Search Results (25)

Medium-throughput forensic toxicology laboratories are increasingly expected to detect highly polar metabolites while working under tight resource and time constraints. To meet these requirements, a workflow is proposed that includes two stages: The first is computational metabolite prediction, followed by capillary zone electrophoresis (CZE), and the second stage is mass spectrometry (MS). The predictive step generates plausible metabolites and relevant physicochemical properties, which help guide early separation strategies. CZE then provides a rapid, low-cost way to test these predictions, identify informative samples, and exclude those unlikely to yield meaningful findings. Only samples that warrant further investigation proceed to targeted LC–MS/MS or high-resolution MS for confirmation. This approach shifts analytical effort toward the least resource-intensive stages, reducing unnecessary MS runs and improving turnaround time without compromising evidentiary standards. In practice, the workflow also improves day-to-day laboratory efficiency by overcoming equipment limitations and helping analysts focus on samples with genuine interpretive value. This stepwise combination of techniques is therefore suitable for routine forensic casework, where analytical decisions must be transparent, reproducible, and defensible. Full article

Near-critical and supercritical carbon dioxide (SC-CO₂) is extensively utilized in high-pressure separation, extraction, polymer processing, and carbon capture and utilization (CCU) technologies owing to its tunable density, low viscosity, high diffusivity, and environmentally benign nature. Reliable phase equilibrium data are indispensable for process design and optimization, especially in the near-critical region characterized by pronounced non-idealities, high compressibility, and density fluctuations. This review synthesizes experimental phase behaviour studies for binary mixtures of CO₂ with diverse components, including hydrocarbons, alcohols, ethers, esters, ketones, water, monomers/polymers, ionic liquids (ILs), and deep eutectic solvents (DESs), compiling extensive vapour–liquid equilibrium (VLE), liquid–liquid equilibrium (LLE), and critical data across industrially relevant pressure (up to 40 MPa) and temperature (up to 400 K) ranges. It critically evaluates analytical (sampling and non-sampling) and synthetic methodologies, addressing challenges in CO₂-rich phase handling, depressurization artefacts, and near-critical phenomena, while assessing data consistency against established reliability criteria. Key trends emerge, such as enhanced solubility with increasing pressure and CO₂ density, chain-length dependencies in hydrocarbons and alcohols, and Lewis acid–base interactions driving solvation in polar systems. The review highlights gaps in multicomponent data and proposes integrating high-quality experiments with advanced thermodynamic modelling to enhance predictive accuracy. Future directions emphasize high-precision in situ techniques, expanded datasets for complex mixtures, and novel CO₂-philic solvents to advance sustainable SC-CO₂ applications. Full article

A zero-dimensional, non-isothermal analytical framework was developed to assess solid oxide fuel cell (SOFC) performance across a broad range of operating conditions. The model integrates the anode, electrolyte, interlayers, and cathode, while resolving the distinct physicochemical processes within each layer. Electrochemical impedance spectroscopy (EIS), followed by distribution of relaxation times (DRT) analysis, was implemented to probe relevant cell polarization resistances under open-circuit and load conditions. The modeling framework couples mass and charge transport, electrochemical reactions, and non-isothermal heat transfer, with multilayer discretization applied to capture localized material properties and operating conditions. It enables the estimation of electrolyte ionic conductivity and total ohmic resistance by accounting for microstructural and geometric parameters, while also quantifying activation energies, exchange current densities, and gas-diffusion-related polarization resistances. Simulations were conducted for an SOFC operating on pure hydrogen with varying oxygen concentrations at 700 °C, 660 °C, 620 °C, and 580 °C. The results were validated against experimental data. The analysis revealed that ohmic overpotential dominates total cell losses, even at high current densities, underscoring the importance of minimizing ionic resistance to improve overall SOFC performance. Full article

Herbicides are widely used agrochemicals and are increasingly recognised as contaminants of emerging concern in aquatic environments due to their extensive application, environmental persistence, and potential ecological and human health impacts. Their determination in water presents significant analytical challenges, as these compounds occur at trace to ultra-trace levels and encompass a wide range of chemical properties, including highly polar and ionic species as well as transformation products. This review provides a critical overview of recent advances in separation technologies for the analysis of herbicides in water, based on peer-reviewed studies published between 2020 and 2025 retrieved from the PubMed and Scopus databases. The discussion focuses on developments in sample preparation, extraction strategies, chromatographic separation, and detection techniques, with particular attention to analytical performance and sustainability. The reviewed studies demonstrate that solid-phase extraction remains central to achieving the lowest detection limits, while miniaturised and greener extraction approaches are increasingly adopted to reduce solvent consumption and simplify workflows. Advances in chromatographic separation and detection, especially liquid chromatography coupled to tandem mass spectrometry, have further enhanced sensitivity and selectivity for a broad range of herbicides. Overall, this review highlights current analytical capabilities and emerging trends, outlining future directions for reliable and sustainable monitoring of herbicides in aquatic environments. Full article

Silicon nanowire field-effect transistors (Si NWFETs), thanks to their highly efficient integration into numerous electronic devices, represent promising tools for pH measurements and molecular biosensing due to their high sensitivity to ionic charges on their surface. To obtain a highly sensitive, stable, and low-noise signal in liquid media, the use of a reference electrode is necessary. Among potential reference electrodes, Ag/AgCl electrodes have proven to be the easiest to miniaturize and, consequently, the most widely used in Si NWFETs. However, their integration in such devices remains complex. The choice of the type of Ag/AgCl reference electrode and its positioning vary considerably depending on the device configuration and the analyte, and whether the measurements are carried out in dynamic or static environments. Here, we report a consolidated overview focused on the reference electrode implementation in Si NWFETs, presenting the advantages and disadvantages of different strategies encountered, and illustrating our points with several examples of miniaturized electrochemical biosensors and ion-sensitive field-effect transistors. Finally, in order to understand the effects of the Ag/AgCl electrode in Si NWFETs and its influence on the polarization of the device or the analyte, a comparative study of different device configurations from the literature is also presented. 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

In this article, the mechanism of relaxation polarization currents occurring at a constant temperature (isothermal process) in crystals with ionic-molecular chemical bonds (CIMBs) in an alternating electric field was investigated. Methods of the quasi-classical kinetic theory of dielectric relaxation, based on solutions of the nonlinear system of Fokker–Planck and Poisson equations (for the blocking electrode model) and perturbation theory (by expanding into an infinite series in powers of a dimensionless small parameter) were used. Generalized nonlinear mathematical expressions for calculating the complex amplitudes of relaxation modes of the volume-charge distribution of the main charge carriers (ions, protons, water molecules, etc.) were obtained. On this basis, formulas for the current density of relaxation polarization (for transient processes in a dielectric) in the k-th approximation of perturbation theory were constructed. The isothermal polarization currents are investigated in detail in the first four approximations (k = 1, 2, 3, 4) of perturbation theory. These expressions will be applied in the future to compare the results of theory and experiment, in analytical studies of the kinetics of isothermal ion-relaxation (in crystals with hydrogen bonds (HBC), proton-relaxation) polarization and in calculating the parameters of relaxers (molecular characteristics of charge carriers and crystal lattice parameters) in a wide range of field parameters (0.1–1000 MV/m) and temperatures (1–1550 K). Asymptotic (far from transient processes) recurrent formulas are constructed for complex amplitudes of relaxation modes and for the polarization current density in an arbitrary approximation k of perturbation theory with a multiplicity r by the polarizing field (a multiple of the fundamental frequency of the field). The high degree of reliability of the theoretical results obtained is justified by the complete agreement of the equations of the mathematical model for transient and stationary processes in the system with a harmonic external disturbance. This work is of a theoretical nature and is focused on the construction and analysis of nonlinear properties of a physical and mathematical model of isothermal ion-relaxation polarization in CIMB crystals under various parameters of electrical and temperature effects. The theoretical foundations for research (construction of equations and working formulas, algorithms, and computer programs for numerical calculations) of nonlinear kinetic phenomena during thermally stimulated relaxation polarization have been laid. This allows, with a higher degree of resolution of measuring instruments, to reveal the physical mechanisms of dielectric relaxation and conductivity and to calculate the parameters of a wide class of relaxators in dielectrics in a wide experimental temperature range (25–550 K). Full article

The electrooxidation (EO) of three important environmental contaminants, anticorrosive 1H-benzotriazole (BTA), plasticizer dibutyl phthalate (DBP), and non-ionic surfactant Triton X-100 (tert-octylphenoxy[poly(ethoxy)] ethanol, t-OPPE), was studied as a possible means to improve their elimination from wastewaters, which are an important emission source. EO was performed in a batch reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode. Different supporting electrolytes were tested: NaCl, H₂SO₄, and Na₂SO₄. Results were analysed from the point of their efficacy in terms of degradation rate, kinetics, energy consumption, and transformation products. The highest degradation rate, shortest half-life, and lowest energy consumption was observed in the electrolyte H₂SO₄, followed by Na₂SO₄ with only slightly less favourable characteristics. In both cases, degradation was probably due to the formation of persulphate or sulphate radicals. Transformation products (TPs) were studied mainly in the sulphate media and several oxidation products were identified with all three contaminants, while some evidence of progressive degradation, e.g., ring-opening products, was observed only with t-OPPE. The possible reasons for the lack of further degradation in BTA and DBP are too short of an EO treatment time and perhaps a lack of detection due to unsuitable analytical methods for more polar TPs. Results demonstrate that BDD-based EO is a robust method for the efficient removal of structurally diverse organic contaminants, making it a promising candidate for advanced water treatment technologies. Full article

Novel peptides based on common amino acid building blocks may serve as possible drug candidates; however, their flexible structures may require stabilization via the incorporation of conformational constraints. The insertion of unusual amino acids is a feasible option that may provide improved pharmacokinetic and pharmacodynamic properties of such peptide-type drugs. The stereochemical purity of these kinds of building blocks must be verified by an efficient separation technique, such as high-performance liquid chromatography. Here, we present and discuss the results of the stereoselective separation mechanism of ß-methylated phenylalanine (ß-MePhe), tyrosine (ß-MeTyr), 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (ß-MeTic), and cyclohexylalanine (ß-MeCha) together with non-methylated Phe, Tyr, Tic, and Cha applying Cinchona alkaloid-based chiral stationary phases (CSPs). The studied zwitterionic CSPs acting as ion exchangers provided optimal performance in the polar ionic mode when methanol or a mixture of methanol and acetonitrile was utilized as the mobile phase together with organic acid and base additives. It was found that the basicity of small amines applied as mobile phase additives did not directly influence the chromatographic ion exchange concept. However, the size of the amines and their concentration led to a reduced retention time following the principles of ion exchange chromatography. On the basis of a systematic study of the effects of the eluent composition on the chromatographic behavior, important structure–retention and enantioselectivity relationships could be revealed. Through a temperature study, it has become evident that the composition of the eluent and the structure of analytes markedly affect the thermodynamic properties. Full article

The Bozhushan in southeastern Yunnan is a composite granite body that was formed by multi-phase magmatic intrusion. The genesis of the tourmaline-supergroup minerals occurring therein remains uncertain, as it has been the subject of only a limited number of studies. This investigation employs an integrated analytical approach combining EPMA, LA-ICP-MS, and boron isotope geochemistry, supplemented by detailed field geological investigations and petrographic observations of tourmaline textural characteristics. This study aims to elucidate the genetic relationships between distinct tourmaline varieties, establish temporal correlations between mineral crystallization stages and magmatic–hydrothermal evolution processes, and evaluate the petrogenetic significance of tourmaline geochemical signatures for regional mineralization events. This study analyzes tourmaline-supergroup minerals in granitic pegmatites and aplites, which occur as nodular, radial, and columnar aggregates. Most tourmaline crystals exhibit well-defined rhythmic zoning patterns, which are clearly observable under cross-polarized light microscopy. Chemical composition analysis has identified two tourmaline species: schorl and dravite. The formation of tourmaline is primarily of magmatic origin and is characterized by a magmatic–hydrothermal transition. It predominantly belongs to the alkali subgroup and is formed in Li-poor granitoids and associated pegmatites and aplites, Ca-poor metapelites, metapsammites, and quartz-tourmaline rocks. The inter-ionic substitution mechanism in this system is predominantly governed by Fe²⁺Mg₋₁ and (X_vacAl)(NaR²⁺)₋₁ exchange equilibria. Additionally, geochemical evidence indicates that the primary ore-forming fluids originate from granitic magmas, which are likely sourced from the partial melting of metasedimentary rocks. During the late Yanshan period, the upwelling of granitic magma in the Bozhushan area introduced a substantial heat source and mineralizing fluids, which interacted with the Cambrian units to form tungsten–tin mineralization. The geochemical data on tourmaline indicate that the Bozhushan granite body has considerable potential for ore mineralization. Full article

The glycosylation process plays a crucial role in the structural integrity and biological activity of glycoproteins, where glycans are attached to a protein backbone. There are many kinds of glycans, the most common being N-glycans, which can be arranged into three classes, that is, complex, hybrid, and high mannoses, forming a structurally very diverse set of polar compounds that are difficult to detect and separate. Most commonly, N-glycans are labeled before separation by charged or fluorescence tags for better MS or fluorescence detection, respectively. This study examines the influence of ionic strength and organic modifier selection on the separation of fluorescently labeled dextran ladders in Hydrophilic Interaction Liquid Chromatography (HILIC). Using a Glycan BEH Amide column and varying the ammonium formate buffer concentration along with acetonitrile and methanol ratios, we investigated analyte retention, separation efficiency, and post-column conductivity changes. Our findings reveal that changes in the ionic strength of the mobile phase do not contribute to changes in selectivity, neither when acetonitrile nor methanol were used as organic modifiers to the mobile phase. However, the addition of methanol significantly changes the separation mechanism where two different prevailing separations mechanisms can be identified. It was assumed that the addition of methanol influences the folding pattern of dextrans around the permanent positive charge on the added tag, which influences the changes of separation selectivity. This work presents a systematic approach to altering mobile phase composition (buffer concentration, organic modifier type) to control retention and selectivity in complex glycan analysis. The discovery that methanol significantly alters separation behavior provides a potential new method for refining HILIC separations of polar compounds. Full article

Reversed-phase liquid chromatography (RPLC) relies on a non-polar stationary phase and a more polar hydro-organic mobile phase, where compound retention is primarily governed by hydrophobicity, with more hydrophobic compounds being retained longer. The introduction of secondary equilibria in the chromatographic system through additives, such as anionic surfactants and ionic liquids (ILs), was proposed to mitigate ionic interactions between positively charged analytes and the anionic free silanol groups in non-endcapped stationary phases, thereby preventing increased retention and peak tailing. Additionally, the combined hydrophobic and ionic interactions between cationic analytes and the ions in these additives was demonstrated to create mixed retention mechanisms that influence retention and selectivity. In this regard, this study investigates aqueous chromatographic systems incorporating both the anionic surfactant sodium dodecyl sulfate (SDS) and the IL 1-hexyl-3-methylimidazolium chloride as mobile phase reagents. This combination of reagents modulates the retention, eliminating the need for organic solvents and resulting in highly sustainable HPLC procedures. The chromatographic behavior was assessed using two different C18 columns (Zorbax Eclipse and XTerra-MS). The strength of solute interactions was estimated by calculating equilibrium parameters and the contributions of hydrophobic and ionic interactions through simple mathematical models. Focusing on the retention of six basic drugs (β-adrenoceptor antagonists), the study highlighted the significant role of ionic interactions. The results demonstrate the feasibility of using aqueous systems combining SDS and an IL for the efficient separation of moderately polar basic compounds without the use of organic solvents. Full article

At present, stationary phases based on ionic liquids are a promising and widely used technique in gas chromatography, yet they remain poorly studied. Unfortunately, testing of “new” stationary phases is often carried out on a limited set of test compounds (about 10 compounds) of relatively simple structures. This study represents the first investigation into the physicochemical patterns of retention of substituted (including polysubstituted) aromatic alcohols on two stationary phases of different polarities: one based on pyridinium-based ionic liquids and the other on a standard polar phase. The retention order of the studied compounds on such stationary phases compared to the standard polar phase, polyethylene glycol (SH-Stabilwax), was compared and studied. It was shown that pyridinium-based ionic liquids stationary phase has a different selectivity compared to the SH-Stabilwax. Using a quantitative structure–retention relationships (QSRR) study, the differences in selectivity of the two stationary phases were interpreted. Using CHERESHNYA software, the importance of descriptors on different stationary phases was evaluated for the same data set. Different selectivity of the stationary phases correlates with different contributions of descriptors for the analytes under study. For the first time, we show that in-column dehydration is observed for some compounds (mostly substituted benzyl alcohols). This effect is worthy of further investigation and requires attention when analyzing complex mixtures. It suggests that when testing “new” stationary phases, it is necessary to conduct tests on a large set of different classes of compounds. This is because, in the case of using ionic liquids as an stationary phase, a reaction between the analyte and the stationary phase is possible. Full article

Glioblastoma is a highly malignant brain tumor consisting of a heterogeneous cellular population. The transformed metabolism of glioblastoma cells supports their growth and division on the background of their milieu. One might hypothesize that the transformed metabolism of a primary glioblastoma could be well adapted to limitations in the variety and number of substrates imported into the brain parenchyma and present it their microenvironment. Additionally, the phenotypic heterogeneity of cancer cells could promote the variations among their metabolic capabilities regarding the utilization of available substrates and release of metabolic intermediates. With the aim to identify the putative metabolic footprint of different types of glioblastoma cells, we exploited the possibility for separation of polar and ionic molecules present in culture media or cell lysates by hydrophilic interaction liquid chromatography (HILIC). The mass spectrometry (MS) was then used to identify and quantify the eluted compounds. The introduced method allows the detection and quantification of more than 150 polar and ionic metabolites in a single run, which may be present either in culture media or cell lysates and provide data for polaromic studies within metabolomics. The method was applied to analyze the culture media and cell lysates derived from two types of glioblastoma cells, T98G and U118. The analysis revealed that even both types of glioblastoma cells share several common metabolic aspects, and they also exhibit differences in their metabolic capability. This finding agrees with the hypothesis about metabolic heterogeneity of glioblastoma cells. Furthermore, the combination of both analytical methods, HILIC-MS, provides a valuable tool for metabolomic studies based on the simultaneous identification and quantification of a wide range of polar and ionic metabolites—polaromics. Full article

Due to the favorable features obtained through the incorporation of fluorine atom(s), fluorinated drugs are a group with emerging pharmaceutical importance. As their commercial availability is still very limited, to expand the range of possible candidates, new fluorinated tryptophan analogs were synthesized. Control of enantiopurity during the synthesis procedure requires that highly efficient enantioseparation methods be available. In this work, the enantioseparation of seven fluorinated tryptophans and tryptophan was studied and compared systematically to (i) develop analytical methods for enantioselective separations and (ii) explore the chromatographic features of the fluorotrytophans. For enantioresolution, macrocyclic glycopeptide-based selectors linked to core-shell particles were utilized, applying liquid chromatography-based methods. Application of the polar-ionic mode resulted in asymmetric and broadened peaks, while reversed-phase conditions, together with mobile-phase additives, resulted in baseline separation for all studied fluorinated tryptophans. The marked differences observed between the methanol and acetonitrile-containing eluent systems can be explained by the different solvation abilities of the bulk solvents of the applied mobile phases. Among the studied chiral selectors, teicoplanin and teicoplanin aglycone were found to work effectively. Under optimized conditions, baseline separations were achieved within 6 min. Ionic interactions were semi-quantitatively characterized and found to not influence enantiorecognition. Interestingly, fluorination of the analytes does not lead to marked changes in the chromatographic characteristics of the methanol-containing eluents, while larger differences were noticed when the polar but aprotic acetonitrile was applied. Experiments conducted on the influence of the separation temperature indicated that the separations are enthalpically driven, with only one exception. Enantiomeric elution order was found to be constant on both teicoplanin and teicoplanin aglycone-based chiral stationary phases (L < D) under all applied chromatographic conditions. Full article