Pub Date : 2025-04-10DOI: 10.1016/j.sampre.2025.100181
Nur Fitrah Abdullah Sani , Rico Ramadhan , Noorfatimah Yahaya , Siti Maisharah Sheikh Ghadzi , Ahmad Husaini Mohamed , Sazlinda Kamaruzaman , Wan Nazihah Wan Ibrahim , Nor Suhaila Mohamad Hanapi , Nur Nadhirah Mohamad Zain
Deep eutectic solvents have emerged as a sustainable alternative to conventional organic solvents and ionic liquids, offering advantages such as low toxicity, biodegradability, and cost-effectiveness. Their integration into membrane-based systems has revolutionized extraction, separation, and preconcentration techniques, particularly for organic compounds in aqueous matrices. This review provides a comprehensive analysis of deep eutectic solvent-based membranes, focusing on their classifications, preparation methods, and fabrication strategies. The application of different types of deep eutectic solvent-based membranes is critically evaluated. Special attention is given to the optimization of extraction parameters, and mechanisms governing analyte-membrane interactions. While deep eutectic solvent-based membranes demonstrate significant potential for enhanced selectivity, enrichment, and recovery, challenges such as membrane stability, scalability, and compatibility with analytical instrumentation remain. Addressing these limitations through advanced material engineering and process optimization will be crucial for broader adoption. This review highlights recent advancements, identifies research gaps, and outlines future perspectives to enhance the applicability of deep eutectic solvent-based membranes in analytical and environmental sciences.
{"title":"Advancements in deep eutectic solvent-based membranes for the extraction, separation, and preconcentration of organic compounds","authors":"Nur Fitrah Abdullah Sani , Rico Ramadhan , Noorfatimah Yahaya , Siti Maisharah Sheikh Ghadzi , Ahmad Husaini Mohamed , Sazlinda Kamaruzaman , Wan Nazihah Wan Ibrahim , Nor Suhaila Mohamad Hanapi , Nur Nadhirah Mohamad Zain","doi":"10.1016/j.sampre.2025.100181","DOIUrl":"10.1016/j.sampre.2025.100181","url":null,"abstract":"<div><div>Deep eutectic solvents have emerged as a sustainable alternative to conventional organic solvents and ionic liquids, offering advantages such as low toxicity, biodegradability, and cost-effectiveness. Their integration into membrane-based systems has revolutionized extraction, separation, and preconcentration techniques, particularly for organic compounds in aqueous matrices. This review provides a comprehensive analysis of deep eutectic solvent-based membranes, focusing on their classifications, preparation methods, and fabrication strategies. The application of different types of deep eutectic solvent-based membranes is critically evaluated. Special attention is given to the optimization of extraction parameters, and mechanisms governing analyte-membrane interactions. While deep eutectic solvent-based membranes demonstrate significant potential for enhanced selectivity, enrichment, and recovery, challenges such as membrane stability, scalability, and compatibility with analytical instrumentation remain. Addressing these limitations through advanced material engineering and process optimization will be crucial for broader adoption. This review highlights recent advancements, identifies research gaps, and outlines future perspectives to enhance the applicability of deep eutectic solvent-based membranes in analytical and environmental sciences.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100181"},"PeriodicalIF":5.2,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-07DOI: 10.1016/j.sampre.2025.100180
Juan L. Benedé , Cecilia Cagliero , Emirhan Nemutlu , Francisco Pena-Pereira , Carlo Bicchi , Enrique Javier Carrasco-Correa , Maria Celeiro , Alberto Chisvert , Alessandra Gentili , A. Ruth Godfrey , Mehmet Gumustas , Fragoulis Krokos , Paramee Kumkrong , Maria Llompart , Marcello Locatelli , Zoltan Mester , Sibel A. Ozkan , Stig Pedersen-Bjergaard , Marcela A. Segundo , Marek Tobiszewski , Elefteria Psillakis
This work evaluates the greenness of 174 standard methods with a sample preparation step and their 332 sub-method variations from CEN, ISO, and Pharmacopoeias, used in laboratories for environmental/organic, food, trace element, or pharmaceutical analyses. The widely adopted AGREEprep metric was applied to assess the greenness of the standard methods. The discussion begins with the overall scores of each method, followed by a detailed analysis of individual criteria, that highlights the strengths and weaknesses of the evaluated sample preparation methods in terms of greenness.
The results revealed a generally poor greenness performance, as 67 % of the methods scored below 0.2 on the AGREEprep scale, where 1 represents the highest possible score. Specifically, the percentage of methods scoring below 0.2 was 86 % for methods related to the environmental analysis of organic compounds, 62 % for methods used in food analysis, 62 % for those applied to inorganic and trace metals analysis, and 45 % for methods used in pharmaceutical analysis. The findings obtained in this work reveal that many official methods still rely on resource-intensive, outdated techniques, scoring poorly on key greenness criteria. This discrepancy highlights the urgent need to update standard methods by including contemporary and mature sample preparation methods, as the traditional methodologies currently used often conflict with global sustainability efforts and increase regulatory and societal pressures. As such, this contribution serves not only as a critique of the current state of official standard methods but also as a call to action for their reform. This work was conducted within the framework of the IUPAC project "Greenness of official standard sample preparation methods" (2021-015-2-500).
{"title":"Greenness assessment of 174 CEN, ISO, and pharmacopoeia standard methods and their sub-methods used for environmental, food, trace element and pharmaceutical analyses","authors":"Juan L. Benedé , Cecilia Cagliero , Emirhan Nemutlu , Francisco Pena-Pereira , Carlo Bicchi , Enrique Javier Carrasco-Correa , Maria Celeiro , Alberto Chisvert , Alessandra Gentili , A. Ruth Godfrey , Mehmet Gumustas , Fragoulis Krokos , Paramee Kumkrong , Maria Llompart , Marcello Locatelli , Zoltan Mester , Sibel A. Ozkan , Stig Pedersen-Bjergaard , Marcela A. Segundo , Marek Tobiszewski , Elefteria Psillakis","doi":"10.1016/j.sampre.2025.100180","DOIUrl":"10.1016/j.sampre.2025.100180","url":null,"abstract":"<div><div>This work evaluates the greenness of 174 standard methods with a sample preparation step and their 332 sub-method variations from CEN, ISO, and Pharmacopoeias, used in laboratories for environmental/organic, food, trace element, or pharmaceutical analyses. The widely adopted AGREEprep metric was applied to assess the greenness of the standard methods. The discussion begins with the overall scores of each method, followed by a detailed analysis of individual criteria, that highlights the strengths and weaknesses of the evaluated sample preparation methods in terms of greenness.</div><div>The results revealed a generally poor greenness performance, as 67 % of the methods scored below 0.2 on the AGREEprep scale, where 1 represents the highest possible score. Specifically, the percentage of methods scoring below 0.2 was 86 % for methods related to the environmental analysis of organic compounds, 62 % for methods used in food analysis, 62 % for those applied to inorganic and trace metals analysis, and 45 % for methods used in pharmaceutical analysis. The findings obtained in this work reveal that many official methods still rely on resource-intensive, outdated techniques, scoring poorly on key greenness criteria. This discrepancy highlights the urgent need to update standard methods by including contemporary and mature sample preparation methods, as the traditional methodologies currently used often conflict with global sustainability efforts and increase regulatory and societal pressures. As such, this contribution serves not only as a critique of the current state of official standard methods but also as a call to action for their reform. This work was conducted within the framework of the IUPAC project \"Greenness of official standard sample preparation methods\" (2021-015-2-500).</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100180"},"PeriodicalIF":5.2,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1016/j.sampre.2025.100178
Maryam Mallek , Damia Barcelo
The effects of microplastics (MPs) in wastewater, sludge, and landfills are analyzed and discussed, focusing on their pathways into the environment. The application of sludge as a soil amendment and the reuse of treated wastewater in agriculture have been further proven to contribute to the introduction of MPs into terrestrial ecosystems. MPs present a capacity to accumulate in plants together with co-contaminants such as heavy metals and pharmaceuticals, posing additional risks to food safety and soil quality. This review underscores the need to align analytical practices with sustainability by adopting environmentally friendly methods. A critical discussion is presented on the analysis of MPs, encompassing an in-depth examination of analytical methodologies, challenges in sample preparation, and potential solutions. Techniques such as Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy, and Pyrolysis-GC–MS (Py-GC–MS) are highlighted for their effectiveness in MP identification, combined with treatment approaches like density separation, enzymatic digestion, and oxidation. MPs appear in various forms, including synthetic fibers, microbeads, and fragmented particles, with their distribution being influenced by polymer types. Low-density polymers like polyethylene (PE) and polypropylene (PP) tend to remain in the water phase, whereas high-density polymers such as polyester (PES/PEST) and polytetrafluoroethylene (PTFE) accumulate in solid matrices like sludge and sediments. Inconsistencies in measurement units are a significant issue in microplastic analysis. Concentrations are typically reported as items per liter (for water) or items per kilogram (for soil), However, mass-based units such as µg/L are rarely employed, complicating data comparison. Another essential component is the determination of MP size, which is largely dependent on analytical equipment detection limits and resolution. Most studies focus on MPs ranging from 20–50 µm to a few millimeters, with limited research addressing MPs smaller than 0.1 µm, known as nanoplastics (NPs). Lastly, sustainable management approaches for addressing the worldwide problem of plastic pollution will be presented.
{"title":"Sustainable analytical approaches for microplastics in wastewater, sludge, and landfills: Challenges, fate, and green chemistry perspectives","authors":"Maryam Mallek , Damia Barcelo","doi":"10.1016/j.sampre.2025.100178","DOIUrl":"10.1016/j.sampre.2025.100178","url":null,"abstract":"<div><div>The effects of microplastics (MPs) in wastewater, sludge, and landfills are analyzed and discussed, focusing on their pathways into the environment. The application of sludge as a soil amendment and the reuse of treated wastewater in agriculture have been further proven to contribute to the introduction of MPs into terrestrial ecosystems. MPs present a capacity to accumulate in plants together with co-contaminants such as heavy metals and pharmaceuticals, posing additional risks to food safety and soil quality. This review underscores the need to align analytical practices with sustainability by adopting environmentally friendly methods. A critical discussion is presented on the analysis of MPs, encompassing an in-depth examination of analytical methodologies, challenges in sample preparation, and potential solutions. Techniques such as Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy, and Pyrolysis-GC–MS (Py-GC–MS) are highlighted for their effectiveness in MP identification, combined with treatment approaches like density separation, enzymatic digestion, and oxidation. MPs appear in various forms, including synthetic fibers, microbeads, and fragmented particles, with their distribution being influenced by polymer types. Low-density polymers like polyethylene (PE) and polypropylene (PP) tend to remain in the water phase, whereas high-density polymers such as polyester (PES/PEST) and polytetrafluoroethylene (PTFE) accumulate in solid matrices like sludge and sediments. Inconsistencies in measurement units are a significant issue in microplastic analysis. Concentrations are typically reported as items per liter (for water) or items per kilogram (for soil), However, mass-based units such as µg/L are rarely employed, complicating data comparison. Another essential component is the determination of MP size, which is largely dependent on analytical equipment detection limits and resolution. Most studies focus on MPs ranging from 20–50 µm to a few millimeters, with limited research addressing MPs smaller than 0.1 µm, known as nanoplastics (NPs). Lastly, sustainable management approaches for addressing the worldwide problem of plastic pollution will be presented.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100178"},"PeriodicalIF":5.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-17DOI: 10.1016/j.sampre.2025.100179
Natalia A. Gomez , Anabela S. Lorenzetti , Damian A. Uriarte , Carolina Acebal , Juan M. Padró , Antonio Canals , Mariano Garrido , Claudia E. Domini
The main objective of this review is to provide an overview of the coupling between microextraction techniques (mainly based on the use of vortex and ultrasound) and different optical techniques in order to demonstrate that their combination can be a valid and accessible option for the determination of chemical species at trace or ultra-trace level. This revaluation of conventional optical techniques, including detection by digital imaging, is related to the concept of democratic analytical chemistry, and refers to the possibility of generating quality results even in laboratories with limited resources and little access to sophisticated instrumentation. In addition, the development of greener solvents and new adsorbent materials expand the capacity and versatility of the microextraction techniques, making them more effective and environmentally friendly options. In summary, the article aims to draw the attention of researchers to techniques that usually fall into disuse but, in combination with appropriate preconcentration procedures, can be attractive and economical choices for routine analysis of organic and inorganic species.
{"title":"Revaluing optical techniques in the light of vortex- and ultrasound-assisted microextraction","authors":"Natalia A. Gomez , Anabela S. Lorenzetti , Damian A. Uriarte , Carolina Acebal , Juan M. Padró , Antonio Canals , Mariano Garrido , Claudia E. Domini","doi":"10.1016/j.sampre.2025.100179","DOIUrl":"10.1016/j.sampre.2025.100179","url":null,"abstract":"<div><div>The main objective of this review is to provide an overview of the coupling between microextraction techniques (mainly based on the use of vortex and ultrasound) and different optical techniques in order to demonstrate that their combination can be a valid and accessible option for the determination of chemical species at trace or ultra-trace level. This revaluation of conventional optical techniques, including detection by digital imaging, is related to the concept of democratic analytical chemistry, and refers to the possibility of generating quality results even in laboratories with limited resources and little access to sophisticated instrumentation. In addition, the development of greener solvents and new adsorbent materials expand the capacity and versatility of the microextraction techniques, making them more effective and environmentally friendly options. In summary, the article aims to draw the attention of researchers to techniques that usually fall into disuse but, in combination with appropriate preconcentration procedures, can be attractive and economical choices for routine analysis of organic and inorganic species.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100179"},"PeriodicalIF":5.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-16DOI: 10.1016/j.sampre.2025.100177
Juan L. Benedé , Francisco Pena-Pereira
Microwave-assisted digestion (MAD) is a widely used technique for the preparation of samples for elemental analysis. Significant advances toward more efficient and less hazardous MAD methods have been described in recent years, even though no systematic evaluation has been carried out in terms of green sample preparation. The present work evaluates the effectiveness and environmental impact of recent MAD methods through the lens of AGREEprep, a recognized metric tool that identifies the greenness attributes of sample preparation methods. The metric tool was employed for the assessment of 38 decomposition methods for food analysis, including MAD methods involving decreasing amounts of oxidizing agents, considering supplemental reagents and assistances, such as oxygen pressure, hydrogen peroxide, ultraviolet irradiation, and microwave-induced combustion. In addition, conventional decomposition methods and alternative approaches involving infrared heating have been considered in the assessment. The 38 methods received overall scores in a wide range of 0.14 to 0.52, being MAD methods without acid consumption and those involving combustion the greenest methods (scores from 0.40 to 0.52). By systematically evaluating key criteria, such as reagent usage, energy consumption, process safety, and waste generation, AGREEprep provides a comprehensive view of MAD methods that can contribute to further improvements toward more sustainable analytical practices.
{"title":"On the greenness of recent microwave-assisted digestion methods: An evaluation with AGREEprep","authors":"Juan L. Benedé , Francisco Pena-Pereira","doi":"10.1016/j.sampre.2025.100177","DOIUrl":"10.1016/j.sampre.2025.100177","url":null,"abstract":"<div><div>Microwave-assisted digestion (MAD) is a widely used technique for the preparation of samples for elemental analysis. Significant advances toward more efficient and less hazardous MAD methods have been described in recent years, even though no systematic evaluation has been carried out in terms of green sample preparation. The present work evaluates the effectiveness and environmental impact of recent MAD methods through the lens of AGREEprep, a recognized metric tool that identifies the greenness attributes of sample preparation methods. The metric tool was employed for the assessment of 38 decomposition methods for food analysis, including MAD methods involving decreasing amounts of oxidizing agents, considering supplemental reagents and assistances, such as oxygen pressure, hydrogen peroxide, ultraviolet irradiation, and microwave-induced combustion. In addition, conventional decomposition methods and alternative approaches involving infrared heating have been considered in the assessment. The 38 methods received overall scores in a wide range of 0.14 to 0.52, being MAD methods without acid consumption and those involving combustion the greenest methods (scores from 0.40 to 0.52). By systematically evaluating key criteria, such as reagent usage, energy consumption, process safety, and waste generation, AGREEprep provides a comprehensive view of MAD methods that can contribute to further improvements toward more sustainable analytical practices.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100177"},"PeriodicalIF":5.2,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143681937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-15DOI: 10.1016/j.sampre.2025.100176
Alejandra Molina-Balmaceda, Valentina Rojas-Candia, Juan José Triviño, Daniel Arismendi, Pablo Richter
In the realm of green analytical chemistry, there is growing interest in sorbent phases derived from natural materials like grapefruit peels as promising alternatives to commercial sorbent phases. Initially, the effectiveness of grapefruit peels in their natural state was compared to activated carbons treated with activating agents as a sorbent phase in rotating disk sorptive extraction (RDSE). The conditions for synthesizing activated carbon were optimized by adjusting the activating agent variables, proportions, and temperatures to obtain an efficient material for extracting ethylparaben (EP), propylparaben (PP), ibuprofen (Ibu), triclosan (TCS), bisphenol A (BPA), and 17-α-ethinylestradiol (EE2) using rotating disk sorption extraction technique from aqueous samples. The optimal conditions were determined to be activation with ZnCl2 at a 1:1.2 ratio (material: activating reagent) and carbonization at 400 °C (AC400(Z1.2)). Characterization revealed a hydrophilic microporous material with a large surface area and aromatic structure, confirming its potential as a sorbent phase for aqueous sample preparation. The application of AC400(Z1.2) sorbent phase in RDSE in river water confirmed its effectiveness, revealing EP, PP, Ibu, TCS, and BPA in concentrations ranging from 0.18 to 2.8 µg l-1, with EE2 concentration below the limit of detection. Reusability studies demonstrate that this material can be reused for the simultaneous extraction of analytes in at least two consecutive extractions without requiring additional treatment between extractions. This material proves to be an economical and bio-based alternative to commercial sorbent phases. Finally, its application in RDSE was evaluated using green analytical chemistry metrics (AGREEprep and BAGI), resulting in a methodology with a low environmental impact.
{"title":"Grapefruit peel activated carbon for multi-analyte microextraction in water analysis through rotating disk sorptive extraction","authors":"Alejandra Molina-Balmaceda, Valentina Rojas-Candia, Juan José Triviño, Daniel Arismendi, Pablo Richter","doi":"10.1016/j.sampre.2025.100176","DOIUrl":"10.1016/j.sampre.2025.100176","url":null,"abstract":"<div><div>In the realm of green analytical chemistry, there is growing interest in sorbent phases derived from natural materials like grapefruit peels as promising alternatives to commercial sorbent phases. Initially, the effectiveness of grapefruit peels in their natural state was compared to activated carbons treated with activating agents as a sorbent phase in rotating disk sorptive extraction (RDSE). The conditions for synthesizing activated carbon were optimized by adjusting the activating agent variables, proportions, and temperatures to obtain an efficient material for extracting ethylparaben (EP), propylparaben (PP), ibuprofen (Ibu), triclosan (TCS), bisphenol A (BPA), and 17-α-ethinylestradiol (EE2) using rotating disk sorption extraction technique from aqueous samples. The optimal conditions were determined to be activation with ZnCl<sub>2</sub> at a 1:1.2 ratio (material: activating reagent) and carbonization at 400 °C (AC400(Z1.2)). Characterization revealed a hydrophilic microporous material with a large surface area and aromatic structure, confirming its potential as a sorbent phase for aqueous sample preparation. The application of AC400(Z1.2) sorbent phase in RDSE in river water confirmed its effectiveness, revealing EP, PP, Ibu, TCS, and BPA in concentrations ranging from 0.18 to 2.8 µg <span>l</span><sup>-1</sup>, with EE2 concentration below the limit of detection. Reusability studies demonstrate that this material can be reused for the simultaneous extraction of analytes in at least two consecutive extractions without requiring additional treatment between extractions. This material proves to be an economical and bio-based alternative to commercial sorbent phases. Finally, its application in RDSE was evaluated using green analytical chemistry metrics (AGREEprep and BAGI), resulting in a methodology with a low environmental impact.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100176"},"PeriodicalIF":5.2,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143681877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-14DOI: 10.1016/j.sampre.2025.100175
Ana Y. Simão , Luana M. Rosendo , Pedro Dinis , Cláudia Margalho , Maristela Andraus , Mário Barroso , Eugenia Gallardo
New psychoactive substances (NPS), including synthetic cathinones and phenethylamines, pose significant challenges due to their evolving chemical structures and health impacts. This study aimed to optimize and validate a methodology for detecting and quantifying a number of synthetic cathinones [methylone, ethylone, pentedrone, 4-chloroethcathinone (4-CEC), penthylone, α-pyrrolidinopentiophenone (α-PVP), 3,4-methylenedioxypyrovalerone (MDPV), 4‑chloro-α-pyrrolidinovalerophenone (4-Cl-α-PVP), as well as phenethylamine 2,5-dimethoxy-4(n)-propylphenethylamine (2C-P)], in hair samples using microextraction by packed sorbent (MEPS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). We developed an environmentally friendly and cost-effective MEPS procedure, which was validated for selectivity, linearity, precision, accuracy, and recovery. Results demonstrated that the method effectively detects analytes with limits of quantification as low as 10 pg/mg. The method successfully identifies MDPV in concentrations consistent with those observed in chronic and acute drug consumption cases, proving its suitability in forensic and clinical toxicology. This approach offers a robust solution for forensic and clinical applications, by combining efficient sample clean-up with precise analytical capabilities.
{"title":"Microextraction by packed sorbent for the determination of selected synthetic cathinones and 2C-P in hair","authors":"Ana Y. Simão , Luana M. Rosendo , Pedro Dinis , Cláudia Margalho , Maristela Andraus , Mário Barroso , Eugenia Gallardo","doi":"10.1016/j.sampre.2025.100175","DOIUrl":"10.1016/j.sampre.2025.100175","url":null,"abstract":"<div><div>New psychoactive substances (NPS), including synthetic cathinones and phenethylamines, pose significant challenges due to their evolving chemical structures and health impacts. This study aimed to optimize and validate a methodology for detecting and quantifying a number of synthetic cathinones [methylone, ethylone, pentedrone, 4-chloroethcathinone (4-CEC), penthylone, α-pyrrolidinopentiophenone (α-PVP), 3,4-methylenedioxypyrovalerone (MDPV), 4‑chloro-α-pyrrolidinovalerophenone (4-Cl-α-PVP), as well as phenethylamine 2,5-dimethoxy-4(n)-propylphenethylamine (2C-P)], in hair samples using microextraction by packed sorbent (MEPS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). We developed an environmentally friendly and cost-effective MEPS procedure, which was validated for selectivity, linearity, precision, accuracy, and recovery. Results demonstrated that the method effectively detects analytes with limits of quantification as low as 10 pg/mg. The method successfully identifies MDPV in concentrations consistent with those observed in chronic and acute drug consumption cases, proving its suitability in forensic and clinical toxicology. This approach offers a robust solution for forensic and clinical applications, by combining efficient sample clean-up with precise analytical capabilities.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100175"},"PeriodicalIF":5.2,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A spherical ordered mesoporous silica functionalized with octadecylsilane ligand (SM-C18) was successfully synthesized and characterized, showing 647 m2/g of surface area, 45 Å of pore size, 4–6 μm of particle diameter and 0.37 mmol/g of functionalization degree. 1.5 mg of SM-C18 were packed into EPREP micro-solid phase extraction (µSPEed) cartridges for use with a handheld programmable digital analytical syringe (digiVOL®) to develop a sample preparation protocol for the analysis of two tropane (TAs) and twenty-one pyrrolizidine (PAs) alkaloids. The SM-C18 demonstrated greater retention capacity compared with commercial C18/hydrophilic amorphous silica sorbent. The optimized extraction conditions were as follows: 100 µL of methanol (2 cycles) and 100 µL of H2O (2 cycles) for conditioning, 100 µL of H2O-reconstituted sample (10 cycles), for a total of 1 mL of sample loaded, and 100 µL of methanol (2 cycles) for elution, followed by subsequent analysis by UHPLC-MS/MS. The method was successfully validated, showing good recoveries ranging between 91 and 97 %, low quantification limits and absence of matrix effect for the twenty-tree alkaloids. Additionally, cartridges packed with SM-C18 material allow for better reusability compared to the commercial material, as it has been demonstrated that they can be used for at least 75 extractions. This significantly enhances the method's sustainability. Finally, it was applied to 25 samples of flower extract supplements (FES). In two different batches of the sample obtained from Convolvulus arvensis flowers (FES4a and FES4b), atropine and scopolamine were quantified.
{"title":"Spherical C18-functionalized ordered mesoporous silica packed on micro-solid phase extraction cartridges for simultaneous determination of twenty-three alkaloids in flower extract supplements","authors":"Begoña Fernández-Pintor , Judith Gañán , Damián Pérez-Quintanilla , Sonia Morante-Zarcero , Isabel Sierra","doi":"10.1016/j.sampre.2025.100174","DOIUrl":"10.1016/j.sampre.2025.100174","url":null,"abstract":"<div><div>A spherical ordered mesoporous silica functionalized with octadecylsilane ligand (SM-C18) was successfully synthesized and characterized, showing 647 m<sup>2</sup>/g of surface area, 45 Å of pore size, 4–6 μm of particle diameter and 0.37 mmol/g of functionalization degree. 1.5 mg of SM-C18 were packed into EPREP micro-solid phase extraction (µSPEed) cartridges for use with a handheld programmable digital analytical syringe (digiVOL®) to develop a sample preparation protocol for the analysis of two tropane (TAs) and twenty-one pyrrolizidine (PAs) alkaloids. The SM-C18 demonstrated greater retention capacity compared with commercial C18/hydrophilic amorphous silica sorbent. The optimized extraction conditions were as follows: 100 µL of methanol (2 cycles) and 100 µL of H<sub>2</sub>O (2 cycles) for conditioning, 100 µL of H<sub>2</sub>O-reconstituted sample (10 cycles), for a total of 1 mL of sample loaded, and 100 µL of methanol (2 cycles) for elution, followed by subsequent analysis by UHPLC-MS/MS. The method was successfully validated, showing good recoveries ranging between 91 and 97 %, low quantification limits and absence of matrix effect for the twenty-tree alkaloids. Additionally, cartridges packed with SM-C18 material allow for better reusability compared to the commercial material, as it has been demonstrated that they can be used for at least 75 extractions. This significantly enhances the method's sustainability. Finally, it was applied to 25 samples of flower extract supplements (FES). In two different batches of the sample obtained from <em>Convolvulus arvensis</em> flowers (FES4a and FES4b), atropine and scopolamine were quantified.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100174"},"PeriodicalIF":5.2,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-07DOI: 10.1016/j.sampre.2025.100172
Mussab Uddin , Faizah Mohammad Yunus , Zaharaddeen Muhammad , Muggundha Raoov , Andrew William King , Waleed Alahmad , Sibel A. Ozkan
The emergence of antibiotic contamination in food, water, and environmental matrices has necessitated the development of efficient, sensitive, and environmentally sustainable analytical methods. Deep eutectic solvents (DESs) have attracted significant attention as green alternatives to conventional solvents owing to their tunable properties, low toxicity, and biodegradability. This review comprehensively explores recent advancements in DES-based microextraction techniques for antibiotic detection, including solid-phase microextraction, liquid-liquid microextraction, and vortex-assisted approaches. Integration with cutting-edge analytical instruments, such as high-performance liquid chromatography with mass spectrometry and ion-mobility spectrometry, has enhanced the selectivity and sensitivity of trace-level antibiotics.
Key challenges, such as DES viscosity and scalability, were critically examined alongside emerging solutions, including novel DES formulations and functional additives for improved extraction efficiency. This review underscores the role of DES-based microextraction in facilitating greener analytical practices, and highlights its potential for broader applications in environmental monitoring, pharmaceutical residue analysis, and food safety. By identifying the current limitations and offering strategies for future research, this review provides a valuable resource for advancing sustainable antibiotic extraction approaches.
{"title":"Advances in microextraction techniques utilizing deep eutectic solvents for the extraction of antibiotics","authors":"Mussab Uddin , Faizah Mohammad Yunus , Zaharaddeen Muhammad , Muggundha Raoov , Andrew William King , Waleed Alahmad , Sibel A. Ozkan","doi":"10.1016/j.sampre.2025.100172","DOIUrl":"10.1016/j.sampre.2025.100172","url":null,"abstract":"<div><div>The emergence of antibiotic contamination in food, water, and environmental matrices has necessitated the development of efficient, sensitive, and environmentally sustainable analytical methods. Deep eutectic solvents (DESs) have attracted significant attention as green alternatives to conventional solvents owing to their tunable properties, low toxicity, and biodegradability. This review comprehensively explores recent advancements in DES-based microextraction techniques for antibiotic detection, including solid-phase microextraction, liquid-liquid microextraction, and vortex-assisted approaches. Integration with cutting-edge analytical instruments, such as high-performance liquid chromatography with mass spectrometry and ion-mobility spectrometry, has enhanced the selectivity and sensitivity of trace-level antibiotics.</div><div>Key challenges, such as DES viscosity and scalability, were critically examined alongside emerging solutions, including novel DES formulations and functional additives for improved extraction efficiency. This review underscores the role of DES-based microextraction in facilitating greener analytical practices, and highlights its potential for broader applications in environmental monitoring, pharmaceutical residue analysis, and food safety. By identifying the current limitations and offering strategies for future research, this review provides a valuable resource for advancing sustainable antibiotic extraction approaches.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100172"},"PeriodicalIF":5.2,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577967","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The increasing occurrence of micropollutants and the need for their monitoring in environmental matrices have driven the demand for more efficient and accurate analytical methods. In particular, sample preparation procedures are essential for addressing the complexity of environmental samples while ensuring high sensitivity. To meet these demands, various nanomaterials (NMs) have been proposed as extractive phases for development of miniaturized sorbent-based extraction approaches. These NMs, ranging from carbon-based nanostructures and metal-based or metal oxide nanoparticles, to metal–organic composites, are at the forefront of innovation due to their exceptional surface areas, tunable properties, ease of functionalization and, in some cases, green production routes. On the other hand, the development of (semi)automated platforms has facilitated high-throughput and reproducible sample processing, significantly reducing the use of reagents, time, and labor. This review highlights the pivotal role of NMs and automation in advancing sample preparation methodologies over the past five years, in alignment with green sample preparation (GSP) guidelines. Additionally, the integration of emerging technologies, such as 3D printing, is discussed in the context of developing modern sample preparation methods. Recent contributions involving miniaturized platforms, green nanosorbents, and the integration of processing steps with automation, are evaluated for their potential to provide highly efficient, cost-effective solutions for monitoring micropollutants in environmental matrices.
{"title":"Recent advances in environmental sample preparation: Nanomaterials, automation, and sustainable strategies","authors":"Federico Belén , Julián Gutiérrez , Valeria Springer","doi":"10.1016/j.sampre.2025.100171","DOIUrl":"10.1016/j.sampre.2025.100171","url":null,"abstract":"<div><div>The increasing occurrence of micropollutants and the need for their monitoring in environmental matrices have driven the demand for more efficient and accurate analytical methods. In particular, sample preparation procedures are essential for addressing the complexity of environmental samples while ensuring high sensitivity. To meet these demands, various nanomaterials (NMs) have been proposed as extractive phases for development of miniaturized sorbent-based extraction approaches. These NMs, ranging from carbon-based nanostructures and metal-based or metal oxide nanoparticles, to metal–organic composites, are at the forefront of innovation due to their exceptional surface areas, tunable properties, ease of functionalization and, in some cases, green production routes. On the other hand, the development of (semi)automated platforms has facilitated high-throughput and reproducible sample processing, significantly reducing the use of reagents, time, and labor. This review highlights the pivotal role of NMs and automation in advancing sample preparation methodologies over the past five years, in alignment with green sample preparation (GSP) guidelines. Additionally, the integration of emerging technologies, such as 3D printing, is discussed in the context of developing modern sample preparation methods. Recent contributions involving miniaturized platforms, green nanosorbents, and the integration of processing steps with automation, are evaluated for their potential to provide highly efficient, cost-effective solutions for monitoring micropollutants in environmental matrices.</div></div>","PeriodicalId":100052,"journal":{"name":"Advances in Sample Preparation","volume":"14 ","pages":"Article 100171"},"PeriodicalIF":5.2,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619453","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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