that allow a characterization with a spatial resolution in the range of a few microns. Although developed for in situ TEM, the present transfer method is also applicable to transferring nanomaterials to similar chips for performing further studies or even for using them in potential electrical/optoelectronic/sensing devices. [ABSTRACT FROM AUTHOR]

The present research proposes investigating deep eutectic solvents for extracting Pb from biological samples for further determination by GF AAS. Among the synthesized solvents, the DES obtained from choline chloride and oxalic acid (ChCl : Ox) in a molar ratio 1 : 1 presented the best lead (Pb) extraction efficiency. Subsequently, it was characterized by Fourier Transform Infrared Spectroscopy (FTIR). For extraction, the optimized conditions were: 40 mg of sample, 400 μL of DES (ChCl : Ox) added, and 30 min at 95±5 °C. The supernatant was diluted, and the Pb was determined by GF AAS. The optimized instrumental conditions for Pb determination were 900 °C and 2100 °C, pyrolysis and atomization temperatures, respectively, using Pd as a chemical modifier. The limits of detection and quantification were 0.04 and 0.12 μg g−1, respectively. The method's accuracy was evaluated by analyzing the certificate reference materials, and good agreement was obtained between the determined and certificate values. The greenness of the proposed method was evaluated by green star and eco‐scale metrics. Thus, the proposed method proved simple, efficient, and eco‐friendly for determining Pb in biological samples. [ABSTRACT FROM AUTHOR]