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HPLC remains one of the most widely used measurement techniques for chemical analysis. Capillary LC, which utilizes narrow diameter columns operated at lower flow rates than analytical-scale LC, continues to gain adoption based on its reduced mobile phase consumption and increased sensitivity when coupled to MS detection. This tutorial offers practical insights into the most critical aspects of translating analytical-scale separations to the capillary scale. The selection of pumping systems, detectors, and the potential for performance loss due to extra-column effects are examined within the context of separations using columns with inner diameters ≤ 0.3 mm. Column choices within this diameter range are also detailed, both in terms of stationary phase support options and general commercial availability. The impact of these various factors on the effective development/translation of LC methods down to flow rates under 10 µL/min is described to provide readers with a basis for implementing these strategies within their own analytical workflows.

Ultrashort-chain (USC) per- and polyfluoroalkyl substances (PFAS) are small and very polar compounds with carbon chain lengths shorter than C4. Their ubiquitous and high levels of occurrence in environmental aquatic systems are emerging as a significant concern, rivaling the well-established issues associated with long-chain PFAS contamination. Therefore, it is important to analyze both USC and long-chain PFAS together in water samples to comprehensively assess and address the full spectrum of PFAS contamination. The high polarity of USC PFAS poses a challenge for standard chromatographic practices in PFAS analysis, primarily due to insufficient chromatographic retention. In this study, a simple and reliable workflow was developed for the simultaneous analysis of C1 to C14 perfluoroalkyl carboxylic and sulfonic acids, along with other groups of PFAS, in both potable and non-potable waters. The chromatographic separation was conducted using a polar-embedded reversed-phase LC column with an inert coating on the hardware. Three different water matrices (tap water, bottled water, sewage treatment wastewater) were chosen for method evaluation to demonstrate the applicability of the developed workflow for measuring 45 PFAS compounds in diverse water samples. A dilute-and-shoot workflow was evaluated by accuracy and precision analysis at five fortification levels, ranging from 2 to 250 ng/L. Eighteen isotopically labeled PFAS, serving as extracted internal standards, were added to the samples at 100 ng/L to validate the accuracy of the entire workflow. Calibration standards were prepared in reverse osmosis water due to its cleanliness for all analytes. The calibration ranges varied among different analytes, spanning from 1 – 1000 ng/L. All analytes and extracted internal standards exhibited recovery values ranging from 70% to 130% of the nominal concentration across all fortification levels. Satisfactory method precision was demonstrated with %RSD values below 20%. Additional potable and non-potable waters collected from various source waters were tested to further demonstrate that the established workflow is suitable for the accurate quantification of targeted PFAS in a wide range of water matrices.

With this work, we present a comprehensive tutorial for the analysis of oligonucleotides (ONs, 5 to 100 mer) using ion-pair reversed-phase liquid chromatography (IP-RPLC) on ultra-short columns (20 × 2.1 mm). We explore the impact of ion-pairing (IP) agents on ON retention and demonstrate that while IP agents significantly influence absolute retention, their effect on selectivity is often minimal. Our findings emphasize the utility of systematic method development, including software-assisted retention modeling, to optimize gradient steepness and temperature such that resolution can be optimized for both sequence and length variants. We recommend the use of low-adsorption column hardware to minimize nonspecific interactions, which is to the benefit of improving method robustness, peak shapes and recovery (especially of shortmer impurities). Our results confirm the utility of so-called ultra-short column formats as is demonstrated by way of the example, quick run time separations and high-throughput ON analyses. The study establishes practical guidelines for developing robust, reproducible, and high-efficiency IP-RPLC methods for ONs which will be of assistance to analysts working on new therapeutics and new sequencing and diagnostic reagents alike.

Rapid cell viability assessments are essential in a growing number of fields, including clinical analysis, healthcare, drug development and food safety. Electrokinetic (EK) methodologies have proved to be robust and reliable platforms of the analysis of cells, including viability assessments. Discussed here are applications of two EK phenomena, dielectrophoresis and electrophoresis, which can discriminate cells by their viability status and also sort and separate cells into separate viable and nonviable fractions, so further analysis can be performed. For each EK method, the operating principle is presented, followed by a brief historical overview and a detailed analysis of recent reports published between 2015 and 2024. The concluding remarks include a summary of the content of this review article and present a future perspective on the expected future advances on EK-based systems for the assessment and separation of cells based on their viability status.

A novel thin-film solid-phase microextraction (TF-SPME) device based on glass vials internally coated with silver nanoparticles (AgNPs) was developed for the first time, and used for determining five phenols in wastewater, bottled water, and irrigation water samples by high-performance liquid chromatography coupled to a photodiode array detector (HPLC-PDA). Different AgNPs were synthesized varying the ratio of metallic salt versus the reduction agent, and the pH of the synthesis. The preparation of the TF-SPME glass vial device was optimized in terms of the type of AgNPs used and the number of layers of AgNPs. Besides, the TF-SPME procedure was also optimized. The TF-SPME method was very simple, only requiring the addition of 18 mL of water and 5 min of agitation, followed by the disposal of the water and addition of the 750 µL as desorption solvent, and direct HPLC-PDA injection. The entire method showed adequate analytical performance, with limits of detection ranging from 3 to 8 μg·L-1, and intra-day and inter-day precision (as RSD), both evaluated with different vials and therefore showing inter-batch precision, with values between 8.70 and 16.4 %, and 6.0 and 19.7 %, respectively. The TF-SPME-HPLC-PDA procedure was compared with previous methods for the determination of phenols, both in terms of analytical performance and greenness assessments applying different metrics, showing clear advantages.

Flavonoids have been the topic of numerous studies for decades because they possess varied interesting bioactivities including e.g. antioxidant and anticancer properties. In particular, some flavonoids possess chiral features, due to the presence of one or two chiral carbon atoms on their aglycone root. They include flavans, isoflavans, flavanones, flavanonols, flavanols and auronols. In addition, other chirality centres may be observed on the carbohydrate groups attached to the aglycone root, but these will not be considered in the present paper. However, as stereoisomers usually have different bioactivity, analysis methods focusing on these specific flavonoid classes should be of interest to better understand their mode of action and their biosynthetic pathways. In the present review, we have examined chromatographic analyses in the liquid phase (LC) and the supercritical phase (SFC) in achiral and chiral modes to analyse chiral flavonoids. One- and two-dimensional methods are reported, and the different detection modes are also examined. Note that this review did not aim at being comprehensive, but rather at displaying the diversity and main features of current methods.

Mobile phase composition remains the major experimental parameter influencing the separation process in reversed-phase high-performance liquid chromatography (RP-HPLC). Its influence on the retention of solutes is explained by the Hildebrand solubility parameter and solvophobic theory, which also considers molecular characteristics of the participants in a separation process. The main empirical dependences (linear and polynomial) between the retention factor and the composition of mobile phase (retention function) are discussed taking into consideration a wide range of mobile phase compositions. Two direct chromatographic indices are resulting from these equations: the extrapolated value of retention factor for zero organic content in mobile phase composition (log kw) and the solvent strength parameter (S), which for a linear retention function is its slope being constant over the entire mobile phase compositions. Another chromatographic index could result from the retention function for zero content of water in mobile phase, but this situation can be applied only for very hydrophobic solutes. For large domains of mobile phase composition, the retention function cannot be described by a single type of dependence. This explains the paradox of generating by extrapolation different logkwvalues for different organic components. For the mobile phase close to pure water the retention function is different from that at average water concentration.

Review contents the extensive insight into the last 10 years in the history of inverse gas chromatography (IGC). Although this technique seems to be well-known. Every year brings new proposals concerning the procedures enabling the deeper insights in the properties of the surfaces as well as the bulk of various materials. Meetings organized by the universities and commercial groups indicate the growing society of users. Different versions of IGC are most often used in following the changes of materials properties undergoing technological modifications and/or changes caused by the environment in which such material is applied.The wide group of raw materials, minerals, pharmaceutical components, abrasive articles, cellulosic materials, bacteria biomass, ionic liquids, metal-organic frameworks (MOFs) as well as various hybrid materials were characterized by IGC. Here it is worth to indicate the properties of dentine and enamel during dental treatment or (on the other side) examination of the influence of various external parameters on the transport of gaseous compounds in different geologic materials. The advantages and challenges that arise during such experiments are presented and discussed.

Mass spectrometry is crucial for analysing physicochemical and sensory properties, including colour, astringency, taste, and flavour, predicting ageing characteristics, and addressing stability issues in wine. Polyphenols are key chemical constituents in wine that are associated with health benefits and improve circulatory conditions. Advances in mass spectrometry ionisation techniques such as matrix-assisted laser desorption and ionisation and direct analysis in real-time offer high sensitivity for identifying important polyphenolic constituents in wine. High-resolution mass spectrometry, in combination with liquid chromatography, accurately identify and quantify polyphenolic compounds, even at low concentrations, and provides the possibility for further retrospective analysis and non-targeted analysis using statistical methods of data analysis. Ambient mass spectrometry techniques such as paper spray and low-temperature plasma allow solventless analysis, determining the geographical origin, authentication, and quality control of wine samples. This review will explore the potential benefits of using mass spectrometry to identify various polyphenols and polymeric polyphenols in wine, as well as recent developments and applications. Additionally, we will discuss determining antioxidant activity and total polyphenol content in wine.

Phytosterols (PSs) are bioactive compounds in the sterol family, present in numerous complex food and plant matrices in free and conjugated forms. The interest in these compounds arises for phytotherapeutic purposes, particularly for their action on cholesterol metabolism and impact on cardiovascular diseases. There is a need to develop approaches that can selectively extract target analytes and accurately identify and quantify them with high precision. This work proposed the synthesis of molecularly imprinted polymers (MIPs) for PSs with a sonochemical approach, enabling a rapid polymerization step (5 min). This proposed MIP was able to extract 8 PSs (brassicasterol, stigmastanol, campesterol, campestanol, stigmasterol, β-sitosterol, Δ5-avenasterol, α-spinasterol) from a wide range of plant and food matrices belonging to different classes (Brassicaceae, dried fruits and Leguminosae) and was coupled to ultra-high liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). MIP based on dispersed solid phase extraction (dSPE-MIP) and targeted analysis has proven to be particularly effective in addressing the challenges associated with the complexity of plant-derived matrices, minimising interferences. This was demonstrated by the excellent control of the matrix effect, which was within ±15 %, ensuring the robustness and reliability of the method. The identification and quantification of 8 different PSs was successfully achieved with satisfactory recovery values ranging from 65 % to 100 %. The proposed strategy offers an affordable alternative to classical methods, providing enhanced sensitivity, selectivity and overall performance.

The slow formation and renewal of soil, coupled with the multitude of services it provides to humanity, render this resource a critical component of the biosphere. The maintenance of soil structure and the accumulation of carbon, as well as the maintenance of biodiversity in soils, rely on the contribution of different fractions of soil organic matter. Despite its minor component in soils, the lipid fraction is of particular importance. Its functional diversity offers an inherent diagnostic value regarding soil organic matter, microbial biodiversity and the pedological processes to which the soil is subjected. Soil lipids are comprised of diverse groups of organic compounds, exhibiting structural variations from derivatives of complex organic components (e.g., phosphoglycerides or phospholipids, sphingomyelins, glycosphingolipids) to simpler functional classes which can combine to form other compounds such as wax esters, acylglycerols, sterols, terpenoids, and fatty acids. The analytical strategy for determining lipids in soils commonly involves extracting the lipids, then fractionating, hydrolyzing, derivatizating, identifying, and/or measuring them by chromatography. These sample treatment procedures for lipid analysis in this complex matrix are typically traditional. While sustainable sample preparation procedures are not yet fully implemented, the analysis of intact lipids by liquid chromatography coupled to mass spectrometry detection is becoming more common to avoid fractionation and derivatization. This paper reviews current sample preparation strategies for the analysis of soil lipids and presents some alternatives to the traditional methods used for soil lipid extraction, fractionation, and derivatization.

The separation and analysis of chiral compounds is an important topic in various fields such as research, pharmaceutical industry, food control, agrochemistry, biochemistry, forensics and toxicology, etc. The interest in the mentioned fields is mainly due to the fact that enantiomers could react with the chiral environment. Therefore, their separation and analysis are a challenging issue because the use of these compounds can be related to humans and animals’ lives as well as to the environment (e.g., soil and water). Their separation can be performed with different analytical techniques such as high-performance liquid chromatography, gas chromatography, supercritical fluid chromatography, and microfluidic technique (capillary electrophoresis and capillary electrochromatography-CEC). Usually the direct resolution method is applied making use of a chiral stationary phase (CSP). This tutorial is aimed at illustrating the main features of CEC using a packed capillary, e.g., employing a silica-vancomycin CSP. The synthesis of the CSP, the instrumentation of CEC coupled with UV and mass spectrometry detectors, method optimization, and two selected applications are presented and discussed.

Food analysis plays an important role in preserving the integrity and quality of food. Despite these noble goals, most official methods for the analysis of nutrients (vitamins, carotenoids, etc.) antioxidants (polyphenols, etc.), and contaminants (pesticides, veterinary drugs, mycotoxins etc.) still rely on time-consuming, complex, and polluting procedures of sample preparation. To solve this discrepancy, the scientific community has frantically been working to make extraction procedures faster and safer, resorting to miniaturization, automation, low-energy consumption, and solvents/sorbents from renewable resources. This review provides an overview of the most sustainable extraction methods in food analysis, developed over the last ten years (2014–2024), including relevant examples of both liquid phase and sorbent-based techniques. Particular emphasis is placed on solutions aimed at improving the method sustainability such as smart devices, neoteric solvents, and composite sorbents, discussing the latest advancements and future trends in this sector.

The review compiles a selection of the recently published chemical research on stilbenes, stilbene glucuronides, and stilbenoids. The basic structure of stilbene group compounds is 1,2-diphenylethene. They can be isolated from spruce, pine, and other conifers, and specifically from wood bark, needles, heartwood, and roots.Stilbenes and stilbenoids possess antioxidative, anti-inflammatory, and antimicrobial impacts what for they are used in pharmaceuticals. They decrease of glucose and triglyceride concentrations in plasma. Especially, they are used for treatment of cancer, liver injuries, and Alzheimer's disease.Lately, extraction of stilbene group compounds from wood materials was done with alcohol, water, or nonpolar solvents. Moreover, they were extracted with supercritical fluid and hot water extraction methods. Rectified extracts were studied with liquid and/or gas chromatography. Mass spectrometry with negative electrospray ionization was the prevalent method for their identification. HPLC-MS methods were preferred over GC to identify dimeric stilbenes and oligomeric stilbenoids.

This review is aimed at providing an overview of the application of liquid chromatography-high resolution mass spectrometry (LC-HRMS) in the metabolomic study of cereal grains, with special emphasis on wheat, maize, barley, and rice. The significant role of untargeted metabolomics in identifying and quantifying metabolites is highlighted, thereby elucidating biochemical pathways involved in flavour, disease detection, and the development of disease-resistant varieties. The use of stable isotope labelling for enhanced compound annotation and the exploration of metabolic pathways involved in plant defence mechanisms and stress resilience are also discussed. The integration of cutting-edge analytical techniques is becoming of fundamental importance to enhance the understanding of metabolic reconfigurations in response to various conditions, thereby contributing to the improvement of cereal quality and ensuring food safety. The potential health benefits of phytochemicals in human nutrition and the role of specific metabolites as biomarkers for crop resistance and susceptibility to diseases, pests, and abiotic stresses are discussed. Overall, valuable insights into the advancement of analytical chemistry and its applications in agricultural science are provided by this review.

Edible flowers have been consumed from ancient times and it was believed to deliver medicinal properties. This study explored some common edible flowers from Assam, India, such as Night Jasmine (Nyctanthus arbortristis), Drumstick (Moringa oleifera), Pumpkin (Cucurbita spp.), and Nongmangkha (Phlogacanthus thyrsiflorus), to assess their nutritional values, phytochemical characteristics, antioxidant potential, and mineral content. Additionally, the study aimed to analyze the presence of various phenolic compounds in these flowers using HPLC. Nongmangkha flowers exhibited the highest total phenolic content (TPC) of 118.12 mg GAE/g and total flavonoid content (TFC) of 75.36 mg QE/g. Drumstick flowers showed the highest ash content at 6.55 % and also the highest DPPH radical scavenging activity at 89.76 %. Potassium was found among all these flowers ranged from 11.95 to 4.412 mg/g, zinc 0.046 to 0.130 mg/g and iron 0.235 to 0.513 mg/g. HPLC screening showed that, Night jasmine flowers had gallic acid, resorcinol, caffeic acid, p-coumeric acid, ferulic acid. The findings of this study are valuable for understanding the nutritional composition of these edible flowers. Additionally, further scientific research is needed on their bioaccessibility and bioavailability, as well as on the application of these flowers in the development of food products

This study investigated the physicochemical and antioxidant properties of stingless bee (Tetragonula carbonaria) cerumen from Australia, while also identifying some phenolic constituents using High-Performance Thin-Layer Chromatography (HPTLC). The antioxidant activity of the ethanolic T. carbonaria cerumen extracts was determined using a Ferric Reducing Antioxidant Power (FRAP) assay and a HPTLC-DPPH approach was used to identify the constituents that contribute to the antioxidant activity of the cerumen samples. For the determination of the total phenolic content (TPC), a modified Folin-Ciocalteu assay was carried out. The FRAP values ranged from 5.19 ± 0.40 to 16.2 ± 0.70 mmol Fe2+/kg of raw cerumen and the TPC values from 3.77 ± 0.12 to 81.3 ± 2.04 mg GAE/g of raw cerumen. The HPTLC analysis revealed the presence of gallic acid and kaempferol in the ethanolic T. carbonaria cerumen extracts which contribute to the antioxidant activity of the samples. The findings of the study demonstrate the antioxidant activity of Australian T. carbonaria cerumen and highlight the importance of more research into its chemical composition, bioactivity and potential therapeutical use.

Since the introduction of Quality by Design for production of biopharmaceuticals, the global biopharma industry has been advancing towards developing highly efficient and sensitive platforms for monitoring product quality attributes. Incorporating mass-spectrometry-based multi-attribute monitoring (MAM) as a novel tool for identifying and characterizing post-translational modifications in biotherapeutics has gained increasing traction. The ability of MAM to monitor multiple critical quality attributes coupled with new peak detection functions in a single workflow is highly desirable to the biopharmaceutical industry. This review examines and discusses the evolution and adaptation of MAM for routine product quality assessment. MAM applications in biotherapeutic characterization, comparability, and chemometrics have also been discussed, along with the gaps and future perspectives of the MAM implementation in biopharmaceutical drug development. Primary focus has been kept on major developments in last 6 years (2018–2024).

A new derivatization reagent, phthalylglycyl chloride (PG-Cl), for the analysis of urinary amino acids was demonstrated using reversed-phase ultra-high performance liquid chromatography coupled to electrospray ionization-quadrupole-time-of-flight mass spectrometer. The study compares the limits of detection and quantification for different sample preparation techniques with the commonly used and effective method of derivatization using dansyl chloride. The stability of the derivatives was investigated, and the study includes an example of urinary amino acid analysis using PG-Cl derivatization. The optimal values for pH, temperature, and concentration of the derivatization reagent were established. Limits of quantification in the range of 0.5–500 µg/mL were obtained for different amino acids. The possibility of phthalylglycyl chloride usage for non-target screening applications and targeted analysis of amino acids in urine was discussed. An advantages and issues of PG-Cl in comparison with commonly used acyl-chlorides (FMOC-Cl and DNS-Cl) provided and discussed.

Rice husk ash is an important waste of agricultural industry that, within the framework of the circular economy, has been easily converted into a sustainable sorbent material. This was tested in this work for the pre-concentration of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), representative perfluoroalkyl substances as probe environmental pollutants of waters, with HPLC-MS/MS quantification. The preparation involves a rapid microwave-assisted oxidation followed by a hydrothermal treatment, which was studied using a 22 design of experiments. The final material was thoroughly characterized and tested for its affinity to the target analytes by solid-phase extraction in environmental waters and wastewaters. Recoveries in the range 67–113 % (RSD < 11 %, n = 3) were achieved at environmentally relevant concentrations (10, 50, and 100 ng L-1) and the sorbent was reusable for at least ten consecutive extractions. Good linearity (R2 = 0.9997) was observed, with a method quantification limit in the water sample of 10 ng L-1 that allows the analysis of PFOA and PFOS below the established limits. The method was evaluated for greenness using AGREEprep and SPMS metrics, and it was then applied to the analysis of actual water samples from Northern Italy.

Olive oil is the most used vegetable oil for human consumption and its production represents an important economic sector, especially in Mediterranean countries. Olive trees are grown in more than 40 countries around the world on over 10 million hectares. The milling industry generates large quantities of liquid and solid residues, the disposal of which requires sophisticated and rather expensive procedures, given the polluting characteristics of the processing products. Since a considerable measure of olive-derived biomass is generated each year, it could be used as a potential source of bioactive compounds. This work evaluates the possibility of recovering natural antioxidants from by-products of the olive oil mill, through the optimization of extraction processes with green approaches. In the present work, through HPLC-PDA analysis with a validated method, it was possible to characterize a chemical profile of the extracts obtained through an optimized (DoE) and green approach. The waste products of the olive oil companies represent the samples considered in this work, and are derived from the pomace and the washing water of 2-phases, 2.5-phases, and 3-phase extra virgin olive oil (EVO) production plants. The optimized extraction methodology, starting from the 2.5-phase olive pomace, proved to be satisfactory in terms of efficiency by evaluating the effect of parameters such as extraction time and process temperature. The application of this methodology to other types of pomace and agro-industrial by-products has highlighted excellent results in terms of extraction yield, demonstrating the validity of this procedure as also suitable for other solid residues coming from the olive oil mill. Regarding the treatment in vegetation water, the developed protocol allowed the chromatographic profile of the analytes extracted from this matrix to be evaluated, leading to satisfactory results in terms of quantitative yields. Samples of these extracts are also subjected to biological tests in order to evaluate their antioxidant and enzyme inhibition activities.

In a recent untargeted clinical lipidomics study of platelets of coronary artery disease (CAD) patients, medium-chain phosphatidylcholines (MCPCs) with C8 and C10 fatty acyl residues were found significantly upregulated in the patient group with acute coronary syndrome (ACS) as compared to chronic coronary syndrome (CCS) and healthy controls. To support this finding, this work presents the development and optimization of a targeted UHPLC-QTrap-MS/MS method with multiple reaction monitoring acquisition for the quantitative analysis of MCPCs (PC 10:0/8:0, PC 16:0/8:0, PC 10:0/20:4 and PC 10:0/10:0) in platelets for biomarker validation. A systematic optimization of chromatographic and mass spectrometric parameters was performed. A charged surface hybrid CSH C18 (1.7 µm, 130 Å) column and fine-tuned gradient elution with 2-propanol/acetonitrile and ammonium acetate as additive to the mobile phase was employed in the final method in ESI negative mode. Four selected PC standards (PC 6:0/6:0, PC 8:0/8:0, PC 10:0/10:0 and PC 12:0/12:0), which cover well the carbon and retention rime range of the target analytes, were used for the optimization process and calibration. Quantification was based on matrix-matched calibration with these four selected commercially available MCPC standards as surrogate calibrants and PC 6:0/6:0(d22) as internal standard. Furthermore, an organic solvent and fatty acyl carbon number-corrected response factor approach gave also accuracies within acceptance limits of bioanalytical validation guidelines and has more generic applicability. Compared to the previous untargeted RPLC-ESI-QTOF-MS/MS method, the optimized targeted UHPLC-QTrap-MS/MS assay showed increased sensitivity and selectivity for the detection of medium-chain PCs in platelet samples of CAD (LOQs in the range of 0.5–5 nmol/L). The method performance parameters indicated its suitability for a future biomarker validation study of MCPCs in platelets.

The chemoselective probe technique combines the benefits of chemical derivatization and solid-phase extraction, allowing for simultaneous enhancement of analyte ionization efficiency, reduction of matrix interference, and improvement in chromatographic separation. This innovative technique holds great promise for applications in metabolomics research, metabolic tracking, and natural product isolation and purification. This review provides a comprehensive overview of the advancements in chemoselective probes from 2007 to 2024, focusing on the progress in probe design, particularly cleavable linkers. Additionally, it discusses the application of chemoselective probes in LC-MS analysis of small-molecular-weight compounds.

The main trends in the use of liposomes or lipid aggregates as pseudostationary phases in capillary electrokinetic chromatography (EKC) over the past 15 years are reviewed. Due to the ability of liposomes to mimic cell membranes, they have found wide applications in analytical chemistry and especially in the field of biomedical sciences. Various liposomes, lipid aggregates, and liposomal formulations have been adopted as background electrolytes in EKC and ultraviolet detection is by far the most commonly used detection mode. The possibility to vary the type of lipids and their content in the lipid aggregates has increasingly expanded the usage of liposome EKC for solving specific tasks. The presented data shows that there is great potential of liposome EKC in investigations of interactions between lipid membranes and compounds and the applications are typically related to biomedical and pharmaceutical issues, but not limited to these.

Pharmacotoxicology is one of the fields that in recent years is growing exponentially, further reaffirming its proven usefulness in the field of forensic sciences. An interesting goal in this field is to identify and quantify the cause of death. This review paper aims to represent a review of the literature in order to evaluate the state of the art regarding the research in the pharmacotoxicology field in cases of Sudden Cardiac Death (SCD), a frequent problem on several occasions, which can be derived from the use of fatal substances or in such concentrations causing sudden death.In this overview, the most frequently observed biomarkers for SCD were found to be ethanol, illicit drugs, antidepressants, and some common compounds like caffeine and Trenbolone. Concurrently, the most applied instrument configurations is represented by hyphenated liquid (or gas) chromatographic tools coupled with mass spectrometry (LC-MS or GC–MS) in order to reach the high accuracy and confidence levels in the confirmatory analyses, preceded by common sample preparation technique as solid-liquid extraction or liquid-liquid extraction. It was interesting to understand the approaches by which researchers have approached the topic, because on the one hand there are those who have been interested in the comparison between matrices (conventional and not) and on the other hand, who has researched metabolites in order to be able to trace the intake or not of a substance.In particular, this work want to highlight and evaluate, from a medical-legal point of view, which are the main biomarkers and physiological markers of forensic interest and the methods, and instrumental procedures most frequently used for their evaluation. The paper is organized considering the analytical methods divided by types of drugs/substances.

An automated identification and quantification system using gas chromatography-mass spectrometry (AIQS-GC) can screening analysis of approximately 1000 chemical substances. It has been adopted as a Japanese Industrial Standards (JIS) and a provisional analytical manual by the Ministry of the Environment. To address potential helium carrier gas shortages, alternative gases like hydrogen and nitrogen are being considered. Hydrogen, in particular, shows minimal spectral changes when using a dedicated ion source. In this study, hydrogen and dedicated ion sources were applied to the AIQS-GC, with measurement conditions set to match helium's performance. The AIQS-GC met performance criteria for 20 out of 21 substances using hydrogen and a dedicated ion source. However, the sensitivity for all 21 substances decreased, suggesting that correction of quantitative values might be necessary if there is a significant difference in sensitivity reduction between the measured substances and internal standards. The AIQS-GC uses target ion and qualifier ion abundance (QT) ratio for substance identification, but low peak intensities caused some QT ratios, like that of captafol, to exceed standard values, requiring manual spectrum checks for accurate identification. Despite these issues, the AIQS-GC with hydrogen carrier gas and a dedicated ion source offers a new screening method for hazardous substances during helium shortages.

The Abraham's solvation parameter model is an important tool to model and predict distribution properties of compounds in numerous partitioning systems in chemistry, environmental chemistry, medicine, and biology. The evaluation of the distribution properties in extractables and leachables (E&L) studies in pharmaceutical and medical device industries is another major application of this model. This tutorial is aimed at illustrating the applications of the model in E&L studies. Specific examples of the application illustrated in this tutorial include: (a) establishment of equivalent or similar solvents; (b) determination of polarity of solvents, biological tissues, and materials; (c) development of drug product simulating solvents; (d) understanding solvent extraction power for a material; (e) selection of solvent and standards in pretreatment of extraction samples; and (f) chromatography retention prediction for E&L.

Solid-phase analytical derivatization is a versatile sample preparation technique that enhances analysis accuracy, efficiency, reproducibility, and sensitivity. The technique combines the advantages of analytical derivatization and solid-phase extraction, providing a versatile approach for analysing analytes with various functional groups in complex matrices. Analytical derivatization is a technique used for functional group analysis that involves modifying the structure of an analyte to enhance sensitivity and specificity. Solid-phase analytical derivatization is a one-pot procedure that combines analytical derivatization and extraction. In the presence of acids, it can derivatize phenols, carboxylic acids, and other analytes. Furthermore, solid-phase analytical derivatization increases the reaction rate of carbonyl compounds, making it easier to extract aldehydes and ketones rapidly. This technique utilises electrophoresis, chromophores, fluorophores, and functional groups for detection and extraction. It initially began as a batch procedure but has now developed into an automated, microextraction, and derivatization method. Solid-phase analytical derivatization is highly efficient due to the significant excess of the derivatizing reagent relative to the analyte, along with the pre-impregnation of derivatizing reagents, which can speed up the process compared to traditional solution-based derivatization. This tutorial aims to provide detailed insights into the practical aspects of implementing solid-phase analytical derivatization in analytical method development and discuss the prospects and future trends.

The adsorption dynamics of the LL- and DD-enantiomers of Leu-Leu and Gly-Gly on a Chirobiotic V column packed with a CSP bearing glycopeptide antibiotic vancomycin was studied and compared with the adsorption dynamics of the same dipeptides on a Chirobiotic R column packed with a CSP with bonded antibiotic ristocetin A. The column efficiencies were essentially different. The heights equivalent to a theoretical plate (HETP) on Chirobiotic R were 2-4 times larger than on Chirobiotic V, and the shape of van Deemter plots, strongly convex-upwards on the former column, demonstrated minor (Leu-Leu) or lacking (Gly-Gly) convexity on the latter column. This difference is attributed to differences in the binding kinetics of dipeptides to the antibiotics, fast for vancomycin and slow for ristocetin A. Since the kinetic C term of the van Deemter equation cannot explain such a large discrepancy in HETP for the same analyte on two columns, and since the A and B terms for the Chirobiotic R column were essentially larger than for the Chirobiotic V column, it is suggested that binding kinetics influences eddy and longitudinal diffusion processes associated with those terms. It is also hypothesized that unusually high values of van Deemter B coefficients occasionally found in chiral chromatography are not experimental artifacts but the manifestation of coupling the effects of slow adsorption kinetics and longitudinal diffusion.

Headspace solid-phase microextraction (HSSPME) of volatile organic compounds (VOCs) from aqueous samples under vacuum conditions (Vac-HSSPME) allows increasing extraction rates and decreasing detection limits compared to HSSPME under atmospheric pressure. The positive effect of the vacuum on HSSPME of an analyte can be quickly estimated using its Henry's law constant (HLC). According to the two-layer model of evaporation, substantial positive effect of the vacuum can be expected for analytes with HLC lower than 1.6·10−4 atm m3 mol−1 (0.0065 at 25 °C), but the model does not consider possible effects of other important extraction parameters. This research was aimed at the evaluation of the possible effect of vacuum on the equilibration time and extracted amounts of analytes with various HLC and fiber coating-headspace distribution constants (Kfh) using the computational model recently developed in COMSOL Multiphysics® software. It has been proven that HSSPME under vacuum provides faster equilibration of VOCs with all studied Kfh and HLC. The largest vacuum effect on the extracted analyte amount was 3.9–4.0 times at logKfh = 6 and HLC = 10−6–10−3. The substantial (≥1.5 times) vacuum impact should not be expected for analytes with logKfh < 5 for 15-min extraction and logKfh < 5.5 for 30-min extraction. The vacuum impact should be more pronounced when using fiber coatings with a stronger affinity to analytes. The obtained results will be useful for the development of new methods based on Vac-HSSPME and evaluation whether HSSPME is reasonable to conduct under vacuum conditions for faster equilibration and/or lower detection limits.

Miniaturized LC, encompassing capillary and nanoLC, presents significant analytical advantages in enhanced chromatographic performance and detectability and delivers considerable environmental and economic benefits. Despite these advantages, its utilization has primarily remained confined to omics sciences, with limited adoption in the routine targeted analysis of small molecules despite the lack of practical limitations. Initially, miniaturized LC encountered challenges related to scale reduction, necessitating the handling of minute sample volumes and lower flow rates. However, these obstacles have largely been overcome, with various instrumental platforms, columns, and consumables now available for efficient separations at the miniaturized scale. Moreover, the miniaturization of instruments facilitated by capillary and nanoLC has given rise to various portable LC platforms for in-situ analysis in recent years. Currently, researchers are exploring their applicability for diverse analytical purposes. However, the transition from conventional HPLC to miniaturized LC has been slow, and the technical factors limiting this shift still need to be clarified. Limited access to technology is among the primary obstacles identified, as transitioning may entail replacing conventional instruments with miniaturized versions.Additionally, a lack of proper training and background to handle small volumes and flow rates has hindered the widespread adoption of capillary and nano-LC. Notably, expertise in HPLC only sometimes translates to proficiency at the miniaturized scale. Through this review, we aim to facilitate the dissemination of miniaturized LC by providing readers with a comprehensive overview of its current state, showcasing recent advancements, and highlighting remarkable applications beyond omics sciences.

Promethazine (PMZ) is metabolized in the liver giving rise to chiral metabolites, including promethazine sulfoxide (PMZSO) and desmonomethyl promethazine (DMPMZ). Other metabolites, such as dioxopromethazine (DOPMZ), hydroxy promethazine (PMZOH), N-desmethyl-promethazine sulfoxide, and promethazine N-oxide (PMZNO) can also be formed, but information about them is limited. In this work, the enantiomeric metabolic profile of PMZ in ultra-pool human liver microsomes (HLM) was evaluated. For that, a novel enantioselective analytical method, by liquid chromatography coupled with high-resolution mass spectrometry was established and employed to monitor the enantiomers of PMZ and the formation of its main metabolites PMZSO and DMPMZ in two-hours assay with HLM. The enantioseparation optimized conditions were achieved with two immobilized carbamate amylose-based (3‑chloro-5-methylphenylcarbamate) columns: Lux® 3 µm i-Amylose-3 and Chiralpak® IG-U 1.6 µm. The optimized mobile phase for enantioseparation used buffer and ethanol, a green organic solvent, in a low flow rate. The sample preparation was based only in liquid-liquid extraction. (R)-PMZ consistently exhibited higher concentrations than (S)-PMZ, indicating less extension in metabolization. Regarding the metabolites, PMZSO exhibited higher concentrations compared to DMPMZ. A higher concentration for (S)-PMZSO was found when compared to the (R)-PMZSO and (R)-DMPMZ showing higher concentration compared to (S)-DMPMZ, indicating enantioselectivity in the metabolization process. The metabolites, PMZOH or PMZNO and DOPMZ were also identified. The second enantiomer of DOPMZ also showed a higher proportion than the first eluted enantiomer. These results demonstrated enantioselectivity of liver metabolism of PMZ, as well as confirmed PMZOH, PMZNO, and DOPMZ metabolites formation.

Pancreatic hormones are produced in the islets of Langerhans in the pancreas and are secreted to regulate blood sugar levels. Key pancreatic hormones are insulin, glucagon, and somatostatin. The measurement of these peptides/small proteins is essential in the study of the endocrine system, regulating diseases such as diabetes mellitus, but also in doping control and forensics. In this review, we focus on approaches for measuring pancreatic hormones using liquid chromatography-mass spectrometry (LC–MS). A rich variety of LC–MS approaches are used, including variations in LC column dimensions and chemistry, factors that are crucial regarding sensitivity, selectivity, robustness, and speed. In addition, several sample preparation methods are used (protein precipitation, immunopurification, etc.), for the analysis of matrices such as blood, urine, and cell culture medium. There are also several variants for mass spectrometric analysis, both targeted and non-targeted, using both lower and high-resolution instruments. LC–MS allows for sensitive, multi-hormone measurements, confidently distinguishing between hormones and their analogs, metabolites, and degradation products. The speed of analysis can be pushed down to a few minutes, with methods being validated and clinically applied. The review focuses on papers that have been published between 2019 and 2024.

Allantoin represents a compound widely employed in pharmaceutical and cosmetic fields. Its safety has been acknowledged by regulatory bodies such as the US Food and Drug Administration, the European Commission for Cosmetics and Consumer and Health and European Directorate for the Quality of Medicines & HealthCare. This justifies its wide use in dermatological/cosmetic formulations and allows their safe use.Allantoin possesses an asymmetric carbon atom, resulting in two enantiomers, with the (S)-enantiomer predominating in plants, although racemization may potentially occur during manufacturing processes. Notably, literature currently lacks enantioselective LC methods for allantoin analysis.In this study, two zwitterionic Cinchona alkaloid-based chiral stationary phases (CSPs), commercially known as CHIRALPAK® ZWIX(+) (CSP1) and CHIRALPAK® ZWIX(-) (CSP2), were utilized for the enantioseparation of allantoin under polar-ionic conditions. By employing a mobile phase consisting of acetonitrile/methanol/water/acetic acid (96:2:2:0.1, v/v/v/v), nearly complete baseline separation (with α=1.08) of allantoin enantiomers was achieved in less than 15 min with both CSPs. Due to the “pseudo-enantiomeric” nature of the two chiral selectors (quinine-based in CSP1 and quinidine-based in CSP2), an inversion of the enantiomer elution order was observed with the two CSPs under identical experimental conditions. Remarkably, this represents a rare instance where these CSPs demonstrate the ability to enantioseparate a non-ionic, non-ionizable species.The application of a molecular dynamics in silico protocol proved useful in elucidating the retention mechanism in depth, casting light on the central role of the H-bond formation and the involvement of the anionic moiety of the CSP 1.

Lactofen is a chiral restricted-use herbicide, classified as toxicity class I by the Environmental Protection Agency (EPA), commonly used to control broadleaved weeds. While the observed herbicidal activity mostly derives from the (S)-(+)-enantiomer, formulations have been manufactured as a mixture of both enantiomers. In this work, we present a quantitative method for the enantiomeric determination of lactofen in commercial formulations based on the development of a second-order calibration to assist the selectivity of chiral separation under reversed-phase liquid chromatographic mode coupled to diode array detection. Chromatographic conditions were aimed to minimize analysis time and solvent consumption. This approach is feasible because second-order calibration allows for the quantification of overlapping bands and analytes in the presence of interferences. Chromatographic-spectral matrices were processed by unfolded partial least-squares coupled to residual bilinearization. The proposed methodology was evaluated through validation samples, achieving relative errors of predictions of 2–4 %. Finally, commercial formulations were subjected to minimal sample treatment and analyzed, and figures of merit for real samples were determined. The described methodology results suitable for the determination of enantiomeric purity and quality control in commercial lactofen formulations.

A novel design and set up of paper chromatography in the form of radial serpentine arms laying horizontally is proposed. The consumption of mobile phase is reduced to be 1 mL or less as compared to the tens of mL typically used in the conventional set ups for ascending paper chromatography, without any change in the order of the separated components. Greenness measurement based on the ChlorTox value is approximately 25, when comparing to a conventional system that consumes 25 mL of mobile phase. A digital image of the chemical separation makes data analysis more feasible as the image can be kept, and hence, extending the time for data analysis. The Retention Factor (Rf) value from a serpentine shaped stationary phase can be calculated based on measurement of linear distances of the solvent front and those travelled by each component, and converting them to arclengths using the mathematical equation of a catenary wave that produces that particular design. Proof of concept is demonstrated by the separation of food dyes using a two solvent system, where a nonvolatile salt solution is followed by a volatile organic solvent mixture of alcohols and base. Relationships between concentration, color intensity (RGB values), and zone arclength are also demonstrated which indicate possibility of quantitative study on the serpentine design using digital image analysis.

An environmentally friendly and simple dispersive liquid–liquid microextraction method based on a hydrophobic natural deep eutectic solvent (NADES) was developed for the simultaneous preconcentration of Cu and Ni from water samples. The NADES composed of a 1:1 molar ratio of menthol and decanoic acid, presents hydrophobic characteristics and allows to simultaneously extract both analytes avoiding the addition of ligands or emulsifier agents. The extraction was performed in 1.0 min using 0.500 mL of NADES and a sample volume up to 25.0 mL in 0.5 M ammonium chloride-ammonia buffer solution at pH 8.2. The content of Ni and Cu in the NADES phase was determined using Flame Atomic Absorption Spectroscopy. Under optimal conditions, limits of detection of 1.9 µg L−1 for Cu and 4.6 µg L−1 for Ni were obtained, with precision (expressed as RSD% value) better than 5 % for both metals (n = 3). The method was applied to extract and determine Cu and Ni in water samples with different characteristics: tap water, bottled water, river water, dam water, and seawater. The recoveries for spiked water samples ranged between 97 and 110 % for Cu and 92–98 % for Ni, demonstrating the suitability of the method. The environmental impact of the method was assessed using the AGREE, AGREEprep, and ChlorTox metric tools, resulting in scores of 0.58, 0.61, and 0.48 g, respectively.

Nano-scale separation techniques (NSTs) offer significant advantages in relation to drug analysis in a wide range of samples. NSTs, including low flow rate LC systems or capillary or chip based electrophoresis/electrochromatography systems, have become the primary tool for advanced drug analysis, and indispensable technology for sensitive and selective drug analysis. In recent decades, significant advances have been achieved using NSTs for drug analysis. In this review, sample preparation strategies, new advances and applications in NSTs and the contribution toward forensic science applications were reported. In addition, some recent and selected applications with or without mass spectrometry (e.g., low resolution/high resolution -MS) are summarized.

The use of innumerable chemical compounds in food production to enhance agricultural quality and yield has raised significant global concerns regarding food safety. To address these concerns, miniaturized solid sample preparation techniques have emerged as an appealing strategy for analyzing chemical residues in complex samples, notably those found in food matrices. The efficacy of these miniaturized solid extraction procedures hinges largely on the choice of the sorbent phase. Molecularly imprinted polymers (MIPs) have been introduced as highly selective and versatile sorbent phases for a wide range of miniaturized solid techniques. Their remarkable selectivity is attributed to the creation of distinct cavities during the synthesis process, which subsequently accommodate the target analyte when the sample is applied. This unique characteristic empowers MIP polymers to exhibit exceptional specificity toward the desired analyte. The use of MIPs as sorbent phases in miniaturized sample preparation methods has shown great potential to increase the analytical performance of residue evaluation in food matrices. Therefore, here we present a comprehensive overview of the current landscape of miniaturized solid sample techniques employing MIPs as sorbent phases for the assessment of residues in food samples. Moreover, this review is primarily on recent reports concerning the application of MIPs in solid-phase microextraction (SPME), in-tube SPME, microextraction by packed sorbent (MEPS), disposable pipette extraction (DPX), solid-phase extraction in pipette tip (SPE-PT) and stir bar sorptive extraction (SBSE). Lastly, we will bring some future topics concerning the use of MIPs in miniaturized sample preparation methods for food analysis in order to bring some new avenues for enhancing food products' safety and quality assessment.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/policies/article-withdrawal).This article has been retracted at the request of the authors. The manuscript was submitted before a final round of revision by the authors. As a result, not all authors had the opportunity to review the final manuscript and approve it, and there are a series of errors that should have been rectified prior to publication. These are: • Some figures do not contain the reference to the original source (permissions was obtained to reproduce the figures but this has not been properly represented). • Some sentences in the Introduction were taken verbatim from other sources while no reference was included to the original source. • The authors need to further supplement some data and discussion to improve the paper.The authors apologise for this error.

Nonsteroidal anti-inflammatory drugs (NSAIDs) are a class of drugs with antipyretic, analgesic, and anti-inflammatory effects widely used worldwide. This study aimed at developing an environmentally friendly and high-throughput sample preparation method for the determination of six NSAIDs in urine samples followed by high-performance liquid chromatography coupled to diode-array detection (HPLC-DAD). The experimental workflow consisted of hollow-fiber microporous membrane liquid-liquid extraction (HF-MMLLE) using a supramolecular solvent immobilized into the porous of polypropylene hollow membranes (1 cm length). These membranes were attached to a 96-well plate system to permit multiple extractions simultaneously. Under the optimized conditions, limits of detection (LODs) and limits of quantification (LOQs) ranged from 6.06 to 30.3 µg/L and from 20 to 100 µg/L, respectively. The linear ranges varied from 20 to 1000 µg/L for indomethacin and diclofenac, from 50 to 1000 µg/L for ketoprofen and ibuprofen, and from 100 to 1000 µg/L for naproxen and fenoprofen. The coefficients of determination (R²) ranged from 0.9735 to 0.9997. Intraday precision ranged from 6.13 to 20.11 %, interday precision varied from 2.87 to 20.72 %, and accuracy ranged from 92.49 to 126.89 %. Moreover, the recently proposed Sample Preparation Metric of Sustainability (SPMS) was employed to evaluate the greenness of the sample preparation technique resulting in a score of 8.0, which is highly satisfactory according to the concepts of green analytical chemistry.

In this comparative study, four green evaluation tools, blue applicability grade index (BAGI), Analytical GREEnness (AGREE), Green Analytical Procedure Index (GAPI), and Analytical Eco-Scale were evaluated to assess 16 selected analytical methods including fiber-solid phase microextraction, stir bar sorptive extraction, and thin film microextraction joint to gas and liquid chromatographic as well as spectrofluorimetry techniques. The required parameters and data were extracted from the selected articles and calculations were performed based on the unique evaluation protocol of each tool. A uniform approach was applied in calculations and evaluations. A comparison of selected methods was done by determining the factors affecting greenness. High energy consumption, organic solvents, waste generation, analysis throughput, and the number of determined analytes, are among the crucial parameters that require improvement in the selected methods. The results show that using more than one evaluation tool in evaluating the greenness of analytical methods is very effective in obtaining synergistic results and increasing the understanding of the greenness of analytical methods.

A rapid and sensitive spectrofluorimetric method has been developed for the determination of perampanel in pharmaceutical preparations (assay method) and human plasma (bioanalytical method). The fluorescent product was measured at an excitation wavelength (λex) 294 nm and emission wavelength (λem) 430 nm. The assay method was validated as per the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use (ICH) Q2(R1) guidelines. For the assay method, the fluorescence intensity versus concentration plot was found to be linear over the concentration range 25–175 ng/mL.In case of bioanalytical method, for the extraction of drug from human plasma, a lucid liquid-liquid extraction method using ethyl acetate was employed. The bioanalytical method was validated according to the United States Food and Drug Administration (USFDA) guidelines and it was applied for the quantification of the drug in human plasma with reasonable accuracy and precision. For the bioanalytical method, the fluorescence intensity versus concentration plot was found to be linear over the concentration range 5–150 ng/mL. The impact of endogenous compounds of the plasma matrix on drug fluorescence was also assessed. To assess the greenness of the developed method, Green Analytical Procedure Index (GAPI) and Analytical GREEnness (AGREE) tools were applied and it was inferred that the developed method adheres closely to the principles of green analytical chemistry.

With a global focus on sustainability and environmental impact, scientists have been prompted to adopt eco-friendly practices. Green analytical chemistry (GAC) promotes energy-efficient equipment, reduction of toxic chemicals, and sustainable waste management. Therefore, evaluating and minimizing the environmental impact of analytical procedures is crucial. Given the pivotal role of mass spectrometry and related techniques in analytical chemistry and other applications, there is a growing need, a necessity, to incorporate and expand green metrics in the field. Even though various metrics are currently being developed and used to assess the sustainability of analytical methods, only a few studies are found in the literature that evaluate mass spectrometry analytical strategies, focusing mainly on Analytical Eco-Scale (AES), Green Analytical Procedure Index (GAPI), and Analytical Greenness Metric (AGREE). Thus, this review explores the relevance of green metrics applied to analytical methods linked to mass spectrometry, discussing their implications and challenges. The potential use of GAC metrics for alternative mass spectrometry approaches, including miniaturized instruments and emerging ionization techniques, is also evaluated.

High Performance Liquid Chromatography (HPLC) has been the most used analytical technique for analyzing phenolic compounds and coumarins in aged sugarcane spirit samples. It requires a significant amount of organic solvents, often toxic, as the mobile phase. The use of green bio-based solvents is a good alternative in the implementing more eco-friendly methods. Therefore, this work aims to propose a greener chromatographic method for the determination of phenolic compounds and coumarins in sugarcane spirit samples aged in different woods, using bio-based organic solvents (ethanol and acetic acid) in HPLC system with diode array and fluorescence detectors. Different metric tools (AGREE, ComplexMoGAPI, BAGI and Analytical Eco-scale) were used to evaluate the greenness of the analytical method. The proposed method was rigorously validated: linearity (R2 ≥ 0.9901); LOD (0.05 to 0.55 mg l-1); LOQ (0.25 to 5.00 mg l-1); precision (0.13 % ≤ RSD ≤ 18.6 %). The concentrations of total phenolic compounds and coumarins were up to 7.22 mg l-1. The sugarcane spirit aged in umburana presented the highest concentration of total phenolic compounds and coumarins with emphasis on trans-cinnamic acid (4.74 ± 0.01 mg l-1) and catechin (1.22 ± 0.02 mg l-1). All samples presented coumarin concentrations (

The world is facing challenges in terms of environmental sustainability and rising costs. In this context, miniaturized equipment such as microfluidic devices can be used to manipulate small volumes of fluids in micrometer-sized channels incorporating multiple components such as pumps, valves and mixers. Due to their high flexibility, these devices can provide sustainable alternatives to traditional platforms. The present study focuses on the design of a user-friendly and reliable microfluidic capillary electrophoresis chip for pharmaceutical applications. To meet pharmaceutical requirements in terms of quantification performance and overcome the injection variability usually observed with such microfluidic systems, a reliable and reproducible design for hydrodynamic injection using passive valves has been developed. It has been successfully used for synthetic cathinone analysis.

Tinidazole (TIN), an antimicrobial, is commonly prescribed for the treatment of giardiasis, trichomoniasis and amoeba infections. It presents a monograph in official compendiums by titration and the literature presents some analytical methods, which mostly use methanol and acetonitrile, options opposed to the principles of Green Analytical Chemistry (GAC) and the current trend in chemical-pharmaceutical analyses. Among the principles of GAC, the generation of less waste, the choice of less toxic reagents and solvents, the use of fewer materials, the assessment of costs involved, faster steps and processes are included. In this context, the objective was to develop and validate an eco-friendly method by spectrophotometry in ultraviolet region (UV) for quantitative evaluation of TIN in tablets. Additionally, the proposed method was evaluated for greenness by the Eco-Scale Assessment (ESA). Purified water and ethanol (90:10, v/v) as a diluent, quartz cubette at 318 nm were used. The method was linear in the range of 7–22 µg/mL (0.9999), precise (RSD < 5 %), selective through sample adjuvants and by the forced degradation, exact (100.47 %) and robust against changes in reading wavelength. As for the greenness of the method, it proved to be a green alternative to quantify TIN in tablets according to the ESA.

The presence of pharmaceuticals in water is a major problem worldwide. To alleviate this, this study produced carbon blends from avocado seeds and paper waste and activated them with hydrogen peroxide (H2O2), nitric acid (HNO3) and potassium permanganate (KMnO4). The effectiveness of the adsorbents was tested in removing ibuprofen (IBU) and paracetamol (PRC) from water. Characterization of the adsorbents by SEM, BET, FTIR and TGA revealed that the morphology was porous, with a large surface area and several functional groups bound to the surface. The concentration effect experiments showed that the uptake of IBU and PRC increased with an increasing initial concentration and that these data were consistent with the Freundlich model. The contact time effect showed that the uptake of PRC was rapid in the initial phase for all the adsorbents. However, the rate gradually slowed down and equilibrium was reached after 40 min for BCMN, 60 min for BCMH and BCMP and 120 min for BCM. IBU, on the other hand, showed that equilibrium was reached after 30 min for BCMN, BCMH and BCMP and after 120 min for BCM. These data complemented the PSOM. The model is based on chemisorption, where electrons are transferred and shared, and hydrogen bonding and π-π interactions. The △Ho value confirms that the sorption of IBU and PRC was endothermic. The △So was positive, indicating greater freedom at the solution interface during uptake.

A simple green method for the quantification of sweet orange and lavender essential oils (EOs) content in blends was developed using synchronous fluorescence of the first derivative spectra and sample preparation by surfactant-free microemulsions (SFMEs). Excitation and emission wavelengths pairs (λex/λem) were determined for both EOs (at 336/436 nm for sweet orange and at 330/388 nm for lavender). Optimization was conducted to establish the condition to prepare the SFMEs systems: 50 μL of oily phase containing EO diluted in octan-1-ol (1:4, v/v), 2.0 mL of water and propan-1-ol up to 5.0 mL final volume. Different proportions of EO in the oily phase were evaluated for analytical curves construction. Synchronous fluorescence measurements were performed and the acquired data were corrected by inner filter effect. Considering the first derivative of the synchronous scanning, data were extracted at 316.8 nm (Δλ = 100 nm) and 352.0 nm (Δλ = 58 nm) for sweet orange and lavender EOs, respectively, with correlation coefficients above 0.99. Limits of quantification of 7.97 μg mL−1 and 65.80 μg mL−1 were obtained indicating that 0.46% of sweet orange and 3.69% of lavender EOs can be quantified in mixtures. Simulated blends (25:75%, 50:50% and 75:25%, volume proportions) were also evaluated with recoveries of 71.5 – 128.9% and coefficient of variation between 3.1% – 11.6%. Additionally, the method's greenness was evaluated through three green metrics (Analytical Eco-Scale, GAPI, and AGREE) with consistent results.

As the potential risks on human and aquatic animal exposed to the glucocorticoids in environment, it is essential to detect anti-epidemic pharmaceutical in real water samples. In this work, a core-shell shape, magnetic suspension particle sorbents of Fe3O4@oleic acid@polydopamine (Fe3O4@OA@PDA) were synthesized for magnetic dispersive solid phase microextraction (MDSPME), which possessed considerable dispersibility in water samples and extracted three glucocorticoids through hydrogen bonding with high detection sensitivity. The adsorption process of MDSPME was investigated by thermodynamic and kinetic theory, which demonstrated that the kinetic processes of adsorption were in accordance with the quasi second order kinetic model, and the adsorption isotherm was in accordance with the Freundich model. Combined with high performance liquid chromatography-Ultraviolet spectrophotometer detector, the proposed method had a linear range of 5–200 μg/L with an ultra-low detection limit down to 0.5–1.1 μg/L. The Green Analytical Greenness Metric (AGREE) software was employed to evaluate the greenness of the analytical method. This work presented an effective strategy for creating ultrasensitive and cost-effective probe for detection in anti-epidemic drugs.