Analytical Principles Research Articles

A paper-based device for glyphosate electrochemical detection in human urine: A case study to demonstrate how the properties of the paper can solve analytical issues

In the ever-growing demand for agricultural production, the use of pesticides and the consequential health risks is an issue that remains in the spotlight. The biomonitoring of pesticides in biological matrices is a mandatory task to point out the adverse effects on those people that are particularly exposed (i.e., occupational exposure) and to customize the use of pesticides for safer and more aware agricultural practices (i.e., precision agriculture). To overcome the bottleneck of costs and long sample treatments, we conceived a paper-based analytical device for the fast and smart detection of glyphosate in human urines, which is still the most widespread pesticide. Importantly, we demonstrate how to face the analytical interference given by uric acid to develop an electrochemical sensor for glyphosate detection using paper as a multifunctional material. To this purpose, a sample treatment was pointed out and integrated into a paper strip to decrease the level of uric acid in urines, finally delivering a ready-to-use device that combines lateral and vertical flow. The effective decrease of uric acid after the paper-integrated treatment is verified by direct oxidation in differential pulse voltammetry, whereas glyphosate detection can be carried out by enzyme inhibition assay in chronoamperometry. The system showed a limit of detection for glyphosate of 75 μg/L and a linear range of 100 - 700 μg/L. Additionally, the sustainability of the paper device was assessed and compared with reference chromatographic methods. Overall, this work provides an example of how to design green sensing solutions for addressing analytical challenges in line with the White Analytical Chemistry principles.

Zur Rolle der Silbenquantität in der mittelhochdeutschen Metrik

Abstract The article illustrates and justifies the role of syllable weight for the MHG verse. It counters a 2021 paper by A. Estis, who fundamentally questions the relevance of syllable weight for MHG metrics. The argumentation of the riposte relies on text-analytical findings, methodological aspects (heuristics), the history of the German verse in late medieval and early modern times, last but not least on historical testimonies, namely by Heinrich von Hesler and Nikolaus von Jeroschin. The article concludes with a reformulation of basic analytical principles of MHG metrics, thus trying to forestall some misunderstandings possibly provoked by the traditional terminology of A. Heusler.

Facial Emotion Recognition for Photo and Video Surveillance Based on Machine Learning and Visual Analytics

Modern video surveillance systems mainly rely on human operators to monitor and interpret the behavior of individuals in real time, which may lead to severe delays in responding to an emergency. Therefore, there is a need for continued research into the designing of interpretable and more transparent emotion recognition models that can effectively detect emotions in safety video surveillance systems. This study proposes a novel technique incorporating a straightforward model for detecting sudden changes in a person’s emotional state using low-resolution photos and video frames from surveillance cameras. The proposed technique includes a method of the geometric interpretation of facial areas to extract features of facial expression, the method of hyperplane classification for identifying emotional states in the feature vector space, and the principles of visual analytics and “human in the loop” to obtain transparent and interpretable classifiers. The experimental testing using the developed software prototype validates the scientific claims of the proposed technique. Its implementation improves the reliability of abnormal behavior detection via facial expressions by 0.91–2.20%, depending on different emotions and environmental conditions. Moreover, it decreases the error probability in identifying sudden emotional shifts by 0.23–2.21% compared to existing counterparts. Future research will aim to improve the approach quantitatively and address the limitations discussed in this paper.

A novel simulation model to predict photosynthetic active radiation interception in micro-irrigated citrus production orchards based on tree spacing, canopy geometry, and row orientation

Diurnal and seasonal patterns of photosynthetically active radiation (PAR) intercepted by tree canopies in production orchards have an important role for eco-physiological processes that determine tree water use and productivity. Under well-watered conditions, PAR intercepted by trees is a reliable predictor of crop consumptive water use, which is regulated by tree spacing, tree row orientation, and by the tree canopy dimensions and geometry. Despite its advantages, only rare attempts have been made by the scientific and fruit production communities to develop canopy PAR interception simulators that rely on analytical principles to inform irrigation planning and management decisions. In this article, a novel model is presented that simulates PAR interception by citrus trees based on the canopy geometry and its shading patterns. The article also illustrates preliminary field testing and validation of the model with data collected in commercial citrus production orchards located in the San Joaquin Valley of California. The testing and validation could enable citrus growers and orchard managers to predict the net radiation for mature, micro-irrigated Navel orange and Page mandarin orchards grown with north–south and east–west tree row orientations and different tree densities. Results from the simulations and field validation showed that the canopy PAR light interception contributed 58.8 (± 0.02) and 71.1 (± 1.60) percent to the overall net radiation for the Navel orange orchards during the periods around summer solstice and autumnal equinox, respectively, whereas for the Page mandarin orchards, PAR light interception contributed 63.0 (±5.60) and 85.7 (±18.87) percent to the overall net radiation during the same time periods. Good correlations were found between daily values of PAR and net radiation for these citrus production orchards grown with the two alternative row orientations, which suggest that the proposed model could be used to inform irrigation planning and management decisions for different site-specific citrus orchard features and growing conditions.

Adding Sustainability in Analytical Chemistry Education through Monitoring Aquarium Water Quality

This paper introduces a captivating topic for upper-level analytical chemistry capstone projects, focusing on aquarium water analysis. This provides a more comprehensive understanding of the role of analytical chemistry towards sustainability and its environmental, economic, societal and education dimensions. Regarding the crucial role of maintaining optimal aquarium water quality for the welfare of aquatic life, students are tasked with envisioning and executing the measurement of key parameters, including pH, ammonium, nitrite, and nitrate contents. This hands-on experience not only engages students in real-world applications, but also allows them to delve into essential analytical chemistry principles. They carefully select measurement methods, considering factors such as instrument availability, ease of use, precision and sensitivity requirements, sample size, and matrix effects. Besides fostering the acquisition of technical and soft skills, one notable aspect of this type of project is the exceptionally high student satisfaction. Furthermore, the project’s outcomes have proven to be significant predictors of learning achievements. Additionally, it lays the foundation for exploring potential designs of aquaponics systems and fosters interdisciplinary projects, expanding the practical applications in the field of chemistry education. Overall, these projects exemplify enriching and engaging educational experiences that empower students with valuable skills and knowledge while encouraging them to explore novel avenues in analytical chemistry.

Optimisation of dispersive liquid-liquid microextraction for plasma sample preparation in bioanalysis of CDK4/6 inhibitors in therapeutic combinations for breast cancer treatment

Cyclin D dependent kinase 4 and 6 (CDK 4/6) inhibitors are novel anticancer drugs used in therapeutic combinations with endocrine therapy for breast cancer treatment. Their determination in patient plasma is of high interest as a prerequisite for possible therapeutic drug monitoring. Dispersive liquid-liquid microextraction (DLLME) shows great potential in bioanalytical sample preparation. Its simplicity and speed, along with the suitability for using small amounts of sample and hazardous solvents are some of its main advantages. However, its application on plasma samples is scarce and requires further development. The aim of this work was to explore the applicability of DLLME in the simultaneous extraction of six drugs of interest from human plasma, with an emphasis placed on achieving high extraction recoveries with low sample and solvent consumption. To tackle the low availability and amount of the plasma sample, as well as the complexity of the biological matrix, three novel DLLME modes are proposed: organic sample DLLME (OrS-DLLME), aqueous sample DLLME (AqS-DLLME), and a modified air-assisted DLLME (AA-DLLME). The extractant and disperser type and volume, volume ratios of all the components in the ternary system, effect of pH and salting out were optimised for all three proposed modes of DLLME. Optimised representative DLLME-HPLC-DAD-FLD method was validated and shown to be linear (R > 0.994), precise (RSD ≤13.8%, interday), accurate (bias −13.1–13.1%, interday) and robust (relative effect −3.34–6.08%). Simultaneous extraction of all six drugs with high recoveries (81.65–95.58%) was achieved. Sample volumes used were as low as 50–100 μL, with necessary organic solvent volumes in μL ranges. Greenness scores obtained using the AGREE software were between 0.63 and 0.66, demonstrating compliance with green analytical chemistry principles. Finally, the validated method was successfully applied on breast cancer patient plasma samples.

Green chromatographic methods and in vitro pharmacological analysis of Varronia curassavica leaf derivatives.

Varronia curassavica displays anti-inflammatory, antiulcerogenic, and antioxidant activities. Herein, we employed new UHPLC -UV green chromatographic methods for the analysis of in vitro antioxidant and anti-inflammatory activities of V. curassavica and its embryotoxicity in Zebrafish. Cordialin A, brickellin, and artemetin were purified from the ethanol (EtOH) extract of V. Curassavica leaves and identified using spectrometric techniques. In line with Green Analytical Chemistry principles, the proposed UHPLC methods involve the use of ethanol as organic modifier with low mobile phase consumption, and without sample pretreatment (OLE-UHPLC-UV). The application of the Agree and HPLC-EAT tools for greenness assessment yielded this pattern: HPLC-UV (reference) < UHPLC-UV < OLE-UHPLC-UV. Zebrafish assay results showed that 70% EtOH extract of V. Curassavica leaves exhibited lower toxicity compared to 100% EtOH extract, with LC50 of 164.3 and 122.9 µg/mL, respectively, in 24 h post fertilization. Some embryos exhibited malformation phenotypes in the heart, somites, and eyes, mainly in higher extract concentrations. Extracts and brickellin exhibited higher antioxidant activity in the DPPH• assay, while brickellin + artemetin displayed higher antioxidant activity compared to the extracts and isolated flavones in the O2•- and HOCl/OCl- scavenging assays. Cordialin A and brickellin exhibited low COX-1, COX-2, and phospholipase A2 inhibition.

Application of solidified floating organic droplet dispersive liquid–liquid microextraction for determination of veterinary antibiotic residues in milk samples with greenness assessment

Antibiotics are the most commonly used veterinary drug category worldwide. The extensive utilization of antibiotics in animal farming is one of the main causes of antibiotic resistance, thus posing a hazard to human health. In the current study, solidification of floating organic droplet dispersive liquid–liquid microextraction (SFO-DLLME) was developed as a green sample preparation step for extracting three widely used veterinary antibiotics; enrofloxacin, ciprofloxacin and oxytetracycline in milk samples present in the Egyptian market. SFO-DLLME was based on using 1-undecanol as a low-toxicity extracting solvent. As several effective parameters are required to be optimized in SFO-DLLME, Box–Behnken experimental design was utilized to obtain the best possible extraction results. The analysis of the analytes was performed through the development of two eco-friendly chromatographic techniques. The first method was based on HPLC-UV where the separation was achieved using C18 column with isocratic elution of mobile phase composed of 0.025 M phosphate buffer (pH 3.2): acetonitrile (85: 15 v/v) and UV detection at 278 nm. The second was UPLC-MS/MS method utilizing BEH shield C18 column acetonitrile: 0.1% formic acid in a ratio of 80:20 (v/v) as mobile phase. The two developed methods were validated it was found that they had high recoveries (88.50 %- 94%), enrichment factors(106.2 %- 112.93 %), low limit of detection (0.077 µg/kg − 29 µg/kg), and satisfactory precision RSD ≤ 2. Different brands of market milk samples were analyzed showing no residues of the studied antibiotics, while enrofloxacin was detected in a concentration of 3.74 µg/kg in raw cow milk samples. Finally, the greenness profile of the developed chromatographic methods was evaluated by the Green Analytical Procedure Index, Analytical GREEnness Metric Approach, and White Analytical Chemistry principles confirming their safety on the environment.

What Can Data Justice Mean for Asylum Governance? The Case of Smartphone Data Extraction in Germany

Abstract This article takes new digital surveillance policies in European asylum procedures as an occasion to explore possible principles for an ethical use of digital data on asylum seekers. Drawing on three different conceptions of data justice, and considering their respective analytical focus, objectives and principles, it develops an evaluative framework that helps to unpack what just data-driven governance in the field of asylum can mean. Based on the case of Germany, which introduced a policy to extract data from the smartphones of asylum seekers, the article illustrates how each of the three conceptions of data justice practically informs claims that (de)legitimize dataveillance. The article concludes by highlighting the practical relevance and the shortcomings of established principles such as privacy in balancing the interests between asylum seekers and state authorities. It further argues for a consideration of the structural inequalities of data-based visibility in relation to hierarchies of civic stratification.

A green compliant hand-held selective electrode device for monitoring active pharmaceuticals and the kinetics of their degradation

An in-line smartphone connected to a screen-printed selective electrode hand-held device was used to determine the concentration of distigmine bromide (DB) in its pure and dosage forms as well as its degradation kinetics by continuously measuring the change in the produced emf over time. The main objective, supported by the data presented, is to produce a highly reliable smartphone integrated selective sensor as a portable analyzer with potential high cloud connectivity combining a wide linear dynamic range, the fastest response time with the lowest limits of detection and quantitation while best integrating green analytical chemistry principles. The choice of ionophore used in this approach was guided by computation and the data obtained was compared with traditional analytical techniques. DB, for which there are no previously reported stability-indicating methods and for which four novel such methods are proposed here, was selected as a model drug for this work. At-line UV-spectrophotometry DB assay was obtained by measuring the difference between the spectra of the degradation product and the same concentration of intact drug. The degradation kinetics were studied by this method through tracking the decrease of DB absorbance and/or the increase of a generated degradation product signal over time. Off-line separation based HPLC and TLC stability-indicating methods for DB were also presented. All methods employed in this work were validated for accuracy, precision, specificity, repeatability, linearity, range, detection and quantification limits according to the ICH guidelines and were applied to the analysis of laboratory prepared mixtures as well as commercial products. While all methods proposed were shown to be highly reliable, the smartphone integrated selective sensor is highlighted as a portable analyzer with potential high cloud connectivity and was shown to combine a wide linear dynamic range, the fastest response time with the lowest limits of detection and quantitation while best integrating green analytical chemistry principles.

Environmentally sustainable DRS-FTIR probe assisted by chemometric tools for quality control analysis of cinnarizine and piracetam having diverged concentration ranges: Validation, greenness, and whiteness studies

A novel diffuse reflectance fourier transform infrared spectroscopic method accompanied by chemometrics was optimized to fulfill the white analytical chemistry and green analytical chemistry principles for the quantification of cinnarizine and piracetam for the first time without any prior separation in their challenging pharmaceutical preparation, which has a pretty substantial difference in the concentration of cinnarizine/piracetam (1:16). Furthermore, the suggested method was used for cinnarizine/piracetam dissolution testing as an effective alternative to traditional methods. For the cinnarizine/piracetam dissolution tests, we used a dissolution vessel with 900 mL of phosphate buffer pH 2.5 at 37 °C ± 0.5 °C, then the sampling was carried out by frequent withdrawal of 20 µl samples from the dissolution vessel at a one-minute interval, over one hour, then representative fourier transform infrared spectra were recorded. To create a partial-least-squares regression model, a fractional factorial design with 5 different levels and 2 factors was used. This led to the creation of 25 mixtures, 15 as a calibration set and 10 as a validation set, with varying concentration ranges: 1–75 and 16–1000 μg/mL for cinnarizine/piracetam, respectively. Upon optimization of the partial-least-squares regression model, in terms of latent variables and spectral region, root mean square error of cross-validation of 0.477 and 0.270, for cinnarizine/piracetam respectively, were obtained. The optimized partial-least-squares regression model was further validated, providing good results in terms of recovery% (around 98 to 102 %), root mean square error of prediction (0.436 and 3.329), relative root mean square error of prediction (1.210 and 1.245), bias-corrected mean square error of prediction (0.059 and 0.081), and limit of detection (0.125 and 2.786) for cinnarizine/piracetam respectively. Ultimately, the developed method was assessed for whiteness, greenness, and sustainability using five assessment tools. the developed method achieved a greener national environmental method index and complementary green analytical procedure index quadrants with higher eco-scale assessment scores (91), analytical greenness metric scores (0.87), and red–greenblue 12 algorithm scores (89.7) than the reported methods, showing high practical and environmental acceptance for quality control of cinnarizine/piracetam.

Юридическая аналитика в массмедиа: стратагемно-тактические аспекты

The development of information technologies contributes to an increase in the number of areas where the intersection of media and social phenomena and thus the media discourse with other institutional discourses takes place. The heterogeneous discourses resulting from these processes are characterized by a specific goal and strategic and tactical apparatus, which is of particular interest in terms of discourse studies. The article aims to identify the main communicative goals, strategies and tactics in the genre of analytical article on legal issues. The study uses the texts of English-language analytical articles on legal issues published in electronic versions of the following daily editions: The Times, Financial Times, The Guardian, The New York Times, The Wall Street Journal, The Washington Post in the period 2015–2022. The authors use philosophical, general scientific, as well as special methods and techniques: dialectical, empirical methods, description, induction, deduction, analysis, synthesis, methods of discursive and contextual analysis. The researchers identify the value dominant of the genre, which determines the goal and strategic and tactical characteristics of the analytical article on legal issues: elite legal awareness formation. In accordance with the value dominant, the main communicative goals of the genre are defined and described (informing, explaining, influencing and developing the recipient’s heuristic potential). The paper presents a general communicative media analytical strategy, which includes a set of principles involved in the implementation of this strategy (analyticity, reliability, persuasiveness, striving for objectivity, accessibility, individuality, multimediality, heuristics. The authors describe the strategic principles and provide the analysis of the communicative tactics used by the addressees in combination with the communicative goals of the genre and the media analytical strategy principles.

Development and validation of an eco-compatible UV–Vis spectrophotometric method for the determination of Cu2+ in aqueous matrices

Cu2+ are ubiquitous ions in the ecosystem and are responsible of serious environmental pollution. Indeed, the development of sensitive methods for Cu2+ detection is an urgent demand. In this work, we proposed a new spectrophotometric method for Cu2+ determination in different water matrices (distilled water, drinking water, wastewater, and river water). The method employs a bio-based organic ligand namely tetrasodium iminodisuccinate (IDS) able to form a stable complex with the analyte with a maximum absorption at 710 nm. Within the linear range of 6.3–381 mg L−1, the limit of detection (LOD) was determined to be as 1.43 mg L−1. Moreover, the recovery data of the spiked analysis of drinking/river/wastewater water samples were also satisfactory and verified the feasibility of the method for the analysis of Cu2+ in natural conditions. Finally, the AGREE assessment tool was used for a quantitative evaluation of the proposed method and reference method, in agreement with the green analytical chemistry principles. The results showed the lower environmental impact of the proposed method and the suitability of this novel approach for Cu2+ in water matrices.Graphical abstract

Sample Size Effects on Petrophysical Characterization and Fluid-to-Pore Accessibility of Natural Rocks.

Laboratory-scale analysis of natural rocks provides petrophysical properties such as density, porosity, pore diameter/pore-throat diameter distribution, and fluid accessibility, in addition to the size and shape of framework grains and their contact relationship with the rock matrix. Different types of laboratory approaches for petrophysical characterization involve the use of a range of sample sizes. While the sample sizes selected should aim to be representative of the rock body, there are inherent limitations imposed by the analytical principles and holding capacities of the different experimental apparatuses, with many instruments only able to accept samples at the μm-mm scale. Therefore, a total of nine (three limestones, three shales, two sandstones, and one dolomite) samples were collected from Texas to fill the knowledge gap of the sample size effect on the resultant petrophysical characteristics. The sample sizes ranged from 3 cm cubes to <75 μm particles. Using a combination of petrographic microscopy, helium expansion pycnometry, water immersion porosimetry, mercury intrusion porosimetry, and (ultra-) small-angle X-ray scattering, the impact of sample size on the petrophysical properties of these samples was systematically investigated here. The results suggest that the sample size effect is influenced by both pore structure changes during crushing and sample size-dependent fluid-to-pore connectivity.

Conceptual complexes in multimodal advertising

Several scholars have dealt with the workings of metaphor and metonymy in multimodal advertisements (see Forceville, 2009; Uriós-Aparisi, 2009; or Pérez-Sobrino, 2017, among others). The present study investigates conceptual complexity to broaden the set of analytical categories to be used in multimodal analysis by making use of some of the latest developments on conceptual complexes, or principled combinations of cognitive models (e.g., frames, metaphors, metonymies), as discussed in Ruiz de Mendoza (2017, 2021) to a multimodal context. Work on conceptual complexity in Cognitive Linguistics has taken two main directions. One is provided by Blending Theory, which focuses on accounting for the emergence of new structure not present in the contributing conceptual constructs after selected integration. Another direction studies patterns of conceptual interaction with a view to finding regularities that can be formulated as high-level generalizations. We will adopt this second direction. The main aim of the study is to test these analytical categories and principles of knowledge organization in terms of their communicative impact within a multimodal environment. A subsidiary aim is to further develop the theoretical apparatus underlying this initial work. Analysing a corpus of 62 multimodal advertisements, we found that: (i) the nature of a frame determines its function, i.e., matrix frames are receiving frames, which ‘situationalize’ conceptual structure, whereas donor frames play a focal role; (ii) sometimes there is no frame integration but rather internal development within a given frame, which is possible thanks to the incorporation of an external element that is not integrated, but simply facilitates the development of the frame; (iii) there are also cases in which there is frame composition instead of integration; (iv) metonymy proves to be a licensing factor previous to integration, and (v) high-level non-metaphorical correlations can act as cues for the activation of metaphorical frameworks.

Green analytical chemistry and experimental design: a combined approach for the analysis of zonisamide

Green analytical chemistry principles, as well as experimental design, are a combined approach adopted to develop sensitive reproducible stability indicating HPLC method for Zonisamide (ZNS) determination. The optimal conditions for three chromatographic parameters were determined using a central composite design of the response surface. Kromasil C18 column (150 mm × 4.6 mm, 5 µm) was utilized with ethanol, H2O (30:70 v/v) as a mobile phase at a flow rate of 1 mL/min at 35 °C. Good reproducibility and high sensitivity were achieved along (0.5–10 µg/mL) concentration range. In contrast, the TLC-densitometric method was performed on aluminum plates precoated with silica gel 60F254 as a stationary phase and chloroform: methanol: acetic acid (8:1.5:0.5 by volume) as a developing system. Reproducible results were obtained in the range of (2–10 μg/band). The chromatograms of HPLC and TLC were scanned at 280 nm and 240 nm, respectively. The suggested methods have been validated following ICH guidelines, and no statistically significant differences were detected between the results of the current study and the official USP method. It was also found that using experimental design implements the green concept by reducing the environmental impact. Finally, Eco-Scale, GAPI and AGREE were used to assess the environmental impacts of the suggested methods.

Simultaneous green TLC determination of nirmatrelvir and ritonavir in the pharmaceutical dosage form and spiked human plasma

Quantitative analysis of pharmaceutical compounds up to Nano gram levels is highly recommended to introduce feasible and sensitive tool for determination of the compounds in the pharmaceutical and biological samples. Nirmatrelvir plus ritonavir was recently approved in the US, the UK and Europe as a new co-packaged dosage form for the treatment of COVID-19. The objective of this work was to develop a more sensitive TLC method based on using β-cyclodextrin as a chiral selector additive in the mobile phase for simultaneous determination of nirmatrelvir and ritonavir in pure form, pharmaceutical formulation and spiked human plasma. The analysis procedures were developed using TLC aluminum silica gel plates and methanol–water- 2% urea solution of β-cyclodextrin (40:10:.5, by volume) as a mobile phase with UV detection at 215 nm. The developed method was successfully applied over a linearity range of 10–50 ng/band for both nirmatrelvir and ritonavir. The method was validated for limits of detection and quantitation, accuracy, precision, specificity, system suitability, and robustness. Furthermore, the eco-friendliness of the proposed method was assessed using the analytical eco-scale and the green analytical procedure index. The described method exhibited compliance with green analytical chemistry principles based on common green metric values.

Insight into continuous glucose monitoring: from medical basics to commercialized devices.

According to the latest statistics, more than 537 million people around the world struggle with diabetes and its adverse consequences. As well as acute risks of hypo- or hyper- glycemia, long-term vascular complications may occur, including coronary heart disease or stroke, as well as diabetic nephropathy leading to end-stage disease, neuropathy or retinopathy. Therefore, there is an urgent need to improve diabetes management to reduce the risk of complications but also to improve patient's quality life. The impact of continuous glucose monitoring (CGM) is well recognized, in this regard. The current review aims at introducing the basic principles of glucose sensing, including electrochemical and optical detection, summarizing CGM technology, its requirements, advantages, and disadvantages. The role of CGM systems in the clinical diagnostics/personal testing, difficulties in their utilization, and recommendations are also discussed. In the end, challenges and prospects in future CGM systems are discussed and non-invasive, wearable glucose biosensors are introduced. Though the scope of this review is CGMs and provides information about medical issues and analytical principles, consideration of broader use will be critical in future if the right systems are to be selected for effective diabetes management.

Novel Sorptive Sample Preparation Techniques for Separation Science

The primary analytical challenge is to selectively extract the target analytes using a suitable sample preparation technique and introduce them into the downstream analytical instrument. The critical step in the chemical analysis is sample preparation. Sorptive sample preparation techniques are among the new generation of microextraction approaches, and are compliant with green analytical chemistry principles. A recent intercontinental collaboration between two academic research laboratories—the Aristotle University of Thessaloniki, Greece, and the Florida International University, USA—has yielded a significant number of analytical/bioanalytical methods using fabric phase sorptive extraction (FPSE), magnet integrated fabric phase sorptive extraction (MI-FPSE), and capsule phase microextraction (CPME) for the isolation of various analytes from different complex sample matrices. A brief description of these techniques with regards to principle, synthesis, applications, and advantages and disadvantages along with paradigms is presented.

Development of a Fully Automated Method HS-SPME-GC-MS/MS for the Determination of Odor-Active Carbonyls in Wines: a "Green" Approach to Improve Robustness and Productivity in the Oenological Analytical Chemistry.

The aim of this study was the optimization and validation of a green, robust, and comprehensive method for the determination of volatile carbonyl compounds (VCCs) in wines that could be added as a new quality control tool for the evaluation of a complete fermentation, correct winemaking style, and proper bottling and storage. A HS-SPME-GC-MS/MS method was optimized and automated using the autosampler to improve overall performance. A solvent-less technique and a strong minimization of all volumes were implemented to comply with the green analytical chemistry principles. There were as many as 44 VCC (mainly linear aldehydes, Strecker aldehydes, unsaturated aldehydes, ketones, and many other) analytes under investigation. All compounds showed a good linearity, and the LOQs were abundantly under the relevant perception thresholds. Intraday, 5-day interday repeatability, and recovery performances in a spiked real sample were evaluated showing satisfactory results. The method was applied to determine the evolution of VCCs in white and red wines after accelerated aging for 5 weeks at 50 °C. Furans and linear and Strecker aldehydes were the compounds that showed the most important variation; many VCCs increased in both classes of samples, whereas some showed different behaviors between white and red cultivars. The obtained results are in strong accordance with the latest models on carbonyl evolution related to wine aging.