Triazoles in the environment: An update on sample pretreatment and analysis methods.

Triazoles, due to their high bactericidal performance, have been widely used in the agricultural, clinical, and chemical industry. However, triazoles have been proven to cause endocrine-toxic and organ impairment in humans as a potentially toxic substance. Besides, because of the improper use and difficulty of degradation, triazoles pesticide residues left in the environment could pose a threat to the environment. Therefore, the rapid, reliable, accurate, and high-sensitivity triazoles analysis methods are significantly essential to effectively monitor their presence in various samples and safeguard human health. This review aims to summarize and update the progress of the pretreatment and analytical methods of triazole fungicides in environmental samples from 2012 to 2024. Common pretreatment methods used to extract and purify targets include simple steps (e.g., protein precipitation and coated blade spray), liquid-liquid extraction, solid-phase extraction, and various microextraction methods such as liquid-phase microextraction and solid-phase microextraction, among others. Detection methods mainly include liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry, supercritical fluid chromatography, sensing methods, and capillary electrophoresis. In addition, we elaborate and compare the advantages and disadvantages of different pretreatment and analytical methods, and their development prospects are discussed.

125 Years of Aspirin: Status of Analytical Methods.

Aspirin, an analgesic, antipyretic and non-steroidal anti-inflammatory drug, was a fascinating discovery that became the precursor to one of the oldest pharmaceutical success stories. It was discovered in 1899 by Felix Hoffman and patented in 1900. In 2024, Aspirin turns 125 years old and is still one of the bestselling medicines today. This review aims to celebrate 125 years of Aspirin and show the status of analytical methods available in the literature to evaluate pharmaceutical products based on Acetylsalicylic Acid (ASA). In addition, it contextualizes them with the current needs of green and clean analytical chemistry. ASA, despite being consolidated in the consumer market, embraces continuous improvement as it is a fundamental part of studies for other new purposes and studies with associations with other active ingredients. In the manuscripts available in the literature, ASA is predominantly evaluated by HPLC (41%) and UV-Vis (41%) methods, which use methanol (21.82%) and acetonitrile (18.18%), followed by buffer (16.36%). The most evaluated pharmaceutical matrix is ASA tablets (40%), followed by ASA tablets in combination with other drugs (26%). While ASA continues to innovate in the market through new forms of delivery and combinations, as well as intended purposes, the analytical methods for evaluating its pharmaceutical products do not. They continue with non-eco-efficient analytical options, which can significantly improve and meet the current demand for green and sustainable analytical chemistry.

Programming Fast DNA Amplifier Circuits with Versatile Toehold Exchange Pathway.

DNA amplifier circuits establish powerful tools to dynamically control molecular assembly for computation, sensing, and biological applications. However, the slow reaction speed remains a major barrier to their practical utility. Here, diverse fast DNA amplifier circuits termed toehold exchange polymerization (TEP) and toehold exchange catalysis (TEC) using toehold exchange-mediated assembly as a fundamental mechanism are built. Both TEP and TEC with a duplex and a hairpin can respond within minutes to diverse nucleic acid inputs with high fidelity. In addition, the circuits can amplify live-cell signals for fluorescence imaging target RNA dynamics and discriminating different cell lines. Compared with existing DNA circuits that involve time scales of hours for transducing small signals, TEP and TEC exhibit much faster dynamics, simpler design, and comparable sensitivity. These features make TEP and TEC promising platforms to develop programmable nucleic acid tools and devices and to create fast sensing and processing systems, amenable to wide practical applications.

Ivermectin-based products in the context of green pharmaceutical analysis.

BACKGROUND: Ivermectin (IVE), a broad-spectrum antiparasitic, is used in human and animal health. Analytical methods for evaluating IVE in pharmaceutical products are found in the literature and in official compendiums. However, the vast majority of them do not have an eco-friendly approach. OBJECTIVE AND METHOD: The aim of this review is to present an overview of existing analytical methods for evaluating IVE in pharmaceutical matrices in the context of Green Analytical Chemistry (GAC) and show possibilities for increasing their greenness. RESULTS: GAC is a current alternative to promote sustainable development in laboratories and chemical-pharmaceutical industries, therefore, through its principles, such as reducing the use of aggressive solvents, it is possible to make processes more ecological. However, the vast majority of analytical methods available in the literature and official compendiums do not present an eco-friendly approach. 70% of the methods are by HPLC. Among the various pharmaceutical matrices, the most evaluated are tablets (37%). Of all the solvents used in HPLC, UPLC, HPLC-MS/MS, UV and TLC methods, the combination of methanol and acetonitrile is the most chosen, accounting for more than 50% of occurrences. CONCLUSIONS: Analytical methods for evaluating IVE-based products can be leveraged within the scope of GAC, bringing sustainable work opportunities to analytical development laboratories around the world. HIGHLIGHTS: This review shows an overview of the analytical methods present in the literature and official compendiums to evaluate pharmaceutical IVE matrices, in the context of green analytical chemistry.

Analytical Methods for Assessing Thiol Antioxidants in Biological Fluids: A Review.

Redox metabolism is an integral part of the glutathione system, encompassing reduced and oxidized glutathione, hydrogen peroxide, and associated enzymes. This core process orchestrates a network of thiol antioxidants like thioredoxins and peroxiredoxins, alongside critical thiol-containing proteins such as mercaptoalbumin. Modifications to thiol-containing proteins, including oxidation and glutathionylation, regulate cellular signaling influencing gene activities in inflammation and carcinogenesis. Analyzing thiol antioxidants, especially glutathione, in biological fluids offers insights into pathological conditions. This review discusses the analytical methods for biothiol determination, mainly in blood plasma. The study includes all key methodological aspects of spectroscopy, chromatography, electrochemistry, and mass spectrometry, highlighting their principles, benefits, limitations, and recent advancements that were not included in previously published reviews. Sample preparation and factors affecting thiol antioxidant measurements are discussed. The review reveals that the choice of analytical procedures should be based on the specific requirements of the research. Spectrophotometric methods are simple and cost-effective but may need more specificity. Chromatographic techniques have excellent separation capabilities but require longer analysis times. Electrochemical methods enable real-time monitoring but have disadvantages such as interference. Mass spectrometry-based approaches have high sensitivity and selectivity but require sophisticated instrumentation. Combining multiple techniques can provide comprehensive information on thiol antioxidant levels in biological fluids, enabling clearer insights into their roles in health and disease. This review covers the time span from 2010 to mid-2024, and the data were obtained from the SciFinder® (ACS), Google Scholar (Google), PubMed®, and ScienceDirect (Scopus) databases through a combination search approach using keywords.

Time-of-Flight Secondary Ion Mass Spectrometry Revealing the Organocatalyst Distribution in Functionalized Silica Monoliths.

Hierarchically porous monolithic silica shows promise as a carrier material for immobilized organocatalysts. Conventional analysis usually includes physisorption, infrared spectroscopy and elemental analysis, among others, to elucidate the pore space and degree of functionalization of the material. However, these methods do not yield information about the spatial distribution of the organic species inside the monolithic reactor. In this work, time-of-flight secondary ion mass spectrometry has been applied to characterize the surface of organically functionalized silica monoliths. Cross sections of a silica monolith functionalized with 4-dimethylaminopyridine were analyzed and the results were compared with physisorption and elemental analysis experiments of the same material. This way, insight into the radial distribution of the catalyst could be achieved, which might assist in interpreting the performance of such reactors in heterogeneous flow catalysis.

Understudied and underestimated impacts of organic UV filters on terrestrial ecosystems.

Organic UV filters (OUVFs) are vital components in various personal care products (PCPs) and commercial goods, with the annual consumption estimated at 10,000 tons. Consequently, the unavoidable use of OUVFs in PCPs and other unregulated commercial applications could present a considerable risk to human and environmental health. These chemical entities enter terrestrial ecosystems through wastewater discharge, agriculture, atmospheric deposition, and recreational activities. Compared to aqueous ecosystems, the effects of OUVFs on terrestrial environments should be more studied and potentially underestimated. The present review addresses the abovementioned gap by summarizing 189 studies conducted between 2006 and 2024, focusing on the analytical measures, occurrence, and ecotoxicological effects of OUVFs on terrestrial ecosystems. These studies underscore the harmful effects of certain OUVFs on the development, reproduction, and endocrine systems of terrestrial organisms, highlighting the necessity for comprehensive toxicological assessments to understand their impacts on non-target species in terrestrial ecosystems. Besides, by underscoring the ecological effects of OUVFs, this review aims to guide future research and inform regulatory measures to mitigate the risks posed by these widespread contaminants. Meanwhile, interdisciplinary research is essential, integrating environmental science, toxicology, ecology, and chemistry to tackle OUVF challenges in terrestrial ecosystems.

Analytical approaches and advancement in the analysis of natural and synthetic fiber: A comprehensive review.

BACKGROUND: Accurately determining fiber composition is essential for optimizing material properties across diverse applications in textiles, composites, packaging, and other bio-based materials. Fiber performance in textiles, composites, and bio-based materials depends upon their intricate composition. This review explores advanced analytical techniques for the comprehensive characterization of natural (cellulose-hemicellulose-lignin) and synthetic (polymeric) fibers. Natural fibers primarily consist of cellulose, hemicellulose, and lignin, while synthetic fibers are formed by linking small monomer units, such as nylon, polyester, and acrylics. RESULTS: A variety of analytical methods are employed for fiber composition analysis, including microscopy, spectroscopy, chromatography, thermal analysis, and wet chemical methods. A multi-modal approach employing advanced techniques is essential for in-depth fiber analysis. Spectroscopic methods like Fourier Transform Infrared Spectroscopy (FTIR) offer rapid, non-destructive determination of chemical functionalities. Near-infrared spectroscopy (NIR) offers another efficient approach, particularly when integrated with chemometric techniques like Principal Component Regression (PCR) and Partial Least Squares (PLS) for precise quantification of cellulose, hemicellulose, and lignin. Additionally, thermal analysis methods such as Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and Dynamic Mechanical Analysis (DMA) provide insights into thermal stability and mechanical characteristics of fibers. SIGNIFICANCE: This review emphasizes the importance of an integrated approach utilizing various analytical methods for comprehensive fiber characterization. While traditional wet chemical methods offer limited advantages, the combined use of advanced techniques provides a more holistic understanding of fiber properties. As technology evolves, this integrated approach is expected to shape the future of fiber analysis and its applications across diverse industries.

Antiviral drugs in animal-derived matrices: A review.

The ban of antiviral drugs in food-producing animals in several parts of the world, latest by Commission Delegated Regulation (EU) 2022/1644, has increased the need for food control laboratories to develop analytical methods and perform official controls. However, little is known about antiviral drugs, their use, and its analysis in food-producing animals in the EU. This review aims to provide insights into relevant viruses, antiviral drugs, and animal-derived matrices for analytical method development and monitoring purposes to implement in food control laboratories. For years, animal viruses, such as African swine fever and avian influenza, have caused many outbreaks. Besides, they led to large economic losses due to the applied control measures and a lack of available treatments. Considering these losses and the known effectiveness of authorized human antiviral drugs in different organisms, medicines such as amantadine in Chinese poultry have been misused. Various analytical methods, including screening assays and sensors (published 2016-2023), and mass spectrometry methods (published 2012-2023) have been outlined in this review for the monitoring of antiviral drugs in animal-derived matrices. However, pharmacokinetics information on metabolite formation and distribution of these substances in different animal-derived matrices is incomplete. Additionally, apart from a few countries, there is a lack of available data on the potential misuse of different antiviral drugs in animal-derived matrices. Although a handful of important antiviral drugs, such as influenza, broad-spectrum, antiretroviral, and herpes drugs, and animal-derived matrices, such as chicken muscle, are identified, the priority of the scope should be further specified by closing the aforementioned gaps.

Analytical methods for the determination of xylazine in pharmaceutical, clinical and forensic matrices - A review.

Xylazine, a non-opioid veterinary anaesthetic tranquillizer that is not licensed for human use, has been linked to an increase in overdose fatalities worldwide. The study delves into the forensic aspects of xylazine usage, emphasizing on chemical, clinical and toxicological analyses of drug seizures, bodily fluids and tissues. It advocates for validated analytical methods for determining xylazine. This study provides supporting material to pave the path for the usage and development of relevant and verified alternative screening and confirmation methods for laboratories. Google Scholar, Scopus, Science Direct and PubMed were searched for relevant articles and case reports in relation to xylazine misuse and established analytical methods for forensic investigation until April 2023. A total of 79 articles were evaluated, and 40 publications met the inclusion criteria. The most prevalent xylazine exposures recorded were incidental and intentional misuse/abuse. Common symptoms upon presentation were hypotension, bradycardia, drowsiness and lethargy, although mortality was less prevalent. Solid-phase extraction and liquid-liquid extraction are two extensively used sample preparation techniques. These techniques are used to extract desired analytes from complex matrices. Several analytical techniques have been stated, including GC-MS, LC-MS/MS, HPLC-DAD and others. The analytical procedures used are determined by the matrices involved, the amount of xylazine present, interfering compounds, the degree of precision required and the laboratory infrastructure. In the present context, the LC-MS/MS methods are preferred as the gold standard. In the near future, many analytical techniques such as capillary electrophoresis, PSI-MS, immuno-analytical techniques and SERRS may show significant potential.

PrecivityAD2™ Blood Test: Analytical Validation of an LC-MS/MS Assay for Quantifying Plasma Phospho-tau217 and Non-Phospho-tau217 Peptide Concentrations That Are Used with Plasma Amyloid-ß42/40 in a Multianalyte Assay with Algorithmic Analysis for Detecting Brain Amyloid Pathology.

Alzheimer's disease (AD) is a progressive irreversible neurodegenerative disorder that represents a major global public health concern. Traditionally, AD is diagnosed using cerebrospinal fluid biomarker analysis or brain imaging modalities. Recently, less burdensome, more widely available blood biomarker (BBM) assays for amyloid-beta (Aß42/40) and phosphorylated-tau concentrations have been found to accurately identify the presence/absence of brain amyloid plaques and tau tangles and have helped to streamline AD diagnosis. However, few BBMs have been rigorously analytically validated. Herein, we report the analytical validation of a novel liquid chromatography-tandem mass spectrometry (LC-MS/MS) multiplex method for quantifying plasma phosphorylated-tau217 (p-tau217) and non-phosphorylated-tau217 (np-tau217) peptide concentrations. We combined the p-tau217/np-tau217 concentrations ratio (%p-tau217) and the previously validated LC-MS/MS multiplex assay for plasma Aß42/40 into a new multianalyte assay with algorithmic analysis (MAAA; PrecivityAD2™ test) that identifies brain amyloid status based on brain amyloid positron emission tomography. We found (a) the %p-tau217 assay is precise, accurate, sensitive, and linear over a wide analytical measurement range, and free from carryover and interference; (b) the pre-analytical specimen collection, processing, storage, and shipping conditions that maintain plasma tau peptide stability; and (c) using the measured analytical imprecision for plasma Aß42/40 and p-tau217/np-tau217 levels in a worst-case scenario model, the PrecivityAD2 test algorithm for amyloid pathology classification changed for only 3.5% of participants from brain amyloid positive to negative, or from negative to positive. The plasma sample preparation and LC-MS/MS methods underlying the PrecivityAD2 test are suitable for use in the clinical laboratory and valid for the test's intended purpose: to aid in the diagnostic evaluation of individuals aged 55 and older with signs or symptoms of mild cognitive impairment or dementia.

Analytical methods and experimental quality in studies targeting carbonyls in electronic cigarette aerosols.

We provide an extensive review of 14 studies (11 independent and three industry-funded) on emissions generated by Electronic Cigarettes (ECs), specifically focusing on the evaluation of carbonyls present in these emissions and emphasizing a meticulous evaluation of their analytical methods and experimental procedures. Since the presence of carbonyl by-products in EC aerosol is concerning, it is important to evaluate the reliability of emission studies quantifying these compounds by verifying their compliance with the following criteria of experimental quality: authors must 1) supply sufficient information on the devices and experimental procedures to allow for potentially reproducing or replicating the experiments, 2) use of appropriate puffing protocols that approach consumer usage as best as possible, 3) use of appropriate analytical methods and 4) usage of blank samples to avoid false positive detection. Outcomes were classified in terms of the fulfilment of these conditions as reliable in seven studies, partially reliable in five studies, and unreliable in two studies. However, only five studies used blank samples and six studies failed the reproducibility criterion. Carbonyl yields were far below their yields in tobacco smoke in all reproducible studies, even in the partially reliable ones, thus supporting the role of ECs (when properly tested and operated) as harm reduction products. This review highlights the necessity to evaluate the quality of laboratory standards in testing EC emissions to achieve an objective assessment of the risk profile of ECs.

In-Depth Comparison of Adeno-Associated Virus Containing Fractions after CsCl Ultracentrifugation Gradient Separation.

Recombinant adeno-associated viruses (rAAVs) play a pivotal role in the treatment of genetic diseases. However, current production and purification processes yield AAV-based preparations that often contain unwanted empty, partially filled or damaged viral particles and impurities, including residual host cell DNA and proteins, plasmid DNA, and viral aggregates. To precisely understand the composition of AAV preparations, we systematically compared four different single-stranded AAV (ssAAV) and self-complementary (scAAV) fractions extracted from the CsCl ultracentrifugation gradient using established methods (transduction efficiency, analytical ultracentrifugation (AUC), quantitative and digital droplet PCR (qPCR and ddPCR), transmission electron microscopy (TEM) and enzyme-linked immunosorbent assay (ELISA)) alongside newer techniques (multiplex ddPCR, multi-angle light-scattering coupled to size-exclusion chromatography (SEC-MALS), multi-angle dynamic light scattering (MADLS), and high-throughput sequencing (HTS)). Suboptimal particle separation within the fractions resulted in unexpectedly similar infectivity levels. No single technique could simultaneously provide comprehensive insights in the presence of both bioactive particles and contaminants. Notably, multiplex ddPCR revealed distinct vector genome fragmentation patterns, differing between ssAAV and scAAV. This highlights the urgent need for innovative analytical and production approaches to optimize AAV vector production and enhance therapeutic outcomes.

Extraction, Identification, and Quantification of Polyphenols from the Theobroma cacao L. Fruit: Yield vs. Environmental Friendliness.

The cacao fruit is a rich source of polyphenols, including flavonoids and phenolic acids, which possess significant health benefits. The accurate identification and quantification of these bioactive compounds extracted from different parts of the cacao fruit, such as pods, beans, nibs, and cacao shells, require specific treatment conditions and analytical techniques. This review presents a comprehensive comparison of extraction processes and analytical techniques used to identify and quantify polyphenols from various parts of the cacao fruit. Additionally, it highlights the environmental impact of these methods, exploring the challenges and opportunities in selecting and utilizing extraction, analytical, and impact assessment techniques, while considering polyphenols' yield. The review aims to provide a thorough overview of the current knowledge that can guide future decisions for those seeking to obtain polyphenols from different parts of the cacao fruit.

Analytical methods, risk assessment, and mitigation strategies for furan in processed foods in various countries.

This article provides an overview of analytical methods for measuring furan levels in food. Given the potential carcinogenicity of furans in humans, several studies have focused on assessing furan levels in various food products. In this review, we specifically examine furan levels in foods that are central to regional culinary traditions and summarize the results of country-specific risk assessments. Consequently, we have identified foods that contribute significantly to dietary furan exposure in each region. Coffee and baby foods, regardless of region, emerged as the primary sources of furan intake among adults and infants, respectively. Several previous studies have been conducted to develop various mitigation strategies aimed at reducing exposure to furan through food intake. Therefore, in this paper, we categorize effective mitigation strategies into two main groups: alterations to processing conditions and the addition or removal of food additives and ingredients.

Advice to the US FDA to Allow US Pharmacopeia to Create Biological Product Specifications (BPS) to Remove Side-by-Side Analytical Comparisons of Biosimilars with Reference Products.

Pharmacopeia monographs are not intended to establish biosimilarity. However, the US Food and Drug Administration (FDA) has stopped the US Pharmacopeia (USP) from creating monographs for biological drugs due to the need for side-by-side comparisons with the reference products. The USP can create Biological Product Specifications (BPS), not to be labeled as monographs, based on the analytical testing of reference products and validated test methods that will remove the need for side-by-side analytical testing of biosimilars with reference products. Scientific arguments confirm that this plan is logical and capable of creating global quality standards for biosimilars to allow their interchangeability with other biosimilars. While the regulatory agencies have waived many high-cost biosimilar tests, analytical assessment is the most sensitive test; reducing its cost will further enhance the entry of biosimilars with no clinically meaningful difference.

Directional Bias in Molecular Photogearing Evidenced by LED-Coupled Chiral Cryo-HPLC.

Molecular gearing systems are technomimetic nanoscale analogues to complex geared machinery in the macroscopic world. They are defined as systems incorporating intermeshed movable parts which perform correlated rotational motions by mechanical engagement. Only recently, new methods to actively drive molecular gearing motions instead of relying on passive thermal activation have been developed. Further progress in this endeavor will pave the way for unidirectional molecular gearing devices with a distinct type of molecular machine awaiting its realization. Within this work an essential step towards this goal is achieved by evidencing directional biases for the light-induced rotations in our molecular photogear system. Using a custom-designed LED-coupled chiral cryo-HPLC setup for the in situ irradiation of enantiomeric analytes, an intrinsic selectivity for clockwise or counterclockwise rotations was elucidated experimentally. Significant directional biases in the photogearing processes and light-induced single bond rotations (SBRs) are observed for our photogear with directional preferences of up to 4.8 : 1. Harnessing these effects will allow to rationally design and construct a fully directional molecular gearing motor in the future.

Rational Molecular Design of a Fluorescent Probe for Selectively Sensing Human Cytochrome P450 2D6.

Cytochrome P450 2D6 (CYP2D6) is a key enzyme that mediates the metabolism of various drugs and endogenous substances in humans. However, its biological role in drug-drug interactions especially mechanism-based inactivation (MBI), and various diseases remains poorly understood, owing to the lack of molecular tools suitable for selectively monitoring CYP2D6 in complex biological systems. Herein, using a tailored molecular strategy, we developed a fluorescent probe BDPM for CYP2D6. BDPM exhibits excellent specificity and imaging capability for CYP2D6, making it suitable for the real-time monitoring of endogenous CYP2D6 activity in living bio-samples. Therefore, our tailored strategy proved useful for constructing the highly selective and enzyme-activated fluorescent probes. BDPM as a molecular tool to explore the critical roles of CYP2D6 in the pathogenesis of diseases, high-throughput screening of inhibitors and intensive investigation of CYP2D6-induced MBI in natural systems.