Analytica, Volume 6, Issue 3 (September 2025) – 16 articles

The synthesis of new molecularly imprinted polyurethane foam (MIPUF) using an herbicide of atrazine (Atz) as a template for selective solid-phase extraction for Atz was proposed for the first time. The MIPUF was simply synthesized under mild conditions, without requiring an oxygen-free environment. Some household apparatuses were adapted for the preparation, such as a plastic cup and bamboo chopstick. The ready-to-use MIPUF minicolumns could be obtained within 4 h with more than 10 minicolumns. The proposed material was characterized using FT-IR and SEM. The MIPUF minicolumn was used in a solid-phase extraction. The eluate of free Atz was determined using the fluorescence technique without further derivatization at 343 nm. The MIPUF offered a good sensitivity and selectivity over non-molecularly imprinted polyurethane foam (NIPUF), enhancing fluorescence intensity by 15.6 times. The linear equation and linear range for Atz detection at y = 87.25x + 311.58, R² = 0.9887 and 0.2–1.0 µM were obtained. The LOD and LOQ were 35 and 110 nM, respectively. The MIPUF revealed a more selective Atz than some potential pesticides. The ready-to-use minicolumn has been used for sample preparation and Atz assays in surface water in orchards and river water samples with recoveries (%) at 90–110%. Full article

Pesticide residue violations continue to challenge the compliance of Turkish horticultural exports with European Union food safety regulations. This study examined 1138 RASFF alerts (1660 detections) issued between 2020 and 2025 using statistical enrichment, time-series modeling, and unsupervised machine learning. Pepper was the most frequently rejected commodity, with strong enrichments of formetanate (71-fold), pyridaben (35-fold), and acetamiprid (5-fold). Notably, chlorpyrifos and chlorpyrifos-methyl remained among the most commonly detected residues despite EU bans, suggesting continued use of stockpiled or illicit products and prolonged environmental persistence. Rejections peaked during winter and spring, particularly for citrus and greenhouse-grown crops. Clustering and association rule mining revealed modular commodity–pesticide structures and recurrent co-detection patterns. Anomaly detection further identified discrete periods of irregular contamination. Overall, the results indicate that violations are seasonally patterned and structurally embedded. Targeted monitoring aligned with crop calendars and stricter enforcement of legacy pesticide phase-outs could significantly improve compliance and reduce export rejections. Full article

Fundamental research, exploration, extraction, and metallurgical studies of rare earth elements (REEs) require the use of analytical techniques. Recently, emerging developments of analytical instrumentation for REEs have taken place, with some of them having shrunk in size, becoming handheld devices. The Flame and Graphite Furnace AAS, ICP-OES, and MP-AES are standard laboratory techniques used for the analysis of REEs. ICP-MS, ICP-MS/MS, ICP-TOF-MS, HR-ICP-MS, MH-ICP-MS, and MC-ICP-MS are popular techniques for REE analysis thanks to their ultrahigh sensitivity, minimal interference effects, and broad applicability. The INAA, XRF, LIBS, and LA-based ICP-MS techniques are widely employed for the direct analysis of solid samples. The TIMS, SIMS, and SHRIMP are common techniques used for dating isotopic REE deposits. The portable XRF, LIBS, and Raman spectrometer devices can perform on-the-spot in situ analysis, which may help make speedy decisions in the exploration study of REEs. Currently, hyperspectral remote sensing platforms, such as handheld, drone, and satellite-based devices, are preferred for the exploration of REEs due to their cost-effectiveness, which enables the coverage of large areas in a limited amount of time. The use of microanalytical sensors installed on remotely operated vehicles has been successfully applied in analyzing rich REE-bearing deposits in the deep sea. In general, this review provides in-depth information on all essential aspects, from analytical instruments to cutting-edge developments in the analysis of REE-bearing resources. Full article

Halloumi cheese, a traditional Cypriot dairy product with Protected Designation of Origin (PDO) status, is renowned for its unique texture and high melting point. PDO certification is crucial for Halloumi cheese as it ensures the product’s authenticity, protects its traditional production methods and geographical origin, and safeguards consumers and producers against fraud and mislabeling. However, concerns over adulteration, particularly through the addition of skim milk powder, pose challenges to its authenticity and quality control. This study is the first to analyze Halloumi cheese using Brunauer–Emmett–Teller (BET) analysis and Fourier Transform Infrared (FTIR) spectroscopy, providing a novel approach to assessing its composition and authenticity. Furthermore, it marks the first time Halloumi samples have been examined in the context of PDO certification. Alongside PDO-certified Halloumi, two additional sample sets were produced following PDO specifications for moisture, fat, and salt content, with the controlled incorporation of skim milk powder as an adulterant at concentrations of 1% and 5%. Principal component analysis (PCA) was employed to visualize and interpret the spectral data, revealing promising results. Chemometric analysis showed that the specific surface area from BET measurements and the FTIR spectral subregion between 1650 and 1100 cm⁻¹ were key factors, and they were retained for model construction. These findings could play a crucial role in establishing official food fraud detection methodologies, particularly for the Cyprus and EU markets. While this study serves as an initial investigation, additional samples will be tested in future studies to validate these preliminary results and to assess the potential of applying these techniques in real-world food fraud detection scenarios. Full article

The contamination of food and beverages with heavy metals, such as Cd, presents significant health risks, underscoring the need for reliable and sensitive analytical methods. This study introduces the development of a rapid, cost-effective, and environmentally friendly method for Cd determination in cachaça, a traditional Brazilian sugarcane spirit. Magnetic nanoparticles (Fe₃O₄) functionalized with tetraethyl orthosilicate are synthesized and employed as adsorbents in a dispersive magnetic solid-phase extraction procedure. The extracted Cd is quantified using flame atomic absorption spectrometry. A full factorial experimental design is used to optimize key parameters, including the sorbent mass, adsorption time, desorption time, and acid concentration. The method demonstrates excellent analytical performance, with a linear calibration range (R² = 0.99), detection limit of 0.0046 mg L⁻¹, and quantification limit of 0.0200 mg L⁻¹. Moreover, validation results show high precision (coefficient of variation < 9.10%) and accuracy (recovery rates between 92.00% and 120.00%). When analyzing commercial cachaça samples, cadmium was detected in all five specimens. Notably, in one sample the cadmium concentration exceeded Brazil’s maximum permissible limit of 0.0200 mg kg⁻¹, underscoring the importance of this work for ensuring food safety. The proposed method offers a sensitive, reproducible, and sustainable approach for analysis of potentially toxic trace metals in alcoholic beverages, reinforcing its potential for routine monitoring and regulatory compliance. Full article

Merlot red wines rank among the most distinguished varietals globally. This study aimed to characterize the phenolic compound profiles of Merlot wines and assess the influence of geographical origin and vintage on samples from two Albanian wine regions. Using liquid chromatography coupled with tandem mass spectrometry, a total of 31 phenolic compounds were identified and quantified. These were classified into hydroxybenzoic acids and flavan-3-ols (13 compounds), phenolic acids (9), flavonols (5), and stilbenoids (4). The total phenolic content ranged from 294 mg L⁻¹ in wines from the Mati–Mirdita region to 480 mg L⁻¹ in those from the Durrës–Kavaja region, demonstrating significant regional variation. Notably, the hydroxybenzoic acids and flavan-3-ols exhibited the most pronounced differences, with gallic acid concentrations varying from 123 mg L⁻¹ (Mati–Mirdita) to 170 mg L⁻¹ (Durrës–Kavaja). Both regions’ wines were rich in catechin, epicatechin, procyanidin derivatives, trans-caftaric acid, and ethyl gallate. However, procyanidins were found in higher concentrations in the Mati–Mirdita wines, while other phenolics were more abundant in Durrës–Kavaja samples. These findings underscore the influence of geographical and climatic factors on phenolic composition, offering a robust chemical fingerprinting approach for assessing wine authenticity and quality. Full article

The growing demand for functional bakery products necessitates research on the enrichment of wheat bread with pigweed (Amaranthus spp.) and purslane (Portulaca oleracea) flour. Although these plant-based raw materials offer nutritional and environmental benefits, their inclusion in wheat bread formulations poses challenges in the creation of formulations that may compromise the sensory and structural qualities of the final product. The main objective of this work is to systematically determine the optimal amounts of these alternative flour using multimodal bread characterization techniques that include physicochemical, organoleptic, geometric, and optical evaluations, supported by advanced data reduction techniques and regression models. A total of 70 features were analyzed and reduced to 22 for pigweed flour and 15 for purslane flour informative features. Predictive models (R² = 0.85 for pigweed flour, R² = 0.84 for purslane flour) were developed to optimize the inclusion of alternative flour, resulting in appropriate concentrations of 3.69% for pigweed flour and 7.13% for purslane flour. These formulations balance improved nutritional profiles with acceptable sensory and structural properties. The results obtained not only complement the potential of pigweed and purslane as sustainable functional raw materials but also demonstrate the efficacy of an automated, image-based approach to formulating recipes in food manufacturing. Full article

This study analyzes the nutritional quality and mycotoxin contamination of three key feed ingredients—corn, soybean meal (SBM), and sunflower meal (SFM)—imported into Morocco during the years 2019, 2020, and 2021. Samples were collected upon reception at the plant and analyzed in triplicate under standardized laboratory conditions. Chemical composition was evaluated using classical and NIR-based methods, while mycotoxin levels were assessed through ELISA and confirmed by HPLC. Corn samples from Argentina, Brazil, and Ukraine were assessed for their proximate composition and mycotoxin burden. While most nutritional parameters showed no significant differences between origins (p > 0.05), water activity (Aw) and digestible threonine content were significantly affected by origin (p < 0.01). Brazilian corn had the highest Aw (0.716), followed by Argentina (0.680), and Ukraine (0.662), a factor linked to its higher susceptibility to mold and mycotoxin development. Soybean meal from the U.S. and Argentina showed a general positive trend in favor of U.S. imports, with higher average crude protein (the CP content of American soybean meal was 46.912%, compared to 46.610% in Argentine soybean meal), fat, digestible lysine, and metabolizable energy. However, statistical differences were limited to water activity and moisture content (p < 0.05). American soybean meals are generally recognized for their consistent processing quality and superior amino acid digestibility. Sunflower meal, sourced exclusively from Ukraine, showed a steady improvement in crude protein (from 35.97% in 2019 to 36.99% in 2021) and metabolizable energy, alongside reduced crude fiber content, enhancing its nutritional value in poultry diets. The consistent use of Ukrainian SFM in Morocco reflects both supply stability and quality. Regarding mycotoxins, origin had a significant effect on several compounds. Argentine and Brazilian corn showed higher mean levels of fumonisins (1165.26 and 1019.52 ppb), ochratoxin A (2.26 and 3.02 ppb), and zearalenone (36.99 and 21.92 ppb) compared to Ukrainian corn, which consistently had the lowest levels across all major mycotoxins (e.g., fumonisins = 200 ppb; zearalenone = 4.90 ppb). Aflatoxin B1 levels remained constant at 0.2 ppb across all origins. These findings confirm the influence of geographic origin—particularly water activity—on mycotoxin risk in imported maize. Full article

Rapid and accurate assessment of nutritional quality, particularly crude protein content and essential nutrient concentrations, remains a major challenge in the food and feed industries. In this study, laser-induced breakdown spectroscopy (LIBS) was combined with advanced chemometric modeling to predict the levels of crude protein and key macro- and micronutrients (Ca, Mg, K, Na, Fe, Mn, P, Zn) in 61 barley forage samples composed of whole aerial plant parts ground prior to analysis. LIBS offers a compelling alternative to traditional analytical methods by enabling real-time analysis with minimal sample preparation. To minimize interference from atmospheric nitrogen, nitrogen spectral lines were excluded from the protein calibration model in favor of spectral lines from elements biochemically associated with proteins. We compared the performance of Partial Least Squares (PLSR) regression and Extreme Learning Machine (ELM) using fivefold cross-validation. ELM outperformed PLS in terms of prediction, achieving a coefficient of determination (R²) close to 1 and a ratio of performance to deviation (RPD) exceeding 2.5 for proteins and several nutrients. These results underscore the potential of LIBS-ELM integration as a robust, non-destructive, and in situ tool for rapid forage quality assessment, particularly in complex and heterogeneous plant matrices. Full article

The reaction of zirconium tetrachloride with 2-amino-1,4-benzenedicarboxylic acid in N,N-dimethylformamide with the addition of HCl leads to the formation of zirconium 2-amino-1,4-benzenedicarboxylate. Zirconium 2-amino-1,4-benzenedicarboxylate was characterized by elemental analysis, infrared spectrometry, X-ray diffraction, scanning electron microscopy, and volumetric nitrogen adsorption/desorption. The sample has a constant porosity with an average pore diameter of 7.97 nm and both microporous and mesoporous structure with a large surface area (820 m²/g) corresponding to the type IV adsorption. Zirconium 2-amino-1,4-benzenedicarboxylate was used for solid-phase extraction (SPE) of chlortetracycline hydrochloride from the aqueous solution. The obtained results confirmed the possibility of using the proposed analytical technique as a new, convenient approach to the extraction of chlortetracycline hydrochloride from industrial or other wastewaters, where such substance is contained in insignificant concentrations and its determination requires expensive and complex equipment. In the future, this method can be used not only for the effective removal of pollutants from industrial wastewater with subsequent regeneration of the sorbent, but also as a sample-preparation method for concentrating chlortetracycline hydrochloride from dilute solutions with its subsequent elution and analysis by available methods, for example, spectrophotometry, since the limit of detection is 0.06 mg/L. Experimental data are described by the isotherm of SPE (R² = 0.998–0.999) and show the ability of zirconium 2-amino-1,4-benzenedicarboxylate to extract up to 578 mg/g of sorbent at 5 °C under optimal conditions. Full article

Melamine (MEL) has broad applications and can be released to the aquatic environment from various sources, including industry, agriculture, traffic, and household articles. In addition, MEL derivatives ammeline (AMN), ammelide (AMD), and cyanuric acid (CYA) as well as potential precursors cyromazine (CYRO) and hexa(methoxymethyl)melamine (HMMM) are relevant related substances. However, occurrence and transformation in water resources has not yet been thoroughly investigated. Here, we developed a sensitive analytical method for quantification of these analytes by hydrophilic interaction liquid chromatography (HILIC) coupled to tandem mass spectrometry (MS/MS). Direct injection achieved limits of quantification (LOQs) of 0.1 µg/L (AMN 0.2 µg/L; CYA 1 µg/L), while LOQs could be improved to 0.01 µg/L (CYA 0.05 µg/L) by applying evaporation for analyte pre-concentration. The method was extensively validated, showing good recovery, repeatability, and linearity. The evaluation of the matrix effects revealed method applicability for various water matrices, including surface water and wastewater. During proof-of-concept measurements, HMMM in combination with MEL and its derivatives was found in multiple samples, emphasizing the importance of including precursors. In the future, the developed method with its novelty of covering both MEL derivatives and precursors can be applied for comprehensive monitoring programs elucidating MEL sources and transformation in water resources. Full article

Cement manufacturing is the second largest anthropogenic source of Hg emissions in the environment. Therefore, the establishment of analytical methodologies that can be utilized in the determination of Hg concentration from cement raw materials and cement is of great importance. The total Hg and Hg thermospecies in cement raw materials and cements were determined by thermal desorption techniques with a Zeeman Hg analyzer. No chemical pre-treatment of samples is required for this technique prior to analysis. An optimum single-stage temperature program was applied to determine total Hg at an optimum heating rate of approximately 5 °C s⁻¹ while Hg thermospecies were determined over four stages at an optimum heating rate of approximately 0.2 °C s⁻¹ per stage from ambient temperature to 720 °C. Total mercury concentrations in cement raw materials ranged between 2.19 ng g⁻¹ and 395 ng g⁻¹, while in cement, concentrations ranged between 1.32 ng g⁻¹ and 31.0 ng g⁻¹. The highest Hg contents were found in dust return (580 ng g⁻¹ and 679 ng g⁻¹). Hg thermospecies determination showed that cement raw materials and cements contain one Hg thermospecies that is released at 20–180 °C while dust return contained one to four Hg thermospecies that could be released at 20–180 °C, 180–360 °C, 360–540 °C, and/or 540–720 °C, thus indicating that new Hg compounds are formed during cement production. Full article

The Stability Toolkit for the Appraisal of Bio/Pharmaceuticals’ Level of Endurance (STABLE) is introduced and proposed as a comprehensive tool and software to evaluate the stability of active pharmaceutical ingredients (APIs) under various stress conditions. In the pharmaceutical industry, stability testing is a critical step in the drug development process, ensuring the quality, safety, and efficacy of APIs. Traditional stability tests—such as real-time, accelerated, and forced degradation testing—often face challenges, including inconsistent interpretation and implementation across different regions and organizations. STABLE addresses these challenges by providing a standardized and holistic approach to assessing drug stability across five key stress conditions: oxidative, thermal, acid-catalyzed hydrolysis, base-catalyzed hydrolysis, and photostability. Beyond its role as an evaluation tool, STABLE also serves as a practical guide for chemists, encouraging a more complete and thoughtful approach to stability studies. While many investigations focus solely on acid- and base-catalyzed hydrolysis, other critical conditions—such as photostability—are often underexplored or entirely omitted. By highlighting the importance of evaluating all relevant degradation pathways, STABLE promotes more robust and informed stability testing protocols. The index utilizes a color-coded scoring system to quantify and compare stability, facilitating consistent assessments across different APIs. This paper discusses the methodology of STABLE, including the scoring system and specific criteria applied under each condition. This tool is introduced to reflect intrinsic degradation susceptibility under forced conditions. The software is freely available as an open-source tool at bit.ly/STABLE2025, enabling broader accessibility and implementation across the pharmaceutical research community. Full article

The dichromate ion (Cr₂O₇²⁻), a highly toxic chromium VI species, is widely used in industrial processes, generating serious environmental problems when released into water bodies. This investigation proposes the use of a functionalized polymer as an adsorbent material for its removal in the aqueous phase. Poly(butyl methacrylate) (PBMA) was synthesized and modified by impregnation with resorcinarenes derived from long-chain aliphatic aldehydes. To improve the affinity for the dichromate, the resorcinarenes were functionalized with sulfomethyl groups by treatment with Na₂SO₃. The resulting matrices were characterized using IR-ATR, ¹H-NMR, and ¹³C-NMR, and their adsorbent performance was evaluated via UV-Vis spectroscopy in batch extraction assays. The results showed that the functionalized polymer exhibited a higher adsorption capacity than the base polymer, reaching up to 81.1% removal at pH 5.0 in one hour. These results highlight the potential of PBMA as an effective support and raise a promising research perspective for functionalized resorcinarenes in the development of new materials for the treatment of contaminated water. Full article

The application of high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS) in the analysis of peptide therapeutics demonstrates its capacity to achieve high sensitivity and selectivity, which are essential qualities for the expanding peptide therapeutic industry. Given the challenges posed by hydrophilic peptides in reversed-phase chromatography, we investigated the necessity of a derivatization procedure to improve chromatographic separation and quasimolecular ion fragmentation during MS/MS detection. We investigated how eight different derivatizing agents react with a hydrophilic lysine- and arginine-containing human ezrin peptide-1 (HEP-1) to identify the most suitable one. The results showed that the reaction of HEP-1 with propionic anhydride proceeds most rapidly and completely, providing a high and reproducible yield of the product, which has sufficient retention on the RP column. The 4-propionylated derivative of HEP-1, compared to the other derivatives considered, demonstrates the most pronounced MS/MS fragmentation. The retention time of 2.42 min allows the separation of the substance from the interfering components of the blood plasma matrix and provides a limit of quantification of 5.00 ng/mL, which allows the use of this derivatizing agent for subsequent applications in pharmacokinetic studies, and this approach can improve the analytical parameters of similar peptides in other HPLC-MS/MS studies. Full article

This study focuses on the stabilization of a natural hair dye derived from Lawsonia inermis L. (henna) and Indigofera suffruticosa (indigo). Although various formulations already exist, they are designed for immediate use and cannot be stored. Lawsonia, a primary component of the dye, tends to degrade after release. To ensure its stability, freeze-drying was implemented as a protective measure. Colorimetric analysis confirmed the dye’s ability to maintain an intense, uniform coloration even after multiple washing cycles. Stability tests demonstrate that freeze-drying effectively enhances the dye’s stability and capacity to retain its physical properties and color under various environmental conditions, demonstrating its potential for long-term use. The dye’s pH (5.05) aligns with the natural pH of hair, promoting cuticle sealing and improving hair health. Cytotoxicity tests confirmed the dye’s safety, showing no harmful effects. Gray hair exhibited a total color difference (ΔE) of 64.06 after the initial application, using natural gray hair as a reference. By the third application, ΔE increased to 69.86 and gradually decreased to 68.20 after 15 washing cycles, highlighting its long-term durability. Gray hair exposed to 720 h of UV radiation showed a ΔE of 17.34, whereas dyed gray hair exhibited a ΔE of 2.96 compared to non-UV-exposed samples. This indicates superior resistance to color degradation in dyed hair. Also, SEM imaging revealed the dye’s restorative effects, progressively improving hair cuticle structure with each application. Full article