Microfluidic paper-based analytical device for measurement of pH using as sensor red cabbage anthocyanins and gum arabic.

The objective of this study was to develop and validate a novel microfluidic paper-based analytical device (µPADpH) for determining the pH levels in foods. Anthocyanins from red cabbage aqueous extract (RCAE) were used as its analytical sensor. Whatman No. 1 filter paper was the most suitable for the device due to its porosity and fiber organization, which allows for maximum color intensity and minimal color heterogeneity of the RCAE in the detection zone of the µPADpH. To ensure the color stability of the RCAE for commercial use of the µPADpH, gum arabic was added. The geometric design of the µPADpH, including the channel length and separation zone diameter, was systematically optimized using colored food. The validation showed that the µPADpH did not differ from the pH meter when analyzing natural foods. However, certain additives in processed foods were found to increase the pH values.

Ivermectin-based products in the context of green pharmaceutical analysis.

BACKGROUND: Ivermectin (IVE), a broad-spectrum antiparasitic, is used in human and animal health. Analytical methods for evaluating IVE in pharmaceutical products are found in the literature and in official compendiums. However, the vast majority of them do not have an eco-friendly approach. OBJECTIVE AND METHOD: The aim of this review is to present an overview of existing analytical methods for evaluating IVE in pharmaceutical matrices in the context of Green Analytical Chemistry (GAC) and show possibilities for increasing their greenness. RESULTS: GAC is a current alternative to promote sustainable development in laboratories and chemical-pharmaceutical industries, therefore, through its principles, such as reducing the use of aggressive solvents, it is possible to make processes more ecological. However, the vast majority of analytical methods available in the literature and official compendiums do not present an eco-friendly approach. 70% of the methods are by HPLC. Among the various pharmaceutical matrices, the most evaluated are tablets (37%). Of all the solvents used in HPLC, UPLC, HPLC-MS/MS, UV and TLC methods, the combination of methanol and acetonitrile is the most chosen, accounting for more than 50% of occurrences. CONCLUSIONS: Analytical methods for evaluating IVE-based products can be leveraged within the scope of GAC, bringing sustainable work opportunities to analytical development laboratories around the world. HIGHLIGHTS: This review shows an overview of the analytical methods present in the literature and official compendiums to evaluate pharmaceutical IVE matrices, in the context of green analytical chemistry.

Oral squamous cell carcinoma identification by FTIR spectroscopy of oral biofluids.

OBJECTIVES: This case study evaluated the efficacy of mid-infrared spectroscopy on the identification of oral squamous cell carcinoma, following the assessment of unstimulated whole saliva. STUDY DESIGN AND METHODS: The trial follows a matched case-control design. Saliva samples were characterized through mid-infrared spectroscopy, and chemometric tools were applied to distinguish between case and control participants, further identifying the spectral regions that played a pivotal role in the successful identification of oral squamous cell carcinoma. RESULTS: Mid-infrared spectroscopy was capable to discriminate between cancer patients and matched controls with 100% of correct predictions. Additionally, the spectral regions mostly contributing to the successful prediction were identified and found to be potentially associated with significant molecular changes crucial to the carcinogenic process. CONCLUSION: The application of mid-infrared spectroscopy in saliva analysis may be regarded as an innovative, noninvasive, low cost, and sensitive technique contributing to the identification of oral squamous cell carcionma.

Identification of blood at simulated crime scenes using silver nanoparticles with SERS.

The analysis of substances and samples obtained from a crime scene is very important in solving forensic cases. To determine the variables involved in a crime and to expedite the investigation process, the rapid analysis of body fluids in small quantities and within environments containing diverse components is particularly necessary. For this reason, it is of great importance to analyze biological fluids with rapid, noncontaminating, nondestructive, low-cost, and accurate techniques. In recent years, with advancements in laser technology, spectroscopic methods have been introduced as analytical techniques in forensic medicine and chemical studies. This study focuses on surface-enhanced Raman spectroscopy (SERS) to demonstrate the detection of blood samples in simulated crime scenes. To minimize the background signal from fluorescent biomolecules in blood, dilution was performed with two different components and Raman analysis was performed for four different concentrations of blood. In general, a decrease in noise in the spectra was observed as the blood was diluted. Crime scenes consisting of pure blood, blood diluted with ethanol and distilled water (1:2, 1:4, and 1:8), a blood-mineral water mixture, a blood-cherry juice mixture, and silver nanoparticle-added mixtures were simulated, and their spectra were examined. Chemometric analyses of the data were performed. Despite high noise and low peak intensities, blood-identifying signals were detected when examining different blood concentrations. It was observed that silver nanoparticles provided high enhancement of blood peaks thanks to their strong plasmonic properties.

A green procedure for the determination of bioavailable forms of aluminum in natural waters by electrothermal atomic absorption spectroscopy combined with microextraction technique.

Aluminum is a prevalent element in nature, but bioavailable forms of aluminum are toxic to plants, animals, and humans. The present study is dedicated to the development of an ecologically friendly, fast, simple, reliable, sensitive, and accurate improved procedure for the determination of subtrace concentrations of bioavailable forms of aluminum in natural waters. The procedure includes the separation and pre-concentration of bioavailable forms of aluminum using vortex-assisted liquid-liquid microextraction (VALLME) of ionic associates with salicylaldehyde 4-picolinhydrazone (SAPH) and sodium dodecyl sulfate (DDSNa) by isoamylacetate (200 µl) and direct electrothermal atomic absorption spectroscopy (ET AAS). The SAPH reagent interacts only with water-soluble forms of aluminum. SAPH is used for the pre-concentration of bioavailable forms of aluminum as well as a chemical modifier; it increases the absorbance and the precision of the analytical signal of aluminum. The calibration curve shows the linear dependence in the range of 0.05-86 µg⋅L-1 of the aluminum concentration (R2 = 0.992), with the limit of detection at 0.015 µg⋅L-1 and the limit of quantification at 0.05 µg⋅L-1. The accuracy of the proposed procedure for bioavailable forms of aluminum determination was verified on model solutions and against a reference method on natural samples of river and lake waters (RSD 3.2-5.2%, recovery 97.1-103.4%).

Improving rigor and reproducibility in western blot experiments with the blotRig analysis.

Western blot is a popular biomolecular analysis method for measuring the relative quantities of independent proteins in complex biological samples. However, variability in quantitative western blot data analysis poses a challenge in designing reproducible experiments. The lack of rigorous quantitative approaches in current western blot statistical methodology may result in irreproducible inferences. Here we describe best practices for the design and analysis of western blot experiments, with examples and demonstrations of how different analytical approaches can lead to widely varying outcomes. To facilitate best practices, we have developed the blotRig tool for designing and analyzing western blot experiments to improve their rigor and reproducibility. The blotRig application includes functions for counterbalancing experimental design by lane position, batch management across gels, and analytics with covariates and random effects.

Utility, feasibility, and socio-demographic considerations in the diagnosis of bacterial RTI's by GC-IMS breath analysis.

Diagnosis of respiratory tract infections (RTIs), especially in primary care, is typically made on clinical features and in the absence of quick and reliable diagnostic tests. Even in secondary care, where diagnostic microbiology facilities are available, these tests take 24-48 h to provide an indication of the etiology. This multicentre study used a portable gas chromatography-ion mobility spectrometer (GC-IMS) for the diagnosis of bacterial RTIs. Breath samples taken from 570 participants with 149 clinically validated bacterial and 421 non-bacterial RTIs were analyzed to distinguish bacterial from non-bacterial RTIs. Through the integration of a sparse logistic regression model, we identified a moderate diagnostic accuracy of 0.73 (95% CI 0 · 69, 0 · 77) alongside a sensitivity of 0 · 85 (95% CI 0 · 79, 0 · 91) and a specificity of 0 · 55 (95% CI 0 · 50, 0 · 60). The GC-IMS diagnostic device provides a promising outlook in distinguishing bacterial from non-bacterial RTIs and was also favorably viewed by participants.

Evaluation of analytical greenness metric for an eco-friendly method developed through the integration of green chemistry and quality-by-design for the simultaneous determination of Nebivolol hydrochloride, Telmisartan, Valsartan, and Amlodipine besylate.

In recent years, the field of analytical chemistry has witnessed a notable shift towards the adoption of greener chromatographic methods, aiming to minimize the environmental impact. An effective strategy involves substituting conventional harmful organic solvents with environmentally friendly alternatives, reducing the use of hazardous chemicals that contribute to environmental concerns. However, separating drug substances without the use of buffers and organic solvents presence is a big challenge. To overcome this challenge, a combination of quality-by-design (QbD) and green analytical chemistry (GAC) was employed in this study for method development. A high-performance liquid chromatography (HPLC) method was successfully developed and validated for the simultaneous determination of Nebivolol hydrochloride, Telmisartan, Valsartan, and Amlodipine besylate. The method utilized a mobile phase composed of a mixture of 0.1 % formic acid in water (pH: 2.5) and ethanol. A regular octadecyl silica (ODS) column was employed, and UV detection at 220 nm was utilized. The method exhibited linearity within the concentration range of 25-75 µg/mL for Telmisartan and 150-450 µg/mL for Nebivolol Hydrochloride, Valsartan, and Amlodipine besylate and the correlation coefficient was greater than 0.999 for all the analytes. Limits of detection (LOD) and quantification (LOQ) were determined as 0.01 and 0.04 µg/mL for Telmisartan, 0.06 and 0.20 µg/mL for Nebivolol Hydrochloride, 0.08 and 0.25 µg/mL for Amlodipine besylate, and 0.14 and 0.46 µg/mL for Valsartan, respectively. The developed method underwent thorough validation, encompassing various parameters such as linearity, accuracy, precision, LOD, LOQ, robustness, and ruggedness. The mean recovery values were observed to range between 98.86 % and 99.89 %. The accuracy demonstrated was consistently above 98.98 % for both intra-day and inter-day precisions were with the relative standard deviations less than 2 %. To establish its robustness, a quality-by-design-based experimental design (DoE) approach was implemented. Additionally, the method's environmental friendliness was evaluated using the Analytical Greenness metric (AGREE) an analytical eco scale, both confirming its alignment with sustainable practices and reduced ecological impact. The sustainability of the solvent used in the current study was evaluated by Green Solvents Selecting Tool (GSST) Further, the developed method greenness was evaluated with the green analytical tools such as Analytical method greenness score (AMGS) and using the recently released White Analytical Chemistry (WAC) using RGB assessment tool. By employing this greener approach to chromatography method, this study contributes to the ongoing efforts in analytical chemistry to promote sustainable practices and minimize the environmental footprint of analytical methods.

Why nothing beats NIRS technology: The green analytical choice for the future sustainable food production.

In this perspective paper we argue for the fact that near infrared (NIR) technology, due to its unique properties, will become an indispensable green sensor technology in the future digitalized and sustainable food production. The future of near infrared spectroscopy (NIRS) in green analytics is bright. Ongoing advancements in NIR technology, coupled with increased accessibility and integration with advanced multivariate data analysis such as machine learning and artificial intelligence will further amplify the impact of NIRS across food, agricultural, environmental, and renewable energy domains. The miniaturization, increased portability, and enhanced affordability of NIR instruments, coupled with its integration into emerging technologies, will empower a diverse range of industries and researchers to address pressing global challenges with unprecedented precision and efficiency. The implementation of NIR technology in process analytical technology will enable the transition to future digitalized and sustainable food production. In a future circular economy, where waste streams, co-products and water are reclaimed and valorized, continuous measurements are necessary and in many cases, there are no sensor alternatives to NIR technology.

An Overview of the Analytical Methods for Products based on Clindamycin and Eco-efficiency Perspectives.

BACKGROUND: Clindamycin (CLIN), an antibiotic sold in the form of capsules, injectable solution, gel, and lotion, is easily soluble in water and ethanol. However, it lacks eco-efficient methods for evaluating pharmaceutical products. OBJECTIVE AND METHOD: The objective of this review is to provide an overview of the analytical methods present both in the literature and in official compendia for evaluating pharmaceutical matrices based on CLIN in the context of Green Analytical Chemistry (GAC). RESULTS: Firstly, microbiological methods for evaluating the potency of CLIN final products were not found, which already shows the need to develop new methods. Among the methods found, which are all physicalchemical, the most used method is HPLC (71%) followed by UV-Vis (14%). Among the targets of the methods, capsules and raw materials were the most studied (33% each). Among the choices of analytical conditions for the methods, acetonitrile is the preferred solvent (27.7%), even though CLIN is easily soluble in ethanol. CONCLUSION: Thus, the gap in eco-friendly and sustainable analytical methods is a reality and an opportunity for analytical development centers to provide means for evaluating the quality of CLIN-based products.

Development and validation of a green analytical method for determining fourteen bisphenols in bee pollen by ultra-high-performance liquid chromatography-tandem mass spectrometry.

A new analytical method was developed and validated to determine fourteen bisphenols (A, B, C, E, F, M, P, S, Z, AF, AP, BP, FL, PH) in bee pollen using ultra-high-performance liquid chromatography-tandem mass spectrometry. Two different sample treatments were proposed and evaluated: one based on the QuEChERS (quick, easy, cheap, effective, rugged & safe) approach and the other utilizing microextraction with a supramolecular solvent (SUPRAS). In both cases, average analyte recovery ranged between 71 % and 114 %, and the matrix effect was between -45 % and +5 %, although it was not significant when using the QuEChERS-based method (<±20 %). The environmental impact of both sample treatments was assessed using different analytical metrics, with both procedures classified as environmentally friendly, though slightly better results were obtained for SUPRAS. The method was fully validated, showing that the QuEChERS approach had better overall performance, particularly regarding sensitivity and matrix effect. Consequently, the QuEChERS methodology was applied to determine bisphenols in thirty bee pollen samples from different Spanish regions. Residues of three bisphenols (M, P, and S) were detected, although only bisphenol S was quantified in several samples at low concentration levels (<7 µg kg-1), which is below the established specific migration limit (SML; 50 µg kg-1). However, regarding human health, the estimated daily intake, target hazard quotient, and hazard index assessed were higher than acceptable limits, suggesting a potential risk for human consumers.

Copper and nitrogen-doped carbon quantum dots as green nano-probes for fluorimetric determination of delafloxacin; characterization and applications.

BACKGROUND: Carbon quantum dots (CQDs) have gained much interest recently for being efficient probes. Their cost-effectiveness, eco-friendliness, and unique photocatalytic activities made them distinctive alternatives to other luminescent approaches like fluorescent dyes and luminous derivatization. Meanwhile, delafloxacin (DLF) is a recently approved antibacterial medicine. DLF has been authorized for the treatment of soft-tissue and skin infections as well as pneumonia. Therefore, new eco-friendly, cost-effective, and sensitive tools are needed its estimation in different matrices. RESULTS: In the proposed study, green copper and nitrogen carbon dots (Cu-N@CDs) were synthesized from a green source (plum juice with copper sulphate). Cu-N@CQDs were then characterized using multiple tools including X-ray photon spectroscopy (XPS), FTIR and UV-VIS spectroscopy, Zeta potential measurements, High-resolution transmission electron microscopy (HRTEM), and fluorescence spectroscopy. After gradually adding DLF, the developed quantum dots' fluorescence was significantly enhanced within the working range of 0.5-100.0 ng mL-1. The limits of detection and quantification were 0.08 and 0.27 ng mL-1, respectively. The accuracy of the proposed method ranged from 96.00 to 99.12 % in recovery%, when recovered from milk and plasma samples. SIGNIFICANCE: Cu-N@CDs were utilized and validated for selectively determining DLF in several matrices including pharmaceutical forms, human plasma and in milk samples using spectrofluorimetric technique. The bio-analytical method is simple and could be used in content uniformity testing as well as in therapeutic drug monitoring in human plasma.

Radiometric approaches with carbon-14-labeled molecules for determining herbicide fate in plant systems.

Weeds cause economic losses in cropping systems, leading to the use of 1.7 million tons of herbicides worldwide for weed control annually. Once in the environment, herbicides can reach non-target organisms, causing negative impacts on the ecosystem. Herbicide retention, transport, and degradation processes determine their environmental fate and are essential to assure the safety of these molecules. Radiometric strategies using carbon-14 herbicides (14C) are suitable approaches for determining herbicide absorption, translocation, degradation, retention, and transport in soil, plants, and water. In this work, we demonstrate how 14C-herbicides can be used from different perspectives. Our work focused on herbicide-plant-environment interactions when the herbicide is applied (a) through the leaf, (b) in the soil, and (c) in the water. We also quantified the mass balance in each experiment. 14C-mesotrione foliar absorption increased with oil and adjuvant addition (5-6 % to 25-46 %), and translocation increased only with adjuvant. More than 80 % of 14C-quinclorac and 14C-indaziflam remained in the soil and cover crops species absorbed less than 20 % of the total herbicides applied. In water systems, Salvinia spp. plants removed 10-18 % of atrazine from the water. Atrazine metabolism was not influenced by the presence of the plants. The radiometric strategies used were able to quantify the fate of the herbicide in different plant systems and the mass balance varied from 70 % to 130 %. Importantly, we highlight a critical and practical view of tracking herbicides in different matrices. This technique can aid scientists to explore other pesticides as environmental contaminants.

Advancements in effervescent-assisted dispersive micro-solid phase extraction for the analysis of emerging pollutants.

Emerging pollutants pose an increasing threat to the environment and human well-being, requiring substantial progress in analytical methodologies. Dispersive micro-solid phase extraction (µ-dSPE) has proven successful in detecting and measuring these contaminants, particularly in trace quantities. However, challenges persist in achieving a uniform sorbent distribution and efficient separation from the sample matrix. To address these issues, effervescent-assisted dispersive micro-solid phase extraction (EA-µ-dSPE) was developed. This method uses on-site produced carbon dioxide as a dispersing agent, eliminating the need for vortexing or ultrasonication. Due to the sorbent dispersion in the sample solution, the contact surface between the analyte and the sorbent increases, resulting in increased extraction efficiency, reduced extraction time, and promotes of sustainability. Several parameters are critical to the successful execution of this procedure to extract the analytes, including the type and structure of sorbent, composition of dispersing agents, sorbent separation procedure, and type and properties of desorption solvents. The sorbent plays a critical role in successful extraction of emerging pollutants. It is clear that for the extraction of the analyte on the sorbent, proper interaction must be established between the analyte and the sorbent via physical and chemical interactions. This review thoroughly evaluates the underlying principles of the approach, its potential, and the significant advancements that have been documented. It explores the method's capacity to analyse and identify emerging pollutants, emphasising its potential across various sample matrices for enhanced pollutant identification and quantification.

Food profiling goes green: Sustainable analysis strategies for food authentication.

Omics technologies, such as genomics, proteomics, metabolomics, isotopolomics, and metallomics, are important tools for analytical verification of food authenticity. However, in many cases, their application requires the use of high-resolution technological platforms as well as careful consideration of sample collection, storage, preparation and, in particular, extraction. In this overview, the individual steps and disciplines are explained against the background of the term "Green Chemistry," and the various instrumental procedures for the respective omics disciplines are discussed. Furthermore, new approaches and developments are presented on how such analyses can be made sustainable in the future.

Sustainable approaches to analyzing phenolic compounds: a green chemistry perspective.

Innovative and eco-friendly methodologies for the determination of phenolic compounds, showing a paradigm shift in analytical chemistry toward sustainability. Phenolic compounds, valued for their diverse health benefits, have historically been analyzed using methods that often involve hazardous solvents and energy-intensive processes. This review focuses on green analytical chemistry principles, emphasizing sustainability, reduced environmental impact, and analytical efficiency. The use of DES, specifically Ch: Chl-based DES, emerges as a prominent green alternative for extracting phenolic compounds from various sources. The integration of UAE with DES enhances extraction efficiency, contributing to a more sustainable analytical approach. Furthermore, the review highlights the significance of DLLME and SPME in reducing solvent consumption and simplifying extraction procedures. These techniques exemplify the commitment to making phenolic compound analysis environmentally friendly. The incorporation of portable measurement tools, such as smartphones, into analytical methodologies is a notable aspect discussed in the review. Techniques like UA-DLLME leverage portable devices, making phenolic compound determination more accessible and versatile. Anticipating the future, the review foresees ongoing advancements in sustainable analytical approaches, driven by collaborative efforts across diverse disciplines. Novel solvents, extraction techniques, and portable measurement methods are expected to play pivotal roles in the continuous evolution of green analytical methodologies for the analysis of phenolic compounds. The review encapsulates a transformative journey toward environmentally responsible and efficient analytical practices, paving the way for further research and application in diverse analytical settings.

Efficient and environmentally friendly spectrofluorimetric determination of cariprazine: An analytical and green chemistry approach.

Cariprazine represents a new generation of antipsychotic medication, characterized by its heightened affinity for the D3 receptor. It has recently obtained approval as an adjunctive treatment option for patients diagnosed with major depressive disorder. In this study, a novel approach utilizing fluorescence spectroscopy was developed to analyze cariprazine. The methodology involves the transformation of cariprazine into a fluorescent compound by means of chemical derivatization with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl). Following excitation at 470 nm, the fluorescent derivative displayed peak fluorescence emission at 550 nm. The factors influencing the derivatization process were optimized. Upon reaching the optimal reaction conditions, a linear correlation (r2 = 0.9995) was observed between the fluorescence intensity and concentrations of cariprazine ranging from 20 to 400 ng/ml. Detection and quantitation limits were determined to be 5.85 and 17.74 ng/ml, respectively. The approach was accurate and precise, with percent recovery values ranging from 98.14% to 99.91% and relative standard deviations of less than 2%. Application of the method to the analysis of cariprazine in bulk and commercial capsules forms yielded accurate results. Moreover, adherence to environmentally friendly analytical practices was evident through alignment with the principles of green analysis, as demonstrated by the analytical eco-scale, AGREE, and GAPI greenness assessment tools.

Water as a green solvent for sustainable sample preparation: single drop microextraction of N-nitrosamines from losartan tablets.

Water, renowned for its sustainability and minimal toxicity, is an ideal candidate for environmentally friendly solvent-based microextraction. However, its potential as an extractant solvent in miniaturized sample preparation remains largely unexplored. This paper pioneers using water as the extraction solvent in headspace single-drop microextraction (HS-SDME) for N-nitrosamines from losartan tablets. Autonomous HS-SDME is executed by an Arduino-controlled, lab-made Cartesian robot, using water for the online preconcentration of enriched extracts through direct injection into a column-switching system. Critical experimental parameters influencing HS-SDME performance are systematically explored through univariate and multivariate experiments. While most previously reported methods for determining N-nitrosamines in pharmaceutical formulations rely on highly selective mass spectrometry detection techniques to handle the strong matrix effects typical of pharmaceutical samples, the water-based HS-SDME method efficiently eliminates the interfering effects of a large amount of the pharmaceutical active ingredient and tablet excipients, allowing straightforward analysis using high-performance liquid chromatography with ultraviolet detection (HPLC-UV-Vis). Under optimized conditions, the developed method exhibits linear responses from 100 to 2400 ng g-1, demonstrating appropriate detectability, precision, and accuracy for the proposed application. Additionally, the environmental sustainability of the method is assessed using the AGREEprep methodology, positioning it as an outstanding green alternative for determining hazardous contaminants in pharmaceutical products.

Clinical applications of volatilomic assays.

The study of metabolomics is revealing immense potential for diagnosis, therapy monitoring, and understanding of pathogenesis processes. Volatilomics is a subcategory of metabolomics interested in the detection of molecules that are small enough to be released in the gas phase. Volatile compounds produced by cellular processes are released into the blood and lymph, and can reach the external environment through different pathways, such as the blood-air interface in the lung that are detected in breath, or the blood-water interface in the kidney that leads to volatile compounds detected in urine. Besides breath and urine, additional sources of volatile compounds such as saliva, blood, feces, and skin are available. Volatilomics traces its roots back over fifty years to the pioneering investigations in the 1970s. Despite extensive research, the field remains in its infancy, hindered by a lack of standardization despite ample experimental evidence. The proliferation of analytical instrumentations, sample preparations and methods of volatilome sampling still make it difficult to compare results from different studies and to establish a common standard approach to volatilomics. This review aims to provide an overview of volatilomics' diagnostic potential, focusing on two key technical aspects: sampling and analysis. Sampling poses a challenge due to the susceptibility of human samples to contamination and confounding factors from various sources like the environment and lifestyle. The discussion then delves into targeted and untargeted approaches in volatilomics. Some case studies are presented to exemplify the results obtained so far. Finally, the review concludes with a discussion on the necessary steps to fully integrate volatilomics into clinical practice.