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Set de datos (Dataset). 2022

Chromatographic data for the determination of sulfonamides in waters associated to Fig. 7 (in CSV) of the paper "Preparation and further evaluation of L-menthol-based natural deep eutectic solvents as supported liquid membrane for the hollow fiber liquid-phase microextraction of sulfonamides from environmental waters" published in Advances in Sample Preparation, Díaz-Álvarez, Myriam [0000-0002-0243-9848], Martín Esteban, Antonio [0000-0003-0498-5153]

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Díaz-Álvarez, Myriam
  • Martín Esteban, Antonio
Data were automatically generated by the instrument., In this work, the use of a hydrophobic natural deep eutectic solvent (NADES) as supported liquid membrane (SLM) for hollow fiber liquid-phase microextraction (HF-LPME) of sulfonamides is proposed. The combination of formic acid:L-menthol (1:1) was selected as optimum. The optimized HF-LPME procedure was applied to the analysis of an artificial water containing humic acids, tap and river water samples by HPLC with UV detection at 268 nm. The chromatographic data associated to Fig.7 of paper published in Advances of Sample Preparation are provided as csv files as follows:
Fig7Aa: Milli-Q water; Fig7Ab; artificial water; Fig7Ba: Tap water (a); Fig7Bb: Manzanares river; Fig7Bc: Jarama river. All the samples were spiked with selected sulfonamides at 10 µg/L concentration level., "Hacia un analisis medioambiental verde: nuevos disolventes, materiales y dispositivos (GREENNESS)" (Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe”)., Fig7Aa_Díaz-Álvarez and Martín-Esteban_SAMPRE.csv, Fig7Ab_Díaz-Álvarez and Martín-Esteban_SAMPRE.csv, Fig7Ba_Díaz-Álvarez and Martín-Esteban_SAMPRE.csv, Fig7Bb_Díaz-Álvarez and Martín-Esteban_SAMPRE.csv, Fig7Bc_Díaz-Álvarez and Martín-Esteban_SAMPRE.csv, Peer reviewed




Artículo científico (JournalArticle). 2023

Recent advances and future trends in molecularly imprinted polymers-based sample preparation

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Díaz-Álvarez, Myriam
  • Turiel Trujillo, Esther
  • Martín Esteban, Antonio
18 Pág., Molecular imprinting technology is a well-established technique for the obtainment of tailor-made polymers, so-called molecularly imprinted polymers, with a predetermined selectivity towards a target analyte or structurally related compounds. Accordingly, molecularly imprinted polymers are considered excellent materials for sample preparation providing unprecedented selectivity to analytical methods. However, the use of molecularly imprinted polymers in sample preparation still presents some shortcomings derived from the synthesis procedure itself limiting its general applicability. In this regard, molecularly imprinted polymers use to display binding sites heterogeneity and slow diffusion mass transfer of analytes to the imprinted sites affecting their overall performance. Besides, the performance of molecularly imprinted polymers in organic solvents is excellent, but their selective binding ability in aqueous media is considerably reduced. Accordingly, the present review pretends to provide an updated overview of the recent advances and trends of molecularly imprinted polymers-based extraction, focusing on those strategies proposed for the improvement of mass transfer and selective recognition in aqueous media. Besides, with the progressive implementation of Green Chemistry principles, the different steps and strategies for the preparation of molecularly imprinted polymers are reviewed from a green perspective., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed




Set de datos (Dataset). 2023

FT-IR spectra of selected NADES and their components (L-menthol and formic acid) associated to Figures S1 (in CSV) of the paper "Hydrophobic natural deep eutectic solvents based on L-menthol as supported liquid membrane for hollow fiber liquid-phase microextraction of triazines from water and urine samples" to be published in Microchemical Journal

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Díaz-Álvarez, Myriam
  • Turiel Trujillo, Esther
  • Martín Esteban, Antonio
In this work, the use of a hydrophobic natural deep eutectic solvent (NADES) as supported liquid membrane (SLM) for hollow fiber liquid-phase microextraction (HF-LPME) of triazines is proposed. The combination of formic acid:L-menthol (2:1) was selected as optimum. FT-IR spectra of selected NADES and its components associated to Fig. S1 of paper submitted to Microchemical Journal are provided as csv files as follow: FigS1 (menthol); FigS1 (formic acid); FigS1 /NADES)., "Hacia un analisis medioambiental verde: nuevos disolventes, materiales y dispositivos (GREENNESS)" (Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe”), FigS1 (menthol)_Díaz-Álvarez, Turiel and Martín-Esteban.csv, FigS1 (formic acid)_Díaz-Álvarez, Turiel and Martín-Esteban.csv, FigS1 (NADES)_Díaz-Álvarez, Turiel and Martín-Esteban.csv, Peer reviewed




Set de datos (Dataset). 2023

Chromatographic data for the determination of triazines in water and urine samples associated to Figures 6 and 7 (in CSV) of the paper "Hydrophobic natural deep eutectic solvents based on L-menthol as supported liquid membrane for hollow fiber liquid-phase microextraction of triazines from water and urine samples" to be published in Microchemical Journal

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Díaz-Álvarez, Myriam
  • Turiel Trujillo, Esther
  • Martín Esteban, Antonio
In this work, the use of a hydrophobic natural deep eutectic solvent (NADES) as supported liquid membrane (SLM) for hollow fiber liquid-phase microextraction (HF-LPME) of triazines is proposed. The combination of formic acid:L-menthol (2:1) was selected as optimum.
The optimized HF-LPME procedure was applied to the analysis of an artificial water containing humic acids, tap and river water, and urine samples by HPLC with UV detection at 268 nm. The chromatographic data associated to Fig.6 and 7 of paper submitted to Microchemical Journal are provided as csv files as follows:
Fig6a: Milli-Q water; Fig6b; artificial water; Fig7a: Tap water; Fig7b: River water; Fig7c: Urine river. All the samples were spiked with selected sulfonamides at 5 µg/L concentration level., "Hacia un analisis medioambiental verde: nuevos disolventes, materiales y dispositivos (GREENNESS)" (Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe”)., Fig6a_Díaz-Álvarez_Turiel and Martín-Esteban.csv, Fig6b_Díaz-Álvarez_Turiel and Martín-Esteban.csv, Fig7a_Díaz-Álvarez_Turiel and Martín-Esteban.csv, Fig7b_Díaz-Álvarez_Turiel and Martín-Esteban.csv, Fig7c_Díaz-Álvarez_Turiel and Martín-Esteban.csv, Peer reviewed




Artículo científico (JournalArticle). 2023

Combined cytotoxicity of ZnO nanoparticles and chlorpyrifos in the rainbow trout, Oncorhynchus mikyss, gonadal cell line RTG-2

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Sánchez Argüello, Paloma
  • Franco, Daniel
  • Fernández, M. Dolores
9 Pág., The toxicity of ZnO nanoparticles (ZnO NPs) in aquatic organisms has been extensively studied, but little information is available on the effects associated with their interaction with other contaminants. In this context, the in vitro effects of co-exposure of chlorpyrifos (CPF) and ZnO NPs on fish-derived cells were investigated. A selection of concentrations was tested in single and binary exposures: CPF (0.312 - 75 mg/L) and ZnO NPs (10 - 100 mg/L). Cytotoxicity was measured using commonly used cellular endpoints: Alamar Blue/CFDA-AM for viability and plasma membrane integrity, NRU for lysosomal disruption and MTT for mitochondrial function. In addition, specific mechanisms of toxicity for CPF and ZnO NPs were tested: acetylcholinesterase (AChE) activity and ROS generation, respectively. AChE was by far the most sensitive assay for single exposure to CPF. There was no concentration-response relationship for ROS after single exposure to ZnO NPs, but 10 mg/L produced significant effects only for this cellular endpoint. Co-exposure of CPF with 10 m/L of ZnO NPs produced significant effects in almost all endpoints tested, which were enhanced by co-exposure with 100 mg/L of ZnO NPs. AChE testing of additional co-exposures with bulk ZnO, together with the application of the Independent Action (IA) prediction model, which allowed us to draw more in-depth conclusions on the toxicological behavior of the mixture. Synergism was observed at 0.625 mg/L CPF concentration and antagonism at 5 mg/L CPF in mixtures containing 100 mg/L of both ZnO NPs and bulk ZnO. However, more cases of synergism between CPF and ZnO NPs occurred at intermediate CPF concentrations, demonstrating that nano-sized particles have a more toxic interaction with CPF than bulk ZnO. Therefore it can be argued that in vitro assays allow the identification of interaction profiles of NP-containing mixtures by achieving multiple endpoints with a large number of concentration combinations., The Grant PID2021–122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” and the funding of the project S2018/BAA-4330 of the Community of Madrid are gratefully acknowledged., Peer reviewed




Artículo científico (JournalArticle). 2023

Hydrophobic natural deep eutectic solvents based on L-menthol as supported liquid membrane for hollow fiber liquid-phase microextraction of triazines from water and urine samples

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Díaz-Álvarez, Myriam
  • Turiel Trujillo, Esther
  • Martín Esteban, Antonio
This work proposes the use of a hydrophobic natural deep eutectic solvent (NADES) as a supported liquid membrane (SLM) for hollow fiber liquid phase microextraction (HF-LPME) of triazines. NADES were prepared using L-menthol as hydrogen bond acceptor combined with different hydrogen bond donors of natural origin: carboxlylic acids, alcohols and amines. Studies were carried out to determine whether the prepared NADES met the necessary requirements to be used as a SLM, such as stability in the HF and compatibility with HPLC. Then, the ability of each prepared NADES to extract 6 triazine herbicides by HF-LPME from aqueous samples was evaluated. Among them, the mixture L-menthol: formic acid (molar ratio 1:2) provided better extraction results and was selected as SLM. The influence the different parameters on extraction efficiency such as pH of both sample and acceptor solution, salting-out effect, extraction time and stirring rate on the extraction efficiency was carefully studied and optimized. The optimized HF-LPME procedure was applied to the analysis of aqueous samples such as artificial water containing humic acids, tap water, river water and urine, with excellent clean-up ability for all samples analyzed. Relative recoveries ranged from 68 to 128 %, and the LODs and LOQs obtained for the 6 triazines were 0.75–3.1 µg/L and 2.5–10.3 µg/L, respectively, depending on the analyte and the kind of sample. Additionally, according to the AGREEprep tool assessment, the proposed method appears as a greener approach compared to other microextraction methods reported in the literature for the analysis of triazines in water samples., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the National Thematic Network on Sustainable Sample Treatment (RED2022-134079-T) funded by the Spanish Ministry of Science and Innovation, and the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed




Artículo científico (JournalArticle). 2024

Natural deep eutectic solvents as sustainable alternative for the Ultrasound-Assisted extraction of triazines from agricultural soils

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Turiel Trujillo, Esther
  • Díaz-Álvarez, Myriam
  • Martín Esteban, Antonio
9 Pág., Natural deep eutectic solvents (NADES) have gained much attention as a viable and sustainable alternative to traditional organic solvents in multiple areas of analytical chemistry, including extraction of contaminants from samples of environmental concern. In this work, a total of 68 potential NADES have been assayed and further evaluated as sustainable solvents in the development of an ultrasound (US)-assisted extraction method for triazinic herbicides from agricultural soil samples and final determination by HPLC-UV. Choline chloride (ChCl) was used as hydrogen bond acceptor (HBA), and different carboxylic acids, alcohols and amines were tested as hydrogen bond donors (HBDs) in different molar ratios in order to find the optimum combination able to form appropriated NADES for the extraction of triazines. Among the different ChCl:carboxylic acids mixtures tested, those consisting of ChCl:formic acid and ChCl:acetic acid, both in a molar ratio 1:2, presented the better physico-chemical properties (pH, stability at room temperature, water miscibility, etc.). Concerning amines, NADES could not be obtained at any of the combination assayed whereas, among the alcohols tested, 2,3-butanediol was found to be the most appropriated for NADES formation. A three-level factorial design was then used to further evaluate the effect of time and temperature on the ability of these selected optimum NADES for the US-assisted extraction of triazines from agricultural soil samples. Under optimal conditions, the developed US-assisted extraction method provided quantitative recoveries (from 87 to 104 %) with good reproducibility (RSDs lower than 12 %) and limits of detection (LODs) lower than 0.05 μg g−1 for all target triazines., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the National Thematic Network on Sustainable Sample Treatment (RED2022-134079-T) funded by the Spanish Ministry of Science and Innovation, and the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society. Authors wish thank Mar Albarrán for supplying soil samples., Peer reviewed




Artículo científico (JournalArticle). 2024

Evaluation of deep eutectic solvents in the synthesis of molecularly imprinted fibers for the solid-phase microextraction of triazines in soil samples

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Monnier, Alexia
  • Díaz-Álvarez, Myriam
  • Turiel Trujillo, Esther
  • Martín Esteban, Antonio
11 Pág., Nowadays, molecularly imprinted polymers (MIPs) are well established and are considered excellent materials for performing selective extractions. However, with the progressive implementation of the principles of green chemistry, it is necessary to find greener alternatives for both the synthesis and further use of MIPs in sample preparation. Accordingly, in the present work, different deep eutectic solvents (DES, both hydrophilic and hydrophobic), as an alternative to conventional organic solvents (i.e., toluene), were evaluated as porogens for the synthesis of imprinted fibers (monoliths), using fused silica capillaries as molds, for solid-phase microextraction (SPME). From this study, the polymer prepared with propazine (dummy template), methacrylic acid (monomer), ethylene glycol dimethacrylate (cross-linker), and a formic acid:L-menthol (1:1) DES (porogen) showed the best performance for selective rebinding of triazines. After optimization of the different variables involved in SPME, the new imprinted fibers were successfully applied to the extraction of target analytes (desisopropylatrazine, desethylatrazine, simazine, and atrazine) from soil sample extracts, providing relative recoveries ranging from 75.7 to 120.1%, reaching limits of detection within the range of 6.2-15.7 ng g-1, depending upon the analyte., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the National Thematic Network on Sustainable Sample Treatment (RED2022-134079-T) funded by the Spanish Ministry of Science and Innovation, and the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature., Peer reviewed




Artículo científico (JournalArticle). 2024

Ultrasound-assisted extraction of sulfonamides from soil samples using natural deep eutectic solvents and their determination by liquid chromatography tandem mass spectrometry

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • García Valcárcel, Ana Isabel
  • Martín Esteban, Antonio
8 Pág., In this work, several potential natural deep eutectic solvents (NADES) were evaluated as sustainable solvents in the development of an ultrasound (US)-assisted extraction method for sulfonamides from soil samples and final determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Choline chloride (ChCl) was used as hydrogen bond acceptor (HBA), and different carboxylic acids and alcohols were tested as hydrogen bond donors (HBDs) in different molar ratios in order to find the optimum combination able to form appropriated NADES for the extraction of sulfonamides. Among the different mixtures tested, the one consisting of ChCl:1,3-propanediol in a molar ratio of 1:4 showed the better physico-chemical properties and was selected for the US-assisted extraction of sulfonamides. Under optimum conditions, no matrix effect was observed and quantitative recoveries, ranging from 81.9 % to 103.9 % with relative standard deviations (RSDs) lower than 8 % were obtained, reaching limits of quantification within the range 8.5–31 µg Kg−1, depending upon the analyte. In addition, after evaluation by AGREEprep, Sample Preparation Metric of Sustainability (SPMS) and Blue Applicability Grade Index (BAGI) metrics tools, the proposed method was found to be superior to other published methods in terms of safety and environmental impact with good applicability potential., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the National Thematic Network on Sustainable Sample Treatment (RED2022-134079-T) funded by the Spanish Ministry of Science and Innovation, and the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society. Authors wish to thanks Jennifer Ayala and Esther Turiel for their collaboration in the experimental work and for fruitful comments and discussions during the development of the present work., Peer reviewed




Artículo científico (JournalArticle). 2024

AGREEMIP: The Analytical Greenness Assessment Tool for Molecularly Imprinted Polymers Synthesis

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Marć, Mariusz
  • Wojnowski, Wojciech
  • Pena-Pereira, Francisco
  • Tobiszewski, Marek
  • Martín Esteban, Antonio
9 Pág., Molecular imprinting technology is well established in areas where a high selectivity is required, such as catalysis, sensing, and separations/sample preparation. However, according to the Principles of Green Chemistry, it is evident that the various steps required to obtain molecularly imprinted polymers (MIPs) are far from ideal. In this regard, greener alternatives to the synthesis of MIPs have been proposed in recent years. However, although it is intuitively possible to design new green MIPs, it would be desirable to have a quantitative measure of the environmental impact of the changes introduced for their synthesis. In this regard, this work proposes, for the first time, a metric tool and software (termed AGREEMIP) to assess and compare the greenness of MIP synthesis procedures. AGREEMIP is based on 12 assessment criteria that correspond to the greenness of different reaction mixture constituents, energy requirements, and the details of MIP synthesis procedures. The input data of the 12 criteria are transformed into individual scores on a 0-1 scale that in turn produce an overall score through the calculation of the weighted average. The assessment can be performed using user-friendly open-source software, freely downloadable from mostwiedzy.pl/agreemip. The assessment result is an easily interpretable pictogram and visually appealing, showing the performance in each of the criteria, the criteria weights, and overall performance in terms of greenness. The application of AGREEMIP is presented with selected case studies that show good discrimination power in the greenness assessment of MIP synthesis pathways., Grant PID2021-122327OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed




Artículo científico (JournalArticle). 2025

Natural deep eutectic solvent-based liquid phase microextraction in a 3D-Printed millifluidic flow cell for the on-line determination of thiabendazole in juice samples

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Díaz-Álvarez, Myriam
  • Turiel Trujillo, Esther
  • Martín Esteban, Antonio
Background: At present, 3D printing technology is becoming increasingly popular in analytical chemistry because it enables the rapid and cost-effective manufacture of sample preparation devices, particularly in flow-based operation, opening up new opportunities for the development of automated analytical methods. In parallel, the use of miniaturised methods and sustainable solvents in sample preparation is highly recommended. Accordingly, in this work, a 3D-printed millifluidic device was designed and used for the on-line natural deep eutectic solvent (NADES)-based liquid phase microextraction (LPME) coupled to a spectrofluorometer for, as a proof of concept, the determination of thiabendazole (TBZ) in fruit juice samples.
Results: The millifluidic device was 3D printed by stereolithography and consisted of two patterned plates, each containing a millichannel (acceptor and donor channel). The millichannels were separated by a polypropylene membrane impregnated with optimal NADES, acting as a supported liquid membrane (SLM). Among the NADES investigated, formic acid:L-menthol (1:1 molar ratio) was selected as the SLM, avoiding the use of
conventional harmful organic solvents. The proposed millifluidic device was successfully applied to the determination of thiabendazole in fruit juice samples, achieving LOD and LOQ values of 0.45 μg.L-1 and 1.42 μg.L-1, respectively, which are well below the maximum residue levels (MRLs) set by the European Union. The greenness and applicability of the proposed analytical method were evaluated using the AGREEPrep, SPMS and BAGI tools and compared with other published methods. In general, the proposed method was superior to others, mainly due to its high sensitivity and high sample throughput.
Significance: Several cells were easily designed with different channel geometries (length and depth) to find the optimal dimensions, and then 3D printed and tested in a relatively fast, cheap and simple way, demonstrating the suitability of 3D printing in the fabrication of millifluidic devices as an alternative to traditional fabrication techniques. In addition, the proposed approach is fully compatible with new sustainable solvents, facilitating the development of green sample preparation methods., The Grant PID2021-122327OB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged., Peer reviewed




Artículo científico (JournalArticle). 2024

Bisphenols determination in seminal fluid by miniaturized stir bar sorptive dispersive microextraction as a potential tool in male infertility studies

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • López-Juan, Andreu L.
  • Vállez-Gomis, Víctor
  • Benedé, Juan L.
  • Martín Esteban, Antonio
  • Chisvert, Alberto
In this work, an analytical method for the determination of bisphenols in seminal fluid is presented. These compounds are related to the deterioration in sperm quality due to their highly endocrine disruptive activity. The method is based on miniaturized stir bar sorptive dispersive microextraction (mSBSDME), and the extract is analyzed by liquid chromatography coupled to tandem mass spectrometry. Prior to the extraction, precipitation of the proteins from the sample was conducted with acetonitrile and, subsequently, the supernatant was evaporated and reconstituted in water. Next, a hydrophilic-lipophilic polymer-coated magnetic nanoparticles composite was used as magnetic sorbent in mSBSDME. The ratio of magnetic nanoparticles and polymer used for the synthesis of the sorbent was firstly optimized. A Plackett-Burman design was employed for the evaluation of the critical variables involved in the microextraction step, which were then optimized employing response surface methodologies. Under the optimized conditions, the proposed method was validated, obtaining satisfactory linearity (up to 50 ng mL−1), enrichment factors (6.3–13.6), limits of detection in the low ng mL−1 range, and precision (relative standard deviation below 12 %). Finally, the method was successfully applied to seminal fluid samples from eight volunteers, detecting bisphenol A (BPA) and bisphenol S (BPS) in most of them. This methodology not only broadens the analytical potential of mSBSDME for other complex and low-volume matrices but also contributes to the monitorization of the population exposure to bisphenols and would allow determining its relationship with male reproductive effects in subsequent clinical studies., Grants PID2020-118924RB-I00 and PID2021-122327OB-I00 funded by Spanish Ministry of Science and Innovation (MICIU/AEI/10.13039/501100011033) and by “ERDF A way of making Europe” are greatly appreciated. A.L.L-J also thanks the Generalitat Valencia for the INVESTIGO contract through the project INVEST/2022/109. This article is based upon work from the National Network for Sustainable Sample Preparation (RED2022-134079-T funded by MICIU/AEI/ 10.13039/501100011033) and the Sample Preparation Study Group and Network supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed




Artículo científico (JournalArticle). 2025

Natural deep eutectic solvent-based matrix solid-phase dispersion-ultrasound assisted extraction of pesticides in pears and their determination by liquid chromatography-tandem mass spectrometry

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • García Valcárcel, Ana Isabel
  • Miguel, Esther
  • Martín Esteban, Antonio
In recent years, natural deep eutectic solvents (NADES) have been proposed as sustainable solvents capable of replacing the conventional harmful organic solvents typically used in sample preparation. In this regard, in this work, several NADES have been evaluated for the development of a matrix solid phase dispersion - ultrasound-assisted extraction (MSPD-UAE) method for selected pesticides (thiamethoxam, thiacloprid, pirimicarb, acetamiprid and tebuconazole) from pear (peel and pulp) samples and final determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Among the different NADES and dispersants tested, the one consisting of choline chloride:1,3-propanediol in a 1:4 molar ratio combined with alumina showed the best performance. The effect of the amount of dispersant, the volume of NADES, the temperature of the ultrasonic bath and the duration of sonication was then optimised using response surface methodology (RSM) based on a four-factor, three-level Box-Behnken design. Under optimal conditions, no matrix effect was observed and quantitative recoveries, ranging from 78.5 to 120 % with relative standard deviations (RSDs) lower than 20 % were obtained, reaching limits of quantification within the range 4–10 ng g-1, depending upon the analyte. In addition, after evaluation by Analytical Greenness Metric for Sample Preparation (AGREEprep), Sample Preparation Metric of Sustainability (SPMS) and Blue Applicability Grade Index (BAGI) metrics tools, the proposed method was found to be superior to other published methods in terms of safety and environmental impact with good applicability potential., Grant PID2021-122327OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. This article is based upon work from the National Thematic Network on Sustainable Sample Treatment (RED2022-134079-T) funded by the Spanish Ministry of Science and Innovation, and the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed




Artículo científico (JournalArticle). 2025

Assessment of the greenness of molecularly imprinted polymers used in sample preparation

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Marć, Mariusz
  • Martín Esteban, Antonio
It is now widely accepted that the incorporation of molecularly imprinted polymers (MIPs) into sample preparation techniques has enabled unprecedented selectivity performance of analytical methods for the determination of a wide range of analytes in biological, food and environmental samples. However, according to the Principles of Green Chemistry and the subsequent Principles of Green Sample Preparation, it is clear that MIPs are far from being considered green materials, both due to the common harmful reagents and the experimental conditions used for their synthesis. Accordingly, new greener routes for MIP synthesis have been proposed in recent years. However, although the titles of some of the published papers include terms such as 'green MIP' or 'sustainable MIP', such improved properties have only been assessed intuitively and it is therefore unclear whether such claimed green or sustainable MIPs are actually so. Therefore, in the present review, published papers using apparently green MIPs in sample preparation were evaluated using the recently developed metric tool AGREEMIP. Such a tool is based on the assessment of 12 criteria related to the greenness of the different reagents used, energy requirements and other aspects of MIP synthesis procedures. The final values of performed AGREEMIP assessment ranged from 0.28 to 0.80. The scores obtained after the AGREEMIP assessment clearly show that, although slight improvements have been achieved in terms of greenness, there is an abuse of the use of green-related terms and further development is needed. In this context, some guidelines for greening MIPs are provided., Grant PID2021–122327OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” is gratefully acknowledged. Financial support of these studies from Gdansk University of Technology by the DEC-6/1/2024/IDUB/II.1b/Am grant under the Americium International Career Development - ‘Excellence Initiative - Research University’ program is gratefully acknowledged. This article is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed




Artículo científico (JournalArticle). 2025

Ecotoxicological assessment of different choline chloride-based natural deep eutectic solvents: in vitro and in vivo approaches

DIGITAL.CSIC. Repositorio Institucional del CSIC
  • Sánchez Argüello, Paloma
  • Martín Esteban, Antonio
Natural Deep Eutectic Solvents (NADES) have emerged over the last decade as a promising alternative to organic solvents. NADES are mixtures of two or more natural components interacting each other by hydrogen bonds to form a supramolecular mixture. Efforts have focused on demonstrating their lack of toxicity by studying the responses of different taxonomic groups. In this study, fish cells (RTG-2 line) and freshwater invertebrate embryos (Physa acuta) were used for the ecotoxicological assessment of seven choline chloride (ChCl)-based NADES. Three organic acids and four alcohols were used for the preparation of the NADES investigated. In a first step, the in vitro cytotoxicity of a single exposure to each NADES component, binary mixtures of their corresponding components and the prepared NADES were evaluated. The rank order of in vitro cytotoxicity of the individual components was: organic acids > ChCl > alcohols. NADES produced equal or lower cytotoxic effects than the corresponding mixtures, suggesting that NADES have their own toxicological behaviour, possibly supported by the maintenance of their supramolecular structure up to certain aqueous dilutions. Furthermore, the in vitro assessment showed that NADES prepared with acids were more cytotoxic than NADES prepared with alcohols, which was confirmed by the in vivo assessment. NADES prepared with acids produced embryo lethal effects from 0.025 % at short exposures (48h). For NADES prepared with alcohols embryo toxicity was found from 0.2 %. From our results, it can be concluded that ecotoxicological assessment can help in the selection of component combinations for the design of safe NADES., The authors would like to thank Naroa Ontibero, who spent four months in our laboratory during her undergraduate studies at the University of Alcala de Henares. The Grant PID2021-122327OB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF a way of making Europe” is gratefully acknowledged. This article is based upon work from the Sample Preparation Study Group and Network, supported by the Division of Analytical Chemistry of the European Chemical Society., Peer reviewed