Search Results (84)

Multi-way analysis has become one of the most powerful and versatile chemometric approaches for dealing with the increasing complexity of data generated in modern analytical chemistry. Advances in instrumentation, the widespread use of hyphenated techniques, and the inherently multidimensional nature of many experimental designs require methods capable of preserving structural relationships within datasets. In this context, multi-way tools such as Tucker 3, PARAFAC, or other supervised variants provide rigorous and interpretable descriptions of variability across multiple modes (samples, variables, conditions), enabling the extraction of meaningful patterns, improved noise handling, and enhanced robustness, compared with traditional bilinear approaches. This review offers a critical overview of the most commonly applied multi-way algorithms and their practical use in fields such as environmental chemistry, food science, clinical diagnostics, industrial process monitoring, and pharmaceutical analysis. The essential steps of the workflow, from data acquisition and preprocessing to model selection and interpretation, are discussed, highlighting their impact on model reliability. A dedicated section summarizes the software environments available for performing multi-way analyses, guiding readers in selecting the most suitable tools for their needs. Overall, this review emphasizes how multi-way chemometrics is becoming increasingly crucial for converting complex, high-dimensional data into reliable and actionable chemical knowledge. Full article

Polyphenols are a structurally diverse group of plant secondary metabolites widely recognized for their antioxidant, anti-inflammatory, antimicrobial, and chemoprotective properties, which have stimulated their extensive use in food, pharmaceutical, nutraceutical, and cosmetic products. However, their chemical heterogeneity, wide polarity range, and strong interactions with plant matrices pose major challenges for efficient extraction, separation, and reliable analytical characterization. This review provides a critical overview of contemporary strategies for the extraction, separation, and identification of polyphenols from plant-derived matrices. Conventional extraction methods, including maceration, Soxhlet extraction, and percolation, are discussed alongside modern green technologies such as ultrasound-assisted extraction, microwave-assisted extraction, pressurized liquid extraction, and supercritical fluid extraction. Particular emphasis is placed on environmentally friendly solvents, including ethanol, natural deep eutectic solvents, and ionic liquids, as sustainable alternatives that improve extraction efficiency while reducing environmental impact. The review further highlights chromatographic separation approaches—partition, adsorption, ion-exchange, size-exclusion, and affinity chromatography—and underlines the importance of hyphenated analytical platforms (LC–MS, LC–MS/MS, and LC–NMR) for comprehensive polyphenol profiling. Key analytical challenges, including matrix effects, compound instability, and limited availability of reference standards, are addressed, together with perspectives on industrial implementation, quality control, and standardization. Full article

Synthetic cannabinoids (SCs) represent one of the rapidly growing groups of new psychoactive substances (NPS) on the illicit drug market. SCs mimic the effects of Δ⁹-tetrahydrocannabinol, but they have a greater affinity to the receptors, resulting in more potent psychoactive effects than traditional substances. The toxicity and high abuse potential of SCs could pose serious health risks to their users. The challenges posed by the SCs require innovative monitoring strategies like the analysis of untreated wastewater, known as wastewater-based epidemiology (WBE). In this review article, we summarized the available literature on the detection and quantification of SCs in raw wastewater samples published between 2013 and 2025. We paid special attention to challenges related to different experimental stages of WBE analysis that hinder the accurate measurement of SCs and their metabolites. The reviewed studies show that wastewater analysis reflected the dynamic evolution of the illicit SCs market. As studies on the analysis of SCs in wastewater remain scarce, large monitoring campaigns and research performed in more locations are needed. Modern analytical hyphenated systems such as LC-MS are essential for the sensitive and accurate quantification of SC biomarkers in wastewater and their sound identification. Future studies should address further stability tests, investigation of SC metabolism, and careful selection of the effective SC extraction method from the complex environmental matrix. Full article

The advancement of miniaturized liquid chromatography (M-LC) systems has drawn considerable attention for their ability to enhance sensitivity, expedite analysis, and minimize the environmental impact of chemical usage in various analytical processes. This review explores the fundamental principles and recent innovations in M-LC technology, including diverse pump designs, advanced column techniques, and the reduction in connection devices. Emphasizing the need for components that operate efficiently at the capillary or nanoscale with minimal dead volumes, we also discuss the development of benchtop instruments and mass spectrometry integrations. The review further highlights the growing applications of M-LC in food, environmental, and biological analyses, highlighting its potential as a powerful and emerging tool in separation science. Looking forward, addressing problems such as limited robustness, fabrication complexity, and integration with sensitive detectors will be instrumental to advancing M-LC technology. Modern innovation in microfabrication, materials science, and hyphenated methods holds great promise for allowing real-time, high-throughput, and portable analytical solutions in the near future. Full article

Tocopherols, major lipid-soluble components of vitamin E, are essential natural products with significant nutritional and pharmacological value. Their structural diversity and uneven distribution across vegetable oils require accurate analytical strategies for compositional profiling, quality control, and authenticity verification, amid concerns over food fraud and regulatory demands. Analytical challenges, such as matrix effects in complex oils and the cost trade-offs of green extraction methods, complicate these processes. This review examines recent advances in tocopherol analysis, focusing on extraction and detection techniques. Green methods like supercritical fluid extraction and deep eutectic solvents offer selectivity and sustainability, though they are costlier than traditional approaches. On the analytical side, hyphenated techniques such as supercritical fluid chromatography-mass spectrometry (SFC-MS) achieve detection limits as low as 0.05 ng/mL, improving sensitivity in complex matrices. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) provides robust analysis, while spectroscopic and electrochemical sensors offer rapid, cost-effective alternatives for high-throughput screening. The integration of chemometric tools and miniaturized systems supports scalable workflows. Looking ahead, the incorporation of Artificial Intelligence (AI) in oil authentication has the potential to enhance the accuracy and efficiency of future analyses. These innovations could improve our understanding of tocopherol compositions in vegetable oils, supporting more reliable assessments of nutritional value and product authenticity. Full article

Mass spectrometric (MS) fingerprinting coupled with chemometrics for the detection of plants in plant mixtures is sparsely researched. This paper aims to check its value for herbal adulteration concerning plants with slimming as an indication. Moreover, it is among the first to exploit the full three-dimensional dataset (i.e., time × intensity × mass) obtained with liquid chromatography hyphenated with MS for herbal fingerprinting purposes. The MS parameters were optimized to achieve highly specific fingerprints. Trituration’s (total 55), blanks (total 11) and reference plants were injected in the MS system to generate the dataset. The dataset was complex and humongous, necessitating the application of compression techniques. After compression, Partial Least Squares-Discriminant Analysis (PLS-DA) was performed to generate models validated for accuracy using cross-validation and an external test set. Confusion matrices were constructed to provide insight into the modeling predictions. A complimentary evaluation between data obtained using a previously developed Diode Array Detection (DAD) method and the MS data was performed by data fusion techniques and newly generated models. The fused dataset models were comparable to MS models. For ease of application, MS modeling was deemed to be superior. The future market studies would adopt MS modeling as the preferred choice. A proof of concept was carried out on 10 real-life samples obtained from illegal sources. The results indicated the need for stronger monitoring of (illegal) plant food supplements entering the market, especially via the internet. Full article

The analysis of wastewater is essential in environmental chemistry, particularly for monitoring emerging contaminants and assessing ecological impacts. In this context, hyphenated chromatographic techniques are widely used, with liquid chromatography being one of the most common. However, gas chromatography coupled with mass spectrometry (GC-MS) remains a valuable tool in this field due to its sensitivity, selectivity, and widespread availability in most laboratories. This review examines the application of validated methods for wastewater analysis using GC-MS (MS), highlighting its relevance in identifying micropollutants such as pharmaceuticals, drugs of abuse, pesticides, hormones, and industrial by-products. The validation of analytical methods is crucial to ensuring the reliability and reproducibility of data and the accurate monitoring of contaminants. Key parameters, including sample volume, recovery efficiency, and detection and quantification limits, are discussed, evaluating different approaches to optimising the identification of different classes of contaminants. Additionally, this study explores advances in sample preparation techniques, such as solid-phase microextraction (SPME), dispersive liquid–liquid microextraction (DLLME), and solid-phase extraction (SPE), which enhance efficiency and minimise interferences in the analysis. Finally, future perspectives are discussed, including the integration of emerging technologies such as high-resolution mass spectrometry, the miniaturisation of GC systems, and the development of faster and more sustainable analytical methods. Full article

Three different vegetable oils, namely coconut oil, palm olein and olive oil, were analyzed for mineral oil hydrocarbons (MOHs) in our laboratory and in five commercial laboratories well recognized for their expertise in this field. The analysis consisted of a preliminary quantitative estimation of MOH content by hyphenated liquid chromatography–gas chromatography with flame ionization detection (LC-GC-FID), followed by a confirmatory analysis of MOH components by two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-ToF). The results provided by the six laboratories were compared to check their consistency, which would have led to a hypothetical commercial agreement or dispute scenarios, for instance. The comparison was based merely on information provided by the laboratories in their analytical reports (i.e., the methodology was not challenged, and chromatograms were not reviewed). Additionally, some of the laboratories were willing to provide some more information or details of the analysis. Similar quantitative results were provided by all six laboratories, emphasizing the utility of the current available harmonized guidelines and official standards for this method. However, as regards confirmatory results, discrepancies were observed among some laboratories in terms of the detection of MOH markers at low levels and the interpretation of GCxGC-ToF information. Even taking into account the limitation of this study as regards the reduced number of laboratories included, it highlights the need for harmonizing the GCxGC-ToF confirmatory method for MOHs in order to increase the alignment of results between laboratories for this kind of analysis. Full article

A new hyphenated technique using thin-layer chromatography (TLC) to separate analytes in mixtures, coupled with mid-infrared (MIR) laser spectroscopy for identification and quantification, is presented. The method, which provides a means for rapid screening of analytes that is practical, low-cost, fast, robust, and reproducible, was tested using nitroaromatic and aliphatic nitro high explosives (HEs) as target analytes. HEs are anthropogenic contaminants containing an -NO₂ group. For validation of the new technique, a direct comparison of the 2,4,6-trinitrotoluene (TNT) spectrum, obtained by attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy coupled with TLC, was carried out. The MIR laser spectroscopy-based method was evaluated by calculating the analytical figures of merit regarding the calibration curves’ linearity and the method’s sensitivity and precision. The TNT spectrum obtained by the MIR laser method showed two prominent and characteristic bands of the explosive at approximately 1350 cm⁻¹ and 1550 cm⁻¹ compared to the spectrum acquired by ATR-FTIR. The detection limit calculated for TNT was 84 ng, while the quantification limit was 252 ng. Multivariate analysis was used to evaluate the spectroscopic data to identify sources of variation and determine their relation. Partial least squares (PLS) regression analysis and PLS combined with discriminant analysis (PLS-DA) were used for quantification and classification. The new technique, TLC-QCL, is amenable to a smaller footprint with further developments in MIR laser technology, making it portable for fieldwork. Full article

Advances in combinatorial synthesis and high-throughput screening methods have led to renewed interest in synthetic plant immunity activators as well as priming agents. 3,5-Dichloroanthranilic acid (3,5-DCAA) is a derivative of anthranilic acid that has shown potency in activating defence mechanisms in Arabidopsis and barley. Chemical biology, which is the interface of chemistry and biology, can make use of metabolomic approaches and tools to better understand molecular mechanisms operating in complex biological systems. Here we report on the untargeted metabolomic profiling of barley seedlings treated with 3,5-DCAA to gain deeper insights into the mechanism of action of this resistance inducer. Histochemical analysis revealed the production of reactive oxygen species in the leaves upon 3,5-DCAA infiltration. Subsequently, methanolic extracts from different time periods (12, 24, and 36 h post-treatment) were analysed by ultra-high-performance liquid chromatography hyphenated to a high-resolution mass spectrometer. Both unsupervised and supervised chemometric methods were used to reveal hidden patterns and highlight metabolite variables associated with the treatment. Based on the metabolites identified, both the phenylpropanoid and octadecanoid pathways appear to be main routes activated by 3,5-DCAA. Different classes of responsive metabolites were annotated with flavonoids, more specifically flavones, which were the most dominant. Given the limited understanding of this inducer, this study offers a metabolomic analysis of the response triggered by its foliar application in barley. This additional insight could help make informed decisions for the development of more effective strategies for crop protection and improvement, ultimately contributing to crop resilience and agricultural sustainability. Full article

We developed a selective technique to rapidly measure free chlorine, which is the sum of elemental chlorine (Cl₂), hypochlorous acid (HOCl), and hypochlorite (OCl⁻) in water samples via an electrophilic aromatic substitution reaction hyphenated with liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Sample preparation involved derivatization at 25 °C for 15 min with 3,4,5-trimethoxyphenylacetic acid (TMPAA) in an aqueous solution prior to analysis. Several parameters were evaluated to determine the optimized reaction and for the production of informative MS/MS spectrum of the derivatization product, 2-chloro-3,4,5-trimethoxyphenylacetic acid (Cl-TMPAA). The resulting Cl-TMPAA derivative displayed an informative ESI-MS/MS spectrum characterized by product ions at m/z 232.0142, 200.0245, and 185.0009 from the precursor ion at m/z 259.0379. The linear dynamic range of the method (0.1–10 µg/mL) was fitted to concentration levels relevant to forensic toxicology issues. Compared with other analytical techniques, this newly established LC-MS-based method demonstrated specificity, simplicity, and rapidity. This method enables the detection of free chlorine for forensic investigations in criminal cases. Full article

Mass spectrometry (MS) is the only instrumental analytical technology that utilizes unique properties of matter, that is, its mass (m) and electrical charge (z). In the magnetic and/or electric fields of mass spectrometers, electrically charged native or chemically modified (millions) endogenous and (thousands) exogenous substances, the analytes, are separated according to their characteristic mass-to-charge ratio (m/z) values. Mass spectrometers coupled to gas chromatographs (GC) or liquid chromatographs (LC), the so-called hyphenated techniques, i.e., GC-MS and LC-MS, respectively, enable reliable determination of the concentration of analytes in complex biological samples such as plasma, serum, and urine. A particular technology is represented by inductively coupled plasma-mass spectrometry (ICP-MS), which is mainly used for the analysis of metal ions. The highest analytical accuracy is reached by using mass spectrometers with high mass resolution (HR) or by tandem mass spectrometers, as it can be realized with quadrupole-type instruments, such as GC-MS/MS and LC-MS/MS, in combination with stable-isotope labeled analytes that serve as internal standards, like a standard weight in scales. GC-MS belongs to the oldest and most advanced instrumental analytical technology. From the very beginning, GC-MS found broad application in basic and applied research sciences. GC-MS has played important roles in discovering biochemical pathways, exploring underlying mechanisms of disease, and establishing new evidence-based pharmacological therapy. In this article, we make an inventory of the use of instrumental mass spectrometry in the life sciences and attempt to provide a perspective study on the future of analytical mass spectrometry in clinical science, mainly focusing on GC-MS and LC-MS. We used information freely available in the scientific database PubMed (retrieved in August–November 2024). Specific search terms such as GC-MS (103,000 articles), LC-MS (113,000 articles), and ICP-MS (14,000 articles) were used in the Title/Abstract in the “PubMed Advanced Search Builder” including filters such as search period (1970–2024). In total, around 103,000 articles on GC-MS, 113,000 articles on LC-MS (113,000), and 14,000 articles on ICP-MS were found. In the period 1995–2023, the yearly publication rate accounted for 3042 for GC-MS articles and 3908 for LC-MS articles (LC-MS/GC-MS ratio, 1.3:1). Our study reveals that GC-MS/MS, LC-MS/MS, and their high-resolution variants are indispensable instrumentations in clinical science including clinical pharmacology, internal and forensic medicine, and doping control. Long-tradition manufacturers of analytical instruments continue to provide increasingly customer-friendly GC-MS and LC-MS apparatus, enabling fulfillment of current requirements and needs in the life sciences. Quantitative GC-MS and GC-MS/MS methods are expected to be used worldwide hand in hand with LC-MS/MS, with ICP-MS closing the gap left for metal ions. The significance of analytical chemistry in clinical science in academia and industry is essential. Full article

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. Full article

Mercury (Hg) is a toxic element which impacts on biological systems and ecosystems. Because the toxicity of Hg species is highly dependent on their concentration levels and chemical forms, the sensitive identification of the chemical forms of Hg—i.e., Hg speciation—is of major significance in providing meaningful information about the sources of Hg exposure. In this study, a microfluidic-based device made of high-clarity poly(methyl methacrylate) (PMMA) was fabricated. Then, titanium dioxide nanoparticles (nano-TiO₂s) were attached to the treated channel’s interior with the aid of poly(diallyldimethylammonium chloride) (PDADMAC). After coupling the nano-TiO₂-coated microfluidic-based photocatalyst-assisted reduction device (the nano-TiO₂-coated microfluidic-based PCARD) with high-performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS), a selective and sensitive, hyphenated system for Hg speciation was established. Validation procedures demonstrated that the method could be satisfactorily applied to the determination of mercury ions (Hg²⁺) and methylmercury ions (CH₃Hg⁺) in both human urine and water samples. Remarkably, the zeta potential measured clearly indicated that the PDADMAC-capped nano-TiO₂s with a predominance of positive charges indeed provided a steady force for firm attachment to the negatively charged device channel. The cause of the durability of the nano-TiO₂-coated microfluidic-based PCARD was clarified thus. Full article

Vehicle interior air quality is an issue of growing interest among car manufacturers and customers. GC-MS is the benchmark method for the analysis of indoor air or material emissions. It is suitable for the quantification of target pollutants and the most abundant compounds. It fails, however, to uncover the true molecular complexity of these samples. In the present study, we describe the development of a TD-GC × GC-TOFMS method designed to detect polar and potentially odorous molecules in car material emissions. Attention is paid to the hyphenation of the thermodesorber and the gas chromatograph, both at software and hardware levels, and the constraints due to pressure limitations on the thermodesorber (evaluated at 414 kPa/60 psi at the end of the temperature ramp and at 138 kPa/20 psi at rest). A compromise was made for the 2D column length and diameter to balance separation and pressure (50 × 0.18 × 0.18 cm × mm × µm + 60 cm transfer line selected). On various materials, we were able to observe several hundreds of polar molecules, among them were between 75 and 150 odorants per material. This work lays the foundation for the widespread screening of potential odorants in car material emissions. Full article