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Recent Development in Subcritical Water Extraction and Chromatography

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

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 16888

Special Issue Editor


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Guest Editor
Department of Chemistry, East Carolina University, Greenville, NC 27858, USA
Interests: pharmaceutical analysis; green chemistry; analytical chemistry; environmental chemistry; subcritical water oxidation; subcritical water extraction and chromatography; supercritical fluid extraction and chromatography; gas chromatography and liquid chromatography; separation and analysis of species from environmental and herbal matrices
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Special Issue Information

Dear Colleagues,

Subcritical water is high-temperature and high-pressure water at conditions below its critical point of 374 °C and 218 atm. Under these conditions, subcritical water can have a wide range of polarity, dissociation constant, viscosity, and surface tension. This unique characteristic of subcritical water makes it a highly useful, green, and economical solvent in extraction, chromatography, environmental remediation, and chemical synthesis. The aim of this Special Issue is to focus on the applications of subcritical water in the extraction of organics from various sample matrices and the chromatographic separation of polar and moderately polar analytes in solution mixtrues. We will also accept research on the fundamentals of subcritical water such as the determination and prediction of organic solubility in subcritical water and chemical decomposition under subcritical water conditions.

Prof. Dr. Yu Yang
Guest Editor

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Keywords

  • Subcritical water
  • Extraction
  • Chromatography
  • Organic solubility
  • Chemical decomposition

Published Papers (8 papers)

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Research

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15 pages, 2417 KiB  
Article
Supercritical Fluid Extraction (SFE) of Polar Compounds from Camellia sinensis Leaves: Use of Ethanol/Water as a Green Polarity Modifier
by Sirine Atwi-Ghaddar, Lydie Zerwette, Emilie Destandau and Eric Lesellier
Molecules 2023, 28(14), 5485; https://doi.org/10.3390/molecules28145485 - 18 Jul 2023
Cited by 7 | Viewed by 1431
Abstract
The use of bioactive plant extracts in cosmetic products is a common practice. Most of these extracts are obtained by maceration in organic solvents, and depending on which solvents are used, the polarity and the structure of the target molecules will vary. Polyphenols [...] Read more.
The use of bioactive plant extracts in cosmetic products is a common practice. Most of these extracts are obtained by maceration in organic solvents, and depending on which solvents are used, the polarity and the structure of the target molecules will vary. Polyphenols are polar compounds that often display antioxidant and/or antibacterial activities. To extract them, ethanol/water mixtures are usually selected as green solvents. This solid–liquid extraction (assisted or not) requires the use of high volumes of solvents and many additional steps like mixing, agitation, filtration, and evaporation. Alternatively, supercritical carbon dioxide (SC-CO2) offers many benefits for plant extraction: economical, non-toxic, and naturally concentrated extracts. However, its low polarity is not suitable to solubilize polar compounds. In this study, an experimental design was used to optimize supercritical fluid extraction (SFE) of caffeine and catechins from Camellia sinensis. Catechins are recognized for skin care use (antioxidant) and caffeine is also used for its skin care properties and to prevent excess storage of fat in cells. The temperature, modifier content, and water additive percentage were used as independent variables. The results showed that while the temperature was an insignificant parameter, a higher percentage of water (up to 20% in ethanol) and modifier favored the extraction of the polar target molecules. Additionally, the SFE results were compared with ultrasound-assisted extraction (UAE). Finally, a sequential selective extraction of caffeine from catechins is also presented. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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20 pages, 2797 KiB  
Article
Degradation and Extraction of Organochlorine Pollutants from Environmental Solids under Subcritical Water Conditions
by Aaryn D. Jones, Andrew T. Morehead, Jr. and Yu Yang
Molecules 2023, 28(14), 5445; https://doi.org/10.3390/molecules28145445 - 16 Jul 2023
Viewed by 921
Abstract
A subcritical water degradation and extraction method was developed to remediate environmental soils contaminated by highly recalcitrant organochlorine pollutants. Hydrogen peroxide was used to effectively decompose organochlorine pollutants under subcritical water conditions. As a method optimization study, the static wet oxidation of chlorophenols [...] Read more.
A subcritical water degradation and extraction method was developed to remediate environmental soils contaminated by highly recalcitrant organochlorine pollutants. Hydrogen peroxide was used to effectively decompose organochlorine pollutants under subcritical water conditions. As a method optimization study, the static wet oxidation of chlorophenols was first performed in subcritical water with and without added hydrogen peroxide. Complete oxidation was achieved using an added oxidant, and thus, the oxidation and extraction of chlorophenols from a sand matrix was then attempted. Complete oxidation and extraction with added oxidant were achieved within 30 min at 100 °C. We then investigated the subcritical water degradation and extraction of dieldrin, mirex, and p,p′-DDD. These organochlorine pesticides were not as easily oxidized as the chlorophenols, and the benefit of adding hydrogen peroxide was only clearly observed at 200 °C. Approximately a 20% increase in degradation was noted for each pesticide and insecticide at this temperature. Unfortunately, this difference was not observed with an increase in temperature to 250 °C, except in some cases, where the amount of degradation byproducts was reduced. Dieldrin and p,p′-DDD were essentially destroyed at 250 °C, while all the pesticides and the insecticides were completely removed from the sand at this temperature. The proposed method was then used to remediate a soil sample highly contaminated with DDT. The soil was obtained from the grounds of an old DDT mixing facility in Virginia and has been aging for several decades. Not only was 100% removal of DDT from this soil achieved using the proposed method at 250 °C, but also, the extracted DDT was completely destroyed during the process. The proposed remediation method, therefore, demonstrates a high potential as an efficient and environmentally sound technique for the detoxification of soils. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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10 pages, 1787 KiB  
Article
Hot Water Extraction of Antioxidants from Tea Leaves—Optimization of Brewing Conditions for Preparing Antioxidant-Rich Tea Drinks
by Yan Cheng, Fumin Xue and Yu Yang
Molecules 2023, 28(7), 3030; https://doi.org/10.3390/molecules28073030 - 28 Mar 2023
Cited by 4 | Viewed by 2529
Abstract
There are billions of tea drinkers around the world. However, the optimized tea-brewing temperature and time conditions for achieving a higher concentration of antioxidants in tea drinks have not been thoroughly studied. Finding out the optimized brewing conditions can benefit tea drinkers significantly. [...] Read more.
There are billions of tea drinkers around the world. However, the optimized tea-brewing temperature and time conditions for achieving a higher concentration of antioxidants in tea drinks have not been thoroughly studied. Finding out the optimized brewing conditions can benefit tea drinkers significantly. In this work, we have studied ten antioxidants from seven different popular green, Oolong, black, and scented teas using hot water extraction followed by HPLC analysis. The antioxidant yield was evaluated at 25–100 °C with 5 to 720 min of brewing time. Our results show that the extraction efficiency was enhanced by increasing the water temperature and the highest yield of antioxidants was achieved at 100 °C. The antioxidant yield increased with prolonged brewing time. However, the degradation of antioxidants occurred when tea leaves were extracted for 120 to 720 min. Caffeine was found in all seven tea samples. At 100 °C, the caffein concentration in the tea extract ranged from 7.04 to 20.4 mg/g in Rizhao green tea. Longjing green tea contained the highest concentration of antioxidants (88 mg/g) in the 100 °C extract. Epigallocatechin and caffeine were the most abundant compounds found in all tea samples studied, ranging from 4.77 to 26.88 mg/g. The antioxidant yield was enhanced by increasing the extraction time to up to 60–120 min for all ten compounds studied. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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19 pages, 3274 KiB  
Article
Liver Protection of a Low-Polarity Fraction from Ficus pandurata Hance, Prepared by Supercritical CO2 Fluid Extraction, on CCl4-Induced Acute Liver Injury in Mice via Inhibiting Apoptosis and Ferroptosis Mediated by Strengthened Antioxidation
by Weibo Dai, Xiaoyan Pang, Weiwen Peng, Xinyi Zhan, Chang Chen, Wenchang Zhao, Congyan Zeng, Quanxi Mei, Qilei Chen, Weihong Kuang, Zhanping Gou and Xianjing Hu
Molecules 2023, 28(5), 2078; https://doi.org/10.3390/molecules28052078 - 22 Feb 2023
Cited by 3 | Viewed by 1739
Abstract
Ficus pandurata Hance (FPH) is a Chinese herbal medicine widely used for health care. This study was designed to investigate the alleviation efficacy of the low-polarity ingredients of FPH (FPHLP), prepared by supercritical CO2 fluid extraction technology, against CCl4-induced acute [...] Read more.
Ficus pandurata Hance (FPH) is a Chinese herbal medicine widely used for health care. This study was designed to investigate the alleviation efficacy of the low-polarity ingredients of FPH (FPHLP), prepared by supercritical CO2 fluid extraction technology, against CCl4-induced acute liver injury (ALI) in mice and uncover its underlying mechanism. The results showed that FPHLP had a good antioxidative effect determined by the DPPH free radical scavenging activity test and T-AOC assay. The in vivo study showed that FPHLP dose-dependently protected against liver damage via detection of ALT, AST, and LDH levels and changes in liver histopathology. The antioxidative stress properties of FPHLP suppressed ALI by increasing levels of GSH, Nrf2, HO-1, and Trx-1 and reducing levels of ROS and MDA and the expression of Keap1. FPHLP significantly reduced the level of Fe2+ and expression of TfR1, xCT/SLC7A11, and Bcl2, while increasing the expression of GPX4, FTH1, cleaved PARP, Bax, and cleaved caspase 3. The results demonstrated that FPHLP protected mouse liver from injury induced by CCl4 via suppression of apoptosis and ferroptosis. This study suggests that FPHLP can be used for liver damage protection in humans, which strongly supports its traditional use as a herbal medicine. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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22 pages, 3165 KiB  
Article
Maillard and Hydrolytic Reactions in Subcritical Water Extraction of Bioactive Compounds from Licorice
by Rui Fan and Yanxiang Gao
Molecules 2022, 27(20), 6851; https://doi.org/10.3390/molecules27206851 - 13 Oct 2022
Cited by 9 | Viewed by 1490
Abstract
Nowadays, subcritical water extraction (SWE) techniques are extensively investigated worldwide, while the thermal reactions that inevitably occur under subcritical water conditions are rarely studied. In order to investigate the behaviors of the different reactions during SWE of bioactive compounds from licorice, the Maillard [...] Read more.
Nowadays, subcritical water extraction (SWE) techniques are extensively investigated worldwide, while the thermal reactions that inevitably occur under subcritical water conditions are rarely studied. In order to investigate the behaviors of the different reactions during SWE of bioactive compounds from licorice, the Maillard reaction process was accessed via their products and the hydrolytic reaction was analyzed according to the kinetic parameters. In addition, the contents of total phenolics and flavonoids in the extracts obtained at the different temperatures were determined and total antioxidant capacities were evaluated by HPLC-ABTS+. The results showed that flavonoids and phenolics from licorice as well as new compounds generated via the Maillard reaction contributed to the antioxidant activity of the extracts. The fluorescence, color and absorbance of the extracts showed that the degree of the Maillard reaction increased with the rise of the extraction temperature. The kinetics of extraction for glycyrrhizic acid showed that it was firstly extracted by diffusion, and then was hydrolyzed into glycyrrhetinic acid 3-O-mono-β-D-glucuronide and glycyrrhetinic acid following a first-order mechanism. These findings could provide deep insights into the SWE process and a new method for producing glycyrrhetinic acid 3-O-mono-β-D-glucuronide and glycyrrhetinic acid. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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Review

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32 pages, 3332 KiB  
Review
New Trends in Supercritical Fluid Technology and Pressurized Liquids for the Extraction and Recovery of Bioactive Compounds from Agro-Industrial and Marine Food Waste
by Horacio Fraguela-Meissimilly, José Miguel Bastías-Monte, Claudia Vergara, Jaime Ortiz-Viedma, Roberto Lemus-Mondaca, Marcos Flores, Pamela Toledo-Merma, Sylvia Alcázar-Alay and Manuela Gallón-Bedoya
Molecules 2023, 28(11), 4421; https://doi.org/10.3390/molecules28114421 - 29 May 2023
Cited by 8 | Viewed by 3556
Abstract
Growing consumer interest in healthy foods has led to an increased demand for bioactive compounds derived from eco-technologies. This review highlighted two emerging technologies, pressurized liquid extraction (PLE) and supercritical fluid extraction (SFE), which are based on clean processes aimed at recovering bioactive [...] Read more.
Growing consumer interest in healthy foods has led to an increased demand for bioactive compounds derived from eco-technologies. This review highlighted two emerging technologies, pressurized liquid extraction (PLE) and supercritical fluid extraction (SFE), which are based on clean processes aimed at recovering bioactive compounds from different food sources. We studied how the different processing conditions provide many advantages and a great opportunity to obtain compounds with antioxidant, antibacterial, antiviral, or antifungal activity from plant matrices and industrial biowaste, especially antioxidant compounds (anthocyanins and polyphenols) due to their important role in health promotion. Our research was conducted through a systematic search in different scientific databases related to the PLE and SFE topics. The review analyzed the optimal extraction conditions using these technologies, which lead to the efficient extraction of bioactive compounds, the use of different equipment, and recent combinations of SFE and PLE with other emerging technologies. This has given rise to the development of new technological innovations, new commercial applications, and the detailed recovery of various bioactive compounds extracted from different plant and marine life food matrices. These two environmentally friendly methodologies are fully valid and have great future application prospects in biowaste valorization. They represent a feasible technological tool that can promote the implementation of a circular economy model for the food industry. The underlying mechanisms of these techniques were discussed in detail and supported by current literature. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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23 pages, 709 KiB  
Review
Solubility and Decomposition of Organic Compounds in Subcritical Water
by Erdal Yabalak, Sema Akay, Berkant Kayan, A. Murat Gizir and Yu Yang
Molecules 2023, 28(3), 1000; https://doi.org/10.3390/molecules28031000 - 19 Jan 2023
Cited by 8 | Viewed by 2825
Abstract
In this article, studies on organic solubility and stability in subcritical water reported during the past 25 years have been reviewed. Data on the solubility and decomposition of organic compounds in subcritical water, a green solvent, are needed in environmental remediation, chemistry, chemical [...] Read more.
In this article, studies on organic solubility and stability in subcritical water reported during the past 25 years have been reviewed. Data on the solubility and decomposition of organic compounds in subcritical water, a green solvent, are needed in environmental remediation, chemistry, chemical engineering, medicine, polymer, food, agriculture, and many other fields. For solubility studies, the experimental systems used to measure solubility, mathematical equations derived and applied for the modeling of the experimentally determined solubility data, and the correlation between the predicated and experimental data have been summarized and discussed. This paper also reviewed organic decomposition under subcritical water conditions. In general, the solubility of organics is significantly enhanced with increasing water temperature. Likewise, the percentage of organic decomposition also increases with higher temperature. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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21 pages, 2260 KiB  
Review
Green Extraction Processes for Complex Samples from Vegetable Matrices Coupled with On-Line Detection System: A Critical Review
by Francisco W. Maciel-Silva, Daniel Lachos-Perez, Luz Selene Buller, William G. Sganzerla, Montserrat Pérez, Mauricio A. Rostagno and Tania Forster-Carneiro
Molecules 2022, 27(19), 6272; https://doi.org/10.3390/molecules27196272 - 23 Sep 2022
Cited by 7 | Viewed by 1534
Abstract
The detection of analytes in complex organic matrices requires a series of analytical steps to obtain a reliable analysis. Sample preparation can be the most time-consuming, prolonged, and error-prone step, reducing the reliability of the investigation. This review aims to discuss the advantages [...] Read more.
The detection of analytes in complex organic matrices requires a series of analytical steps to obtain a reliable analysis. Sample preparation can be the most time-consuming, prolonged, and error-prone step, reducing the reliability of the investigation. This review aims to discuss the advantages and limitations of extracting bioactive compounds, sample preparation techniques, automation, and coupling with on-line detection. This review also evaluates all publications on this topic through a longitudinal bibliometric analysis, applying statistical and mathematical methods to analyze the trends, perspectives, and hot topics of this research area. Furthermore, state-of-the-art green extraction techniques for complex samples from vegetable matrices coupled with analysis systems are presented. Among the extraction techniques for liquid samples, solid-phase extraction was the most common for combined systems in the scientific literature. In contrast, for on-line extraction systems applied for solid samples, supercritical fluid extraction, ultrasound-assisted extraction, microwave-assisted extraction, and pressurized liquid extraction were the most frequent green extraction techniques. Full article
(This article belongs to the Special Issue Recent Development in Subcritical Water Extraction and Chromatography)
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