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Deep Eutectic Solvents in Analytical Chemistry
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Deep Eutectic Solvents in Analytical Chemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Analytical Chemistry".

Deadline for manuscript submissions: closed (31 January 2022) | Viewed by 16517

Special Issue Editors

Dr. Giovanni D'Orazio

E-Mail Website
Guest Editor
Cnr- Consiglio Nazionale delle Ricerche Instituto per i Sistemi Biologici (ISB), Rome, Italy
Interests: HPLC; nano-LC; capillary electrophoresis; electrochromatography; mass spectrometry; micro extraction; sample preparation; chiral separations; food analysis; pharmaceutical analysis
Special Issues, Collections and Topics in MDPI journals
Dr. Chiara Dal Bosco

E-Mail Website
Assistant Guest Editor
Department of Chemistry, Sapienza University, P.le Aldo Moro 5, 00185 Rome, Italy
Interests: eco-friendly synthesis of new sorbent materials and neoteric solvents for green sample preparation; development of sustainable sample preparation techniques; liquid chromatography; mass spectrometry; organic micronutrient profiling of foods and biological fluids; analysis of emerging contaminants in foodstuffs; environmental and biological samples
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Since its introduction in 1987, Green Analytical Chemistry (GAC) has been assuming more and more importance, as attested to by the growing number of publications in this field. In particular, from the description of deep eutectic solvents (DESs) by Abbott in 2003 until now, a huge number of papers dealing with the analytical application as neoteric solvents of many kinds of DESs, especially hydrophilic, has been published. Very recently, the interest has moved toward the introduction of hydrophobic DESs for extraction purposes. These solvents, similarly to low transition temperature mixtures (LTTMs), can be considered green, since they are characterized by negligible vapor pressure, low flammability, and a lower toxicity compared to traditional solvents derived from petroleum.

Analytical research on this topic is running faster than the physicochemical studies of these materials, so that there is still a lack of clear and unambiguous definitions of what a DES is. Therefore, despite definitions and the wait for a more rigorous and comprehensive classification, this Special Issue addresses any eutectic liquid of analytical interest (DES, LTTM, (D)ES, etc.) and, as far as possible, in compliance with GAC principles, with the aim of collecting the latest advances in this topic and original applications in the analytical field. These may encompass the use of eutectic solvents as alternative solvents for green sample preparation (for example, for dissolution or digestion of solid samples, as eluent after dispersive solid-phase extraction, as extraction solvent in dispersive liquid–liquid microextraction, etc.), as well as their use as mobile phase additives/modifiers in chromatography.

We warmly invite our colleagues to submit their original contributions (such as research manuscripts, short communications, or reviews) to this Special Issue, believing that the wide collection of the latest knowledge in this field can stimulate new connections between researchers and new ideas for a sustainable development of analytical chemistry.

Dr. Giovanni D'Orazio

Dr. Chiara Dal Bosco 

Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Deep eutectic solvents
  • Eutectic solvents
  • Low transition temperature mixtures
  • Hydrophobic deep eutectic solvents
  • Hydrophilic deep eutectic solvents
  • Sample preparation
  • Microextraction techniques
  • Green analytical chemistry
  • Extraction techniques
  • Environmentally friendly methods
  • Sustainable chromatography

Published Papers (6 papers)

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Research

11 pages, 1292 KiB  
Article
Eutectic Thin-Layer Chromatography as a New Possibility for Quantification of Plant Extracts—A Case Study
by Danuta Raj
Molecules 2022, 27(9), 2960; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27092960 - 05 May 2022
Cited by 2 | Viewed by 2225
Abstract
Deep eutectic solvents (DES), compared to classic ones, have interesting properties, such as the ability to solubilize compounds differing in polarity or increased dissolution of selected chemical compounds. They also offer specific interactions between the mobile and stationary phases. Those features make them [...] Read more.
Deep eutectic solvents (DES), compared to classic ones, have interesting properties, such as the ability to solubilize compounds differing in polarity or increased dissolution of selected chemical compounds. They also offer specific interactions between the mobile and stationary phases. Those features make them promising solvents in chromatographic techniques, including the use in the separation of complicated samples. The first quantitative analysis with eutectic thin-layer chromatography (TLC) is presented in the paper. As a case study, five alkaloids from Chelidonium maius were selected as target compounds. A wide range of terpene-based DESs was investigated to develop the chromatographic system, both pure and after dilution. Moreover, a novel approach was employed to adjust polarity, involving mixing DESs differing in chromatographic properties. This procedure has proved to be effective. The best results were obtained with a 2:1 (wt/wt) mixture of DESs: camphor + phenol and menthol + limonene, with a 20% addition of methanol. The chromatographic system was validated and checked on the real sample, which made it the first applicable and operational quantitative eutectic TLC system. Full article
(This article belongs to the Special Issue Deep Eutectic Solvents in Analytical Chemistry)
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14 pages, 1844 KiB  
Article
Natural Deep Eutectic Solvents as a Key Metal Extractant for Fractionation in Speciation Analysis
by Lena Ruzik and Aleksandra Dyoniziak
Molecules 2022, 27(3), 1063; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27031063 - 04 Feb 2022
Cited by 3 | Viewed by 1435
Abstract
The research aimed to use natural deep eutectic solvents (NADES) as an extractant for fractionation of compounds of selected elements from young barley and to compare it with the fractionation of elements from certified element materials. The use of such a comparison made [...] Read more.
The research aimed to use natural deep eutectic solvents (NADES) as an extractant for fractionation of compounds of selected elements from young barley and to compare it with the fractionation of elements from certified element materials. The use of such a comparison made it possible to prove the possibility of extracting the same forms of elements (species) from different materials, which confirmed the option of using NADES as extractants in speciation analysis. The research was conducted with hyphenated techniques—separation by high-performance chromatography coupled to an isotope-specific detector, mass spectrometry (MS) with ionization in inductively coupled plasma (ICP)—which are widely used in speciation analysis. Natural deep eutectic solvents also help introduce Green Analytical Chemistry principles (GAC). According to the results of our studies, the use of different NADES permit the extraction of various metals from a single sample. Moreover, using other natural solvents of eutectic properties helps extract different species of a given metal. Full article
(This article belongs to the Special Issue Deep Eutectic Solvents in Analytical Chemistry)
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19 pages, 6000 KiB  
Article
A Green Method of Extracting and Recovering Flavonoids from Acanthopanax senticosus Using Deep Eutectic Solvents
by Xinyu Zhang, Jianqing Su, Xiuling Chu and Xiaoya Wang
Molecules 2022, 27(3), 923; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27030923 - 29 Jan 2022
Cited by 28 | Viewed by 3133
Abstract
In recent years, green extraction of bioactive compounds from herbal medicines has generated widespread interest. Deep eutectic solvents (DES) have widely replaced traditional organic solvents in the extraction process. In this study, the efficiencies of eight DESs in extracting flavonoids from Acanthopanax senticosus [...] Read more.
In recent years, green extraction of bioactive compounds from herbal medicines has generated widespread interest. Deep eutectic solvents (DES) have widely replaced traditional organic solvents in the extraction process. In this study, the efficiencies of eight DESs in extracting flavonoids from Acanthopanax senticosus (AS) were compared. Response surface methodology (RSM) was employed to optimize the independent variable including ultrasonic power, water content, solid-liquid ratio, extraction temperature, and extraction time. DES composed of glycerol and levulinic acid (1:1) was chosen as the most suitable extraction medium. Optimal conditions were ultrasonic power of 500 W, water content of 28%, solid-liquid ratio of 1:18 g·mL−1, extraction temperature of 55 °C, and extraction time of 73 min. The extraction yield of total flavonoids reached 23.928 ± 0.071 mg·g−1, which was 40.7% higher compared with ultrasonic-assisted ethanol extraction. Macroporous resin (D-101, HPD-600, S-8 and AB-8) was used to recover flavonoids from extracts. The AB-8 resin showed higher adsorption/desorption performance, with a recovery rate of total flavonoids of up to 71.56 ± 0.256%. In addition, DES solvent could efficiently be reused twice. In summary, ultrasonic-assisted DES combined with the macroporous resin enrichment method is exceptionally effective in recovering flavonoids from AS, and provides a promising environmentally friendly and recyclable strategy for flavonoid extraction from natural plant sources. Full article
(This article belongs to the Special Issue Deep Eutectic Solvents in Analytical Chemistry)
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14 pages, 729 KiB  
Article
Application of a Liquid-Liquid Microextraction Method Based on a Natural Hydrophobic Deep Eutectic Solvent for the Extraction of Plastic Migrants from Kombuchas
by Antonio V. Herrera-Herrera, Ruth Rodríguez-Ramos, Álvaro Santana-Mayor, Bárbara Socas-Rodríguez and Miguel Ángel Rodríguez-Delgado
Molecules 2022, 27(1), 178; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27010178 - 28 Dec 2021
Cited by 8 | Viewed by 1830
Abstract
A vortex-assisted liquid-liquid microextraction, based on a natural hydrophobic deep eutectic solvent made from the monoterpene thymol and octanoic fatty acid, was employed for the analysis of 11 phthalate esters and one adipate in kombucha (a tea-based fermented beverage). Separation and determination were [...] Read more.
A vortex-assisted liquid-liquid microextraction, based on a natural hydrophobic deep eutectic solvent made from the monoterpene thymol and octanoic fatty acid, was employed for the analysis of 11 phthalate esters and one adipate in kombucha (a tea-based fermented beverage). Separation and determination were performed using an ultra-high performance liquid chromatography (UHPLC) system coupled to a single quadrupole mass spectrometer. Confirmatory analyses were carried out through UHPLC tandem mass spectrometry. The full method was validated in terms of matrix effect, matrix-matched calibration, sensitivity, recovery, limits of detection and quantification and repeatability. Satisfactory determination coefficients for quadratic calibration curves (≥0.9938), recovery values (67–120%) and limits of detection (0.07–5.45 µg/L) were obtained. Analysis of 26 kombucha samples reported concentrations for dibutyl phthalate and dimethyl phthalate in the range between the limit of quantification (LOQ) and 16.18 ± 1.14 µg/L, although these phthalates were also detected under the LOQ in some of the analyzed samples. Only one of the samples bottled in plastic containers (7) did not present residues while only five of the 19 samples in glass bottles contained any plasticizer. However, the highest concentration was found in a kombucha bottled in food-grade glass. This work represents the first application in which phthalates and adipates are analyzed in kombuchas. Full article
(This article belongs to the Special Issue Deep Eutectic Solvents in Analytical Chemistry)
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15 pages, 1756 KiB  
Article
Choline Chloride–Lactic Acid-Based NADES As an Extraction Medium in a Response Surface Methodology-Optimized Method for the Extraction of Phenolic Compounds from Hazelnut Skin
by Chiara Fanali, Valeria Gallo, Susanna Della Posta, Laura Dugo, Leone Mazzeo, Marco Cocchi, Vincenzo Piemonte and Laura De Gara
Molecules 2021, 26(9), 2652; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26092652 - 01 May 2021
Cited by 42 | Viewed by 4289
Abstract
Deep eutectic solvents (DESs) are promising green solvents for the extraction of compounds from food byproducts. Hazelnut (Corylus avellana L.) is one of the most commonly cultivated tree nuts worldwide. The skin represents one of the major byproducts of the hazelnut [...] Read more.
Deep eutectic solvents (DESs) are promising green solvents for the extraction of compounds from food byproducts. Hazelnut (Corylus avellana L.) is one of the most commonly cultivated tree nuts worldwide. The skin represents one of the major byproducts of the hazelnut industry and accounts for 2.5% of the total hazelnut kernel weight. It is a rich source of phenolic compounds like flavan-3-ols, flavonols, dihydrochalcones, and phenolic acids. In this work, fifteen DESs based on choline chloride and betaine, with different compositions, were studied in order to test their phenolic compounds extraction efficiency through the determination of their total concentration via Folin–Ciocalteu assay. A qualitative analysis of extracted phenolic compounds was assessed by HPLC with UV and MS detection. Using the DES with the best extraction efficiency, a new ultrasound-assisted solid liquid extraction (UA-SLE) method was optimized though the response surface methodology (RSM), taking into account some extraction parameters. Efficient recovery of extracted phenolic compounds was achieved using a 35% water solution of choline chloride and lactic acid (molar ratio 1:2) as an extraction solvent, working at 80 °C and with a solid-to-solvent ratio of 1:25 gmL−1. The optimized conditions made it possible to recover 39% more phenolic compounds compared to a classic organic solvent. Full article
(This article belongs to the Special Issue Deep Eutectic Solvents in Analytical Chemistry)
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11 pages, 2463 KiB  
Article
Screening, Optimization, and Bioavailability Research of Natural Deep Eutectic Solvent Extracts from Radix Pueraria
by Yan Huang, Jiehong Yang, Yu Zhao, Li Yu, Yu He, Haitong Wan and Chang Li
Molecules 2021, 26(3), 729; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26030729 - 31 Jan 2021
Cited by 17 | Viewed by 2761
Abstract
Natural deep eutectic solvent (NaDES) is generally considered as a greener alternative to fossil solvent, with great potential in various areas. In the present work, 25 different NaDESs were screened for the extraction of puerarin (PUE) and its two natural derivatives from Radix [...] Read more.
Natural deep eutectic solvent (NaDES) is generally considered as a greener alternative to fossil solvent, with great potential in various areas. In the present work, 25 different NaDESs were screened for the extraction of puerarin (PUE) and its two natural derivatives from Radix Pueraria (RP). As the main isoflavone in RP, PUE has a wide range of biological activities. However, its application is restricted due to its poor solubility in water and low oral bioavailability. In this study, the extraction of PUE with NaDESs showed significant advantages compared with traditional solvents. While using L-Pro-Maa (L-proline-malic acid) under optimal conditions, the optimized yields of PUE, 3-MPR and PRX were 98.7 mg/g, 16.3 mg/g and 9.9 mg/g, respectively, which were 2.2-, 2.9- and 3.4-fold higher than that of water. Furthermore, the oral bioavailability of PUE in NaDES extracts was comparatively investigated in rats with HPLC-MS technique. Pharmacokinetic analysis revealed that the relative bioavailability of PUE in L-Pro-Maa extract is 323%. The result indicated that NaDES is not only a sustainable ionic liquid with higher extraction efficiency, but also an enhancer of oral bioavailability of specific natural products. Full article
(This article belongs to the Special Issue Deep Eutectic Solvents in Analytical Chemistry)
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