Analytical Methods for Anatoxin-a Determination: A Review.

Anatoxin-a (ATX-a) is a potent neurotoxin produced by several species of cyanobacteria whose exposure can have direct consequences, including neurological disorders and death. The increasing prevalence of harmful cyanobacterial blooms makes the detection and reliable assessment of ATX-a levels essential to prevent the risk associated with public health. Therefore, the aim of this review is to compile the analytical methods developed to date for the detection and quantification of ATX-a levels alone and in mixtures with other cyanotoxins and their suitability. A classification of the analytical methods available is fundamental to make an appropriate choice according to the type of sample, the equipment available, and the required sensitivity and specificity for each specific purpose. The most widely used detection technique for the quantification of this toxin is liquid chromatography-tandem mass spectrometry (LC-MS/MS). The analytical methods reviewed herein focus mainly on water and cyanobacterial samples, so the need for validated analytical methods in more complex matrices (vegetables and fish) for the determination of ATX-a to assess dietary exposure to this toxin is evidenced. There is currently a trend towards the validation of multitoxin methods as opposed to single-ATX-a determination methods, which corresponds to the real situation of cyanotoxins' confluence in nature.

Comparison of emissions across tobacco products: A slippery slope in tobacco control.

In this narrative review, we highlight the challenges of comparing emissions from different tobacco products under controlled laboratory settings (using smoking/vaping machines). We focus on tobacco products that generate inhalable smoke or aerosol, such as cigarettes, cigars, hookah, electronic cigarettes, and heated tobacco products. We discuss challenges associated with sample generation including variability of smoking/vaping machines, lack of standardized adaptors that connect smoking/vaping machines to different tobacco products, puffing protocols that are not representative of actual use, and sample generation session length (minutes or number of puffs) that depends on product characteristics. We also discuss the challenges of physically characterizing and trapping emissions from products with different aerosol characteristics. Challenges to analytical method development are also covered, highlighting matrix effects, order of magnitude differences in analyte levels, and the necessity of tailored quality control/quality assurance measures. The review highlights two approaches in selecting emissions to monitor across products, one focusing on toxicants that were detected and quantified with optimized methods for combustible cigarettes, and the other looking for product-specific toxicants using non-targeted analysis. The challenges of data reporting and statistical analysis that allow meaningful comparison across products are also discussed. We end the review by highlighting that even if the technical challenges are overcome, emission comparison may obscure the absolute exposure from novel products if we only focus on relative exposure compared to combustible products.

Multi-criteria decision analysis: technique for order of preference by similarity to ideal solution for selecting greener analytical method in the determination of mifepristone in environmental water samples.

This work proposes the use of multi-criteria decision analysis (MCDA) to select a more environmentally friendly analytical procedure. TOPSIS, which stands for Technique for Order of Preference by Similarity to Ideal Solution, is an example of a MCDA method that may be used to rank or select best alternative based on various criteria. Thirteen analytical procedures were used in this study as TOPSIS input choices for mifepristone determination in water samples. The input data, which consisted of these choices, was described using assessment criteria based on 12 principles of green analytical chemistry (GAC). Based on the objective mean weighting (MW), the weights for each criterion were assigned equally. The most preferred analytical method according to the ranking was solid phase extraction with micellar electrokinetic chromatography (SPE-MEKC), while solid phase extraction combined with ultra-high performance liquid chromatography tandem mass spectrometry (SPE-UHPLC-MS/MS) was ranked last. TOPSIS ranking results were also compared to the green metrics NEMI, Eco-Scale, GAPI, AGREE, and AGREEprep that were used to assess the greenness of thirteen analytical methods for mifepristone determination. The results demonstrated that only the AGREE metric tool correlated with TOPSIS; however, there was no correlation with other metric tools. The analysis results suggest that TOPSIS is a very useful tool for ranking or selecting the analytical procedure in terms of its greenness and that it can be easily integrated with other green metrics tools for method greenness assessment.

Current Analytical Methods for the Sensitive Assay of New-Generation Ovarian Cancer Drugs in Pharmaceutical and Biological Samples.

Ovarian cancer, which affects the female reproductive organs, is one of the most common types of cancer. Since this type of cancer has a high mortality rate from gynaecological cancers, the scientific community shows great interest in studies on its treatment. Chemotherapy, radiotherapy, and surgical treatment methods are used in its treatment. In the absence of targeted treatments in these treatment methods, side effects occur in patients, and patients show resistance to the drug. In addition, the underlying causes of ovarian cancer are still not fully known. The scientific world thinks that genetic factors, environmental conditions, and consumed foods may cause this cancer. The most important factor in the treatment of ovarian cancer is early diagnosis. Therefore, the drugs used in the treatment of ovarian cancer are platinum-based anticancer drugs. In addition to these drugs, the most preferred treatment method recently is targeted treatment approaches using poly(adenosine diphosphate ribose) polymerase (PARP) inhibitors. In this review, studies on the sensitive analysis of the treatment methods of these new-generation drugs used in the treatment of ovarian cancer have been comprehensively examined. In addition, the basic features, structural aspects, and biological data of analytical methods used in treatments with new-generation drugs are explained. Analytical studies carried out in the literature in recent years aim to show future developments in how these new-generation drugs are used today and to guide future studies by comprehensively examining and explaining the structure-activity relationship, mechanism of action, toxicity, and pharmacokinetic studies. Finally, in this study, the methods used in the analysis of drugs used in the treatment of ovarian cancer and the studies conducted between 2015 and 2023 were discussed in detail.

Common Methods of Extraction and Determination of Phytomelatonin in Plants.

The presence of melatonin in plants, called phytomelatonin, has gained great interest in recent years. The determination of phytomelatonin levels in plant extracts for both physiological and plant foodstuff studies requires sophisticated techniques due to the low endogenous levels of this indolic compound with hormonal nature. This chapter presents the most common and advanced techniques in the determination of phytomelatonin, with special emphasis on the techniques of extraction, cleaning, separation, detection, identification, and quantification. Multiple examples and recommendations are presented for a clear overview of the pros and cons of phytomelatonin determinations in plant tissues, seeds, and fruits, mainly.

The hidden treasures in endophytic fungi: a comprehensive review on the diversity of fungal bioactive metabolites, usual analytical methodologies, and applications.

This review provides a comprehensive overview of the key aspects of the natural metabolite production by endophytic fungi, which has attracted significant attention due to its diverse biological activities and wide range of applications. Synthesized by various fungal species, these metabolites encompass compounds with therapeutic, agricultural, and commercial significance. We delved into strategies and advancements aimed at optimizing fungal metabolite production. Fungal cultivation, especially by Aspergillus, Penicillium, and Fusarium, plays a pivotal role in metabolite biosynthesis, and researchers have explored both submerged and solid-state cultivation processes to harness the full potential of fungal species. Nutrient optimization, pH, and temperature control are critical factors in ensuring high yields of the targeted bioactive metabolites especially for scaling up processes. Analytical methods that includes High-Performance Liquid Chromatography (HPLC), Liquid Chromatography-Mass Spectrometry (LC-MS), Gas Chromatography-Mass Spectrometry (GC-MS), Nuclear Magnetic Resonance (NMR), and Mass Spectrometry (MS), are indispensable for the identification and quantification of the compounds. Moreover, genetic engineering and metabolic pathway manipulation have emerged as powerful tools to enhance metabolite production and develop novel fungal strains with increased yields. Regulation and control mechanisms at the genetic, epigenetic, and metabolic levels are explored to fine-tune the biosynthesis of fungal metabolites. Ongoing research aims to overcome the complexity of the steps involved to ensure the efficient production and utilization of fungal metabolites.

Solid-State Glass Nanopipette: Modification and Application.

Solid-state glass nanopipettes provide a promising confined space that offers several advantages such as controllable size, simple preparation, low cost, good mechanical stability, and good thermal stability. These advantages make them an ideal choice for various applications such as biosensors, DNA sequencing, and drug delivery. In this review, we first delve into the functionalized nanopipettes for sensing various analytes and the methods used to develop detection means with them. Next, we provide an in-depth overview of the advanced functionalization methodologies of nanopipettes based on diversified chemical kinetics. After that, we present the latest state-of-the-art achievements and potential applications in detecting a wide range of targets, including ions, molecules, biological macromolecules, and single cells. We examine the various challenges that arise when working with these targets, as well as the innovative solutions developed to overcome them. The final section offers an in-depth overview of the current development status, newest trends, and application prospects of sensors. Overall, this review provides a comprehensive and detailed analysis of the current state-of-the-art functionalized nanopipette perception sensing and development of detection means and offers valuable insights into the prospects for this exciting field.

Biomarkers of exposure and effect in human biomonitoring of metal-based nanomaterials: their use in primary prevention and health surveillance.

Metal-based nanomaterials (MNMs) have gained particular interest in nanotechnology industry. They are used in various industrial processes, in biomedical applications or to improve functional properties of several consumer products. The widescale use of MNMs in the global consumer market has resulted in increases in the likelihood of exposure and risks to human beings. Human exposure to MNMs and assessment of their potential health effects through the concomitant application of biomarkers of exposure and effect of the most commonly used MNMs were reviewed in this paper. In particular, interactions of MNMs with biological systems and the nanobiomonitoring as a prevention tool to detect the early damage caused by MNMs as well as related topics like the influence of some physicochemical features of MNMs and availability of analytical approaches for MNMs testing in human samples were summarized in this review. The studies collected and discussed seek to increase the current knowledge on the internal dose exposure and health effects of MNMs, highlighting the advantages in using biomarkers in primary prevention and health surveillance.

Temperature-responsive comprehensive two-dimensional liquid chromatography coupled to high resolution mass spectrometry for the elucidation of the oxidative degradation processes of chemicals of environmental concern.

This study explores the possibilities offered by temperature-responsive liquid chromatography (TRLC) based comprehensive 2-dimensional liquid chromatography in combination with reversed-phase liquid chromatography (RPLC) for the analysis of degradation products formed upon oxidative treatment of persistent organic pollutants, in this case exemplified through carbamazepine (CBZ). The TRLC×RPLC combination offers the possibility to overcome peak overlap and incomplete separation encountered in 1D approaches, while the transfer of the purely aqueous mobile phase leads to refocusing of all analytes on the second dimension column. Consequently, this allows for about method-development free and hence, easier LC×LC. The study focuses on the oxidative degradation of CBZ, a compound of environmental concern due to its persistence in water bodies. The TRLC×RPLC combination effectively separates and identifies CBZ and its degradation products, while offering improved selectivity over the individual TRLC or RPLC separations. This allows gathering more understanding of the degradation cascade and allows real-time monitoring of the appearance and disappearance of various degradation products. The compatibility with high-resolution mass spectrometry is last shown, enabling identification of 21 CBZ-related products, nine of which were not previously reported in CBZ degradation studies. The approach's simplicity, optimization-free aspects, and ease of use make it a promising tool for the analysis of degradation pathways in environmental contaminants.

Bacterial Glycolipid Acting on Protein Transport Across Membranes.

The process of protein transport across membranes involves a variety of factors and has been extensively investigated. Traditionally, proteinaceous translocons and chaperones have been recognized as crucial factors in this process. However, recent studies have highlighted the significant roles played by lipids and a glycolipid present in biological membranes in membrane protein transport. Membrane lipids can influence transport efficiency by altering the physicochemical properties of membranes. Notably, our studies have revealed that diacylglycerol (DAG) attenuates mobility in the membrane core region, leading to a dramatic suppression of membrane protein integration. Conversely, a glycolipid in Escherichia coli inner membranes, named membrane protein integrase (MPIase), enhances integration not only through the alteration of membrane properties but also via direct interactions with membrane proteins. This review explores the mechanisms of membrane protein integration mediated by membrane lipids, specifically DAG, and MPIase. Our results, along with the employed physicochemical analysis methods such as fluorescence measurements, nuclear magnetic resonance, surface plasmon resonance, and docking simulation, are presented to elucidate these mechanisms.

An insight into recent updates on analytical techniques for bioactive alkaloids.

INTRODUCTION: Alkaloids represent a wide class of naturally existing nitrogen-containing organic compounds having diverse biological activities. They are primary bioactive substances extracted from diverse plant parts. Due to their diverse biological activities, they are frequently used as medicines. The alkaloids have diverse pharmacological impacts on the human body; alkaloids are used for prevention, treatment, and reduction of discomfort associated with chronic illnesses. As most alkaloids exist in plants in complex form, combined with numerous other natural plant components, it is essential to recognize and characterize these molecules using different analytical techniques. OBJECTIVES: We aimed to review the literature on the methods and protocols for the analysis of naturally occurring alkaloids. METHODS: We carried out a literature survey using the PubMed, Scopus, and Google Scholar databases and other relevant published materials. The keywords used in the searches were "alkaloids," "analytical methods," "HPLC method," "GC method," "electrochemical methods," and "bioanalytical methods," in various combinations. RESULTS: In this article, several classes of alkaloids are presented, along with their biological activities. Moreover, it includes a thorough explanation of chromatographic techniques, hyphenated techniques, electrochemical techniques, and current trending analytical methods utilized for the isolation, identification, and comprehensive characterization of alkaloids. CONCLUSIONS: The various analytical techniques play an important role in the identification as well as the characterization of various alkaloids from plants, plasma samples, and urine samples. The hyphenation of various chromatographic techniques with mass spectrometry and NMR spectroscopy plays a crucial role in the characterization of unknown compounds.

Analytical methods for determining environmental contaminants of concern in water and wastewater.

Control and prevention of environmental pollution have emerged as paramount global concerns. Anthropogenic activities, such as industrial discharges, agricultural runoff, and improper waste disposal, introduce a wide range of contaminants into various ecosystems. These pollutants encompass organic and inorganic compounds, particulates, microorganisms, and disinfection by-products, posing severe threats to human health, ecosystems, and the environment. Effective monitoring methods are indispensable for assessing environmental quality, identifying pollution sources, and implementing remedial measures. This paper suggests that the development and utilization of highly advanced analytical tools are both essential for the analysis of contaminants in water samples, presenting a foundational hypothesis for the review. This paper comprehensively reviews the development and utilization of highly advanced analytical tools which is mandatory for the analysis of contaminants in water samples. Depending on the specific pollutants being studied, the choice of analytical methods widely varies. It also reveals insights into the diverse applications and effectiveness of these methods in assessing water quality and contaminant levels. By emphasizing the critical role of the reviewed monitoring methods, this review seeks to deepen the understanding of pollution challenges and inspire innovative monitoring solutions that contribute to a cleaner and more sustainable global environment.•Urgent global concerns: control and prevention of pollution from diverse sources.•Varied contaminants, diverse methods: comprehensive review of analytical tools.•Inspiring a sustainable future: innovative monitoring for a cleaner environment.

Mass spectrometric analysis strategies for pyrrolizidine alkaloids.

Pyrrolizidine alkaloids (PAs) in food and natural preparations have received widespread attention due to their hepatotoxicity, genotoxicity, and embryotoxicity. Mass spectrometry (MS), as a high resolution, high sensitive, and high throughput detection tool, has been the most commonly used technique for the determination of PAs. The continuous advancement of new technologies, methods, and strategies in the field of MS has contributed to the improvement of the analytical efficiency and methodological enhancement of PAs. This paper provides an overview of the structure, toxicity properties and commonly employed analytical methods, focusing on the concepts, advances, and novel techniques and applications of MS-based methods for the analysis of PAs. Additionally, the remaining challenges, future perspectives, and trends for PA detection are discussed. This review provides a reference for toxicological studies of PAs, content monitoring, and the establishment of quality control and safety standards for herbal and food products.

Analytical methods and biomonitoring results in hair for the assessment of exposure to endocrine-disrupting chemicals: A literature review.

Endocrine-disrupting chemicals (EDC) are compounds that alter functions of the endocrine system due to their ability to mimic or antagonize endogenous hormones, or that alter their synthesis and metabolism, causing adverse health effects. Human biomonitoring (HBM) is a reliable method to assess human exposure to chemicals through measurement in human body fluids and tissues. It identifies new sources of exposure and determines their distribution, thereby enabling detection of the most exposed populations. Blood and urine are commonly used for HBM of EDC, but their interest is limited for compounds presenting short half-lives. Hair appears as an interesting alternative insofar as it provides a large exposure window. For the present study, we evaluated the relevance of hair in determining EDC exposure. With this in mind, we undertook a literature review focusing on the bioanalytical aspects and performances of methods developed to determine EDC in hair. The literature review was performed through methodical bibliographical research. Relevant articles were identified using two scientific databases: PubMed and Web of Science, with search equations built from a combination of keywords, MeSH terms and Boolean operators. The search strategy identified 2949 articles. After duplicates were removed, and following title, abstract, and full-text screenings, only 31 were included for qualitative synthesis. Hair collection was mainly performed in the back of the head and preparation involved two processes: cutting into small pieces or grounding to powder. The off-line LC-MS/MS method remains the main technique used to assess EDC through hair. Differences regarding the validation of analytical methods and interpretation of HBM results were highlighted, suggesting a need for international harmonisation to obtain reliable and comparable results. External contamination of hair was identified as a main limitation in the interpretation of results, highlighting the need to better understand EDC transfers through hair and to develop relevant hair decontamination processes.

N-Aryl-DABCO Salts as an Unprecedented Sensing Platform for the Detection of Thiols and Selenols.

Quaternary N-aryl-DABCO salts were introduced for the first time as a highly selective sensing platform for thiols and selenols. By employing this platform, a highly sensitive coumarin based "off-on" fluorescent probe was designed and synthesized. The probe possesses a good solubility in water, low background fluorescence, and, most importantly, demonstrates high selectivity to aryl thiols and selenols over their aliphatic counterparts and other common nucleophiles. A dramatic increase in fluorescence intensity is achieved through the selective cleavage of the quaternized DABCO-ring, yielding a piperazine derivatives with a high fluorescence quantum yield (~72 %). Moreover, stability of the probe to the most used reducing agents DTT and TCEP was demonstrated. The limits of detection for p-thiocresol and phenyl selenide were evaluated to be 22 nM and 6 nM, respectively.

Formation and Detection of Gizzerosine in Animal Feed Matrices: Progress and Perspectives.

Gizzerosine is responsible for gizzard erosion and black vomit, owing to excessive gastric acid secretion in poultry. It is a biogenic amine that forms during feed processing. Gizzerosine, a derivative of histamine, is a serious threat to animal feed safety and poultry production because it is more potent after ingestion and more harmful to poultry than histamine. The difficulty of obtaining gizzerosine and the lack of simple, rapid, and sensitive in vitro detection techniques have hindered studies on the effects of gizzerosine on gizzard health and poultry production. In this review, we evaluated the natural formation and the chemical synthesis methods of gizzerosine and introduced seven detection methods and their principles for analyzing gizzerosine. This review summarizes the issues of gizzerosine research and suggests methods for the future development of gizzerosine detection methods.

Ferritin: A Biomarker Requiring Caution in Clinical Decision.

OBJECTIVES: To determine the ferritin inter-assay differences between three "Conformité Européenne" (CE) marked tests, the impact on reference intervals (RI), and the proportion of individuals with iron deficiency (ID), we used plasma and serum from healthy blood donors (HBD) recruited in three different Switzerland regions. DESIGN AND METHODS: Heparinized plasma and serum from HBD were obtained from three different transfusion centers in Switzerland (Fribourg, Geneva, and Neuchatel). One hundred forty samples were recruited per center and per matrix, with a gender ratio of 50%, for a total of 420 HBD samples available per matrix. On both matrices, ferritin concentrations were quantified by three different laboratories using electrochemiluminescence (ECL), latex immunoturbidimetric assay (LIA), and luminescent oxygen channeling immunoassay (LOCI) assays, respectively. The degree of agreement between matrices and between the three sites/methods was assessed by Passing-Bablok and we evaluated the proportion of individuals deemed to have ID per method. RESULTS: Overall, no difference between serum and heparinized plasma ferritin values was observed according to Passing-Bablok analyses (proportional bias range: 1.0-3.0%; maximum constant bias: 1.84 µg/L). Significant median ferritin differences (p < 0.001 according to Kruskal-Wallis test) were observed between the three methods (i.e., 83.6 µg/L, 103.5 µg/L, and 62.1 µg/L for ECL, LIA, and LOCI in heparinized plasma, respectively), with proportional bias varying significantly between ±16% and ±32% on serum and from ±14% to ±35% on plasma with no sign of gender-related differences. Affecting the lower end of RI, the proportion of ID per method substantially varied between 4.76% (20/420) for ECL, 2.86% (12/420) for LIA, and 9.05% (38/420) for LOCI. CONCLUSIONS: Serum and heparinized plasma are exchangeable for ferritin assessment. However, the order of magnitude of ferritin differences across methods and HBD recruitment sites could lead to diagnostic errors if uniform RI were considered. Challenging the recently proposed use of uniform ferritin thresholds, our results highlight the importance of method- and region-specific RI for ferritin due to insufficient inter-assay harmonization. Failing to do so significantly impacts ID diagnosis.

Research progress of the detection and analysis methods of heavy metals in plants.

Heavy metal (HM)-induced stress can lead to the enrichment of HMs in plants thereby threatening people's lives and health via the food chain. For this reason, there is an urgent need for some reliable and practical techniques to detect and analyze the absorption, distribution, accumulation, chemical form, and transport of HMs in plants for reducing or regulating HM content. Not only does it help to explore the mechanism of plant HM response, but it also holds significant importance for cultivating plants with low levels of HMs. Even though this field has garnered significant attention recently, only minority researchers have systematically summarized the different methods of analysis. This paper outlines the detection and analysis techniques applied in recent years for determining HM concentration in plants, such as inductively coupled plasma mass spectrometry (ICP-MS), atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS), X-ray absorption spectroscopy (XAS), X-ray fluorescence spectrometry (XRF), laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), non-invasive micro-test technology (NMT) and omics and molecular biology approaches. They can detect the chemical forms, spatial distribution, uptake and transport of HMs in plants. For this paper, the principles behind these techniques are clarified, their advantages and disadvantages are highlighted, their applications are explored, and guidance for selecting the appropriate methods to study HMs in plants is provided for later research. It is also expected to promote the innovation and development of HM-detection technologies and offer ideas for future research concerning HM accumulation in plants.

PFAS ghosts: how to identify, evaluate, and exorcise new and existing analytical interference.

With increasing public awareness of PFAS, and their presence in biological and environmental media across the globe, comes a matching increase in the number of PFAS monitoring studies. As more matrices and sample cohorts are examined, there are more opportunities for matrix interferents to appear as PFAS where there are none (i.e., "seeing ghosts"), impacting subsequent reports. Addressing these ghosts is vital for the research community, as proper analytical measurements are necessary for decision-makers to understand the presence, levels, and potential risks associated with PFAS and protect human and environmental health. To date, PFAS interference has been identified in several matrices (e.g., food, shellfish, blood, tissue); however, additional unidentified interferents are likely to be observed as PFAS research continues to expand. Therefore, the aim of this commentary is several fold: (1) to create and support a publicly available dataset of all currently known PFAS analytical interferents, (2) to allow for the expansion of that dataset as more sources of interference are identified, and (3) to advise the wider scientific community on how to both identify and eliminate current or new analytical interference in PFAS analyses.

Tapping the Full Potential of Infrared Spectroscopy for the Analysis of Technical Lignins.

We present an approach to overcome the challenges associated with the increasing demand of high-throughput characterization of technical lignins, a key resource in emerging bioeconomies. Our approach offers a resort from the lack of direct, simple, and low-cost analytical techniques for lignin characterization by employing multivariate calibration models based on infrared (IR) spectroscopy to predict structural properties of lignins (i. e., functionality, molar mass). By leveraging a comprehensive database of over 500 well-characterized technical lignin samples - a factor of 10 larger than previously used sets - our chemometric models achieved high levels of quality and statistical confidence for the determination of different functional group contents (RMSEPs of 4-16 %). However, the statistical moments of the molar mass distribution are still best determined by size-exclusion chromatography. Analyses of over 500 technical lignins offered also a great opportunity to provide information on the general variability in kraft lignins and lignosulfonates (from different origins). Overall, the effected savings in analysis time (>7 h), resources, and required sample mass combined with non-destructiveness of the measurement satisfy key demands for efficient high-throughput lignin analyses. Finally, we discuss the advantages, disadvantages, and limitations of our approach, along with critical insights into the associated chemical-analytical and spectroscopic challenges.