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1.
Food Chem ; 462: 141024, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39217751

ABSTRACT

With the aim of expanding the potential application scope of mulberries, eleven pH-switchable deep eutectic solvents were screened for the ultrasonic-assisted extraction of mulberry polysaccharides, and a salt/salt aqueous two-phase system was constructed for the efficient separation of mulberry polysaccharides by regulating the system pH. DES-9 (tetraethylammonium chloride: octanoic acid molar ratio = 1: 2) with a critical response pH value of approximately 6.1 was concluded to be the best extraction solvent for extracting mulberry polysaccharides. A maximum polysaccharide extraction yield of 270.71 mg/g was obtained under the optimal conditions. The maximum polysaccharide extraction efficiency was 78.09 % for the pH-driven tetraethylammonium chloride/K2HPO4 aqueous two-phase system. An acidic ß-pyran mulberry polysaccharide with a low-molecular weight of 9.26 kDa and a confirmed monosaccharide composition were obtained. This efficient and environmentally friendly polysaccharide separation method offers a new approach for the efficient extraction and utilization of other plant polysaccharides.


Subject(s)
Deep Eutectic Solvents , Morus , Plant Extracts , Polysaccharides , Morus/chemistry , Polysaccharides/chemistry , Polysaccharides/isolation & purification , Hydrogen-Ion Concentration , Plant Extracts/chemistry , Plant Extracts/isolation & purification , Deep Eutectic Solvents/chemistry , Chemical Fractionation/methods , Molecular Weight , Fruit/chemistry , Sodium Chloride/chemistry
2.
Food Chem ; 462: 141000, 2025 Jan 01.
Article in English | MEDLINE | ID: mdl-39241686

ABSTRACT

Food waste, accounting for about one-third of the total global food resources wasted each year, is a substantial challenge to global sustainability, contributing to adverse environmental impacts. The utilization of food waste as a valuable source for bioactive extraction can be facilitated through the application of DES (Deep Eutectic Solvents). Acknowledging the significant need to tackle this issue, the United Nations integrated food waste management into its Sustainable Development Goals, hence, the present review explores the role of DES in bioactive compounds extraction from food waste. Various extraction processes using the DES system are thoroughly studied and the application of bioactive components as antioxidants, antimicrobials, flavourings, nutraceuticals, functional ingredients, additives, and preservatives is investigated. Most importantly, regulatory considerations and safety aspects of DES in food applications are discussed in-depth along with consumer perception and acceptance of DES in the food sector. The key hypothesis of the review is to evaluate emerging DES systems for their efficiency in bioactive extraction technologies and various food applications. Overall, this review provides a comprehensive understanding of utilizing DES for synthesizing valuable food waste-derived bioactive components, offering a sustainable approach to waste management and the development of high-value products.


Subject(s)
Deep Eutectic Solvents , Sustainable Development , Deep Eutectic Solvents/chemistry , Waste Products/analysis , Waste Management/methods , Humans , Antioxidants/chemistry , Antioxidants/isolation & purification , Food Loss and Waste
3.
Environ Sci Pollut Res Int ; 31(43): 55812-55821, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39245672

ABSTRACT

Organophosphorus pesticides (OPPs) are a group of pesticides that are most widely used in the agricultural sector, and farmers are exposed to these chemicals more than other members of society. In this work, an environmentally friendly, simple, and safe ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) method using alcohol-based hydrophobic deep eutectic solvents (HDESs) followed by gas chromatography-mass spectroscopy (GC-MS) was developed for the extraction and determination of OPPs in the blood of farmers studied in Ravansar cohort. DESs synthesized from thymol as hydrogen bond donor (HBD) and aliphatic alcohols as hydrogen bond acceptor (HBA) have been used as extractants. Under optimal experimental conditions, the reproducibility of the method based on 7 replicate measurements of 10 µg L-1 of OPPs in blood samples was in the range of 1.4-3.8%. The method showed a linearity in the range of 0.01-150 µg L-1. The limits of detection and limits of quantification were between 0.003 and 0.02 µg L-1 and 0.01-0.05 µg L-1, respectively. The matrix effect and accuracy of the method were confirmed by spiking different amounts of OPPs in real blood samples and obtaining relative recoveries in the range of 91-112%. The results showed that the concentration of OPPs in the case group was significantly higher than in the control group, which is because the case group was exposed to OPPs during the spraying of agricultural products.


Subject(s)
Farmers , Gas Chromatography-Mass Spectrometry , Liquid Phase Microextraction , Organophosphorus Compounds , Pesticides , Organophosphorus Compounds/chemistry , Pesticides/blood , Humans , Deep Eutectic Solvents/chemistry , Solvents/chemistry , Hydrophobic and Hydrophilic Interactions , Alcohols/chemistry
4.
Ultrason Sonochem ; 110: 107048, 2024 Nov.
Article in English | MEDLINE | ID: mdl-39241460

ABSTRACT

The present study aims at investigating the application of ultrasound assisted choline chloride (ChCl) - formic acid (FA) deep eutectic solvent (DES) pretreatment of Barley straw. In addition, the efficiency of a wet grinding followed by high intensity ultrasound (HIUS) treatment for production of cellulose nanofibers (CNF) has been evaluated. The DES (using ChCl: FA at 1:9 M ratio) treatment at 45 kHz ultrasound frequency and 3 h of treatment duration resulted in 84.68 ± 1.02 % and 82.96 ± 0.79 % of lignin and hemicellulose solubilisation, respectively. The purification of DES treated solid residue resulted in cellulose with more than 90 % purity. Further, 10 min of wet grinding followed by 40 min of HIUS treatment resulted in more than 80 % nano-fibrillation efficiency. The produced CNF had diameters less than 100 nm in number size distribution and type I cellulose structure. This study confirmed that the developed process offers a sustainable method for producing nanocellulose from agricultural waste.


Subject(s)
Cellulose , Choline , Formates , Hordeum , Hordeum/chemistry , Formates/chemistry , Choline/chemistry , Cellulose/chemistry , Deep Eutectic Solvents/chemistry , Sonication/methods , Ultrasonic Waves
5.
J Agric Food Chem ; 72(37): 20670-20678, 2024 Sep 18.
Article in English | MEDLINE | ID: mdl-39230505

ABSTRACT

Aflatoxins pose a major health concern and require strict monitoring in food products. Existing methods rely on hazardous organic solvents for extraction, prompting the development of a greener alternative. This study explores deep eutectic solvents (DESs) for aflatoxin extraction from pistachios, a valuable food product prone to aflatoxin contamination. The proposed method utilizes DES extraction followed by solid-phase extraction cleanup and ultrahigh-performance liquid chromatography coupled with fluorescence detector analysis. Recovery rates ranged from 85.5 to 99.1% for pistachios spiked with 1-8 ng/g aflatoxins, in compliance with EU regulations, with coefficients of variation less than 2.94%. The method demonstrates good sensitivity with limits of detection and quantification in the range of 0.02-0.22 ng/g and 0.05-0.72 ng/g, respectively. Greenness assessment using AGREEPrep and White Analytical Chemistry metrics confirms its environmental sustainability. This approach offers a promising, safer, and more eco-friendly alternative for aflatoxin extraction from complex food matrices like pistachios.


Subject(s)
Aflatoxins , Deep Eutectic Solvents , Food Contamination , Solid Phase Extraction , Aflatoxins/analysis , Aflatoxins/isolation & purification , Chromatography, High Pressure Liquid/methods , Food Contamination/analysis , Solid Phase Extraction/methods , Solid Phase Extraction/instrumentation , Deep Eutectic Solvents/chemistry , Nuts/chemistry
6.
Mikrochim Acta ; 191(10): 581, 2024 09 07.
Article in English | MEDLINE | ID: mdl-39243346

ABSTRACT

To meet the needs of developing efficient extractive materials alongside the evolution of miniaturized sorbent-based sample preparation techniques, a mesoporous structure of g-C3N4 doped with sulfur as a heteroatom was achieved utilizing a bubble template approach while avoiding the severe conditions of other methods. In an effort to increase the number of adsorption sites, the resultant exfoliated structure was then modified with thymol-coumarin NADES as a natural sorbent modifier, followed by introduction into a nylon 6 polymer via an electrospinning process. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Brunauer-Emmett-Teller (BET) surface area analysis validated S-doped g-C3N4 and composite production. The prepared electrospun fiber nanocomposite, entailing satisfactory processability, was then successfully utilized as a sorbent in on-chip thin film micro-solid-phase extraction of non-steroidal anti-inflammatory drugs (NSAIDs) from saliva samples prior to liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Utilizing a chip device, a thin film µ-SPE coupled with LC-MS/MS analysis yielded promising outcomes with reduced sample solution and organic solvents while extending lifetime of a thin film sorbent. The DES-modified S-doped g-C3N4 amount in electrospun was optimized, along with adsorption and desorption variables. Under optimal conditions, selected NSAIDs were found to have a linear range of 0.05-100.0 ng mL-1 with an R2 ≥ 0.997. The detection limits were ranged between 0.02 and 0.2 ng mL-1. The intra-day and inter-day precisions obtained were less than 6.0%. Relative recoveries were between 93.3 and 111.4%.


Subject(s)
Anti-Inflammatory Agents, Non-Steroidal , Deep Eutectic Solvents , Graphite , Limit of Detection , Nanofibers , Saliva , Tandem Mass Spectrometry , Saliva/chemistry , Tandem Mass Spectrometry/methods , Graphite/chemistry , Nanofibers/chemistry , Humans , Adsorption , Anti-Inflammatory Agents, Non-Steroidal/analysis , Porosity , Deep Eutectic Solvents/chemistry , Chromatography, Liquid/methods , Nitrogen Compounds/chemistry , Solid Phase Microextraction/methods , Solid Phase Extraction/methods
7.
Carbohydr Polym ; 346: 122663, 2024 Dec 15.
Article in English | MEDLINE | ID: mdl-39245517

ABSTRACT

Concerns about food safety and environmental impact from chemical surfactants have prompted interest in natural lignocellulosic materials as alternatives. In this study, we combined hydrated deep eutectic solvent (DES) pretreatment with ultrasound treatment to prepare lignocellulosic nanofibrils (LCNF) from bamboo shoot shells with appropriate surface properties for stabilizing Pickering emulsions. The pretreatment intensity effectively modulated the surface characteristics of LCNF, achieving desirable wettability through lignin retention and in-situ esterification. The resulting LCNF/curcumin Pickering emulsion (CPE) demonstrated curcumin protection and pH-responsive color changes, while the ensuing CPE/PVA composite film exhibited ultraviolet shielding, mechanical strength, oxygen barrier, and antioxidant properties. Furthermore, the CPE/PVA film showed promise as a real-time indicator for monitoring shrimp freshness, maintaining sensitivity to spoilage even after six months of storage. These findings advance the advancement of green LCNF technologies, providing eco-friendly solutions for valorizing bamboo shoot shells and enhancing the application of LCNF in Pickering emulsions.


Subject(s)
Curcumin , Emulsions , Lignin , Nanofibers , Curcumin/chemistry , Lignin/chemistry , Emulsions/chemistry , Animals , Nanofibers/chemistry , Antioxidants/chemistry , Deep Eutectic Solvents/chemistry , Plant Shoots/chemistry , Sasa/chemistry , Wettability , Hydrogen-Ion Concentration
8.
Carbohydr Polym ; 346: 122628, 2024 Dec 15.
Article in English | MEDLINE | ID: mdl-39245529

ABSTRACT

The traditional lignocellulose pretreatment by deep eutectic solvent (DES) was usually conducted under higher acidic, alkaline and high temperature conditions, which leads to the severe degradation of xylan, decreasing the subsequent reducing sugar concentration by enzymatic hydrolysis and further ethanol fermentation. It is essential to develop an effective DES that selectively removes lignin while preventing excessive xylan degradation during lignocellulose pretreatment. An effective ethylene glycol-assisted ternary DES was designed to treat corn straw (CS) at 100 °C for 6 h. 65.51 % lignin removal was achieved, over 93.46 % cellulose and 50.22 % xylan were retained in pretreated CS with excellent enzymatic digestibility (glucan conversion of 77.05 % and xylan conversion of 71.72 %), total sugar conversion could reach 75.93 %, implying the unique capacity to selectively remove lignin while preserving carbohydrate components. Furthermore, the universality of the selective removal of lignin and effective retention of xylan by ternary DES has been successfully proven by other polyols. The enzymatic hydrolysate of ternary DES-pretreated CS fermented over our genetically engineered yeast strain SFA1OE gave a high ethanol yield of 0.488 g/g total reducing sugar, demonstrating the effectiveness of the polyol-assisted ternary DES pretreatment in achieving high-efficiency cellulosic ethanol production.


Subject(s)
Deep Eutectic Solvents , Ethanol , Fermentation , Lignin , Xylans , Zea mays , Lignin/chemistry , Ethanol/chemistry , Ethanol/metabolism , Xylans/chemistry , Hydrolysis , Zea mays/chemistry , Deep Eutectic Solvents/chemistry , Polymers/chemistry , Saccharomyces cerevisiae/metabolism , Cellulose/chemistry , Solvents/chemistry
9.
Bioresour Technol ; 412: 131423, 2024 Nov.
Article in English | MEDLINE | ID: mdl-39236906

ABSTRACT

An innovative binary biol-based deep eutectic solvent (DES), specifically ethylamine hydrochloride-ethylene glycol (EaCl-EG), was developed for efficient pretreatment of eucalyptus biomass. This DES exhibited superior performance in achieving high delignification (85.0%) and xylan removal (80.0%), while preserving a significant amount of cellulose (94.5%) compared to choline chloride-based DES. Notably, the pretreated eucalyptus residues showed a remarkable glucose yield of over 92.5%, representing a substantial enhancement of up to 15 times compared to untreated eucalyptus. Furthermore, the pretreated liquor yielded high-purity lignin with a yield of 97.8%, characterized by well-preserved ß-O-4 structure and nanoscale dimensions. These lignin nanoparticles (LNPs) were subsequently self-assembled into lignin nanobottles (LNBs), adding further value to the pretreatment process. The proposed novel binary EaCl-EG DES presented great potential as an efficient pretreatment solvent for future biomass fractionation processes.


Subject(s)
Biomass , Chemical Fractionation , Deep Eutectic Solvents , Eucalyptus , Lignin , Eucalyptus/chemistry , Lignin/chemistry , Deep Eutectic Solvents/chemistry , Chemical Fractionation/methods , Hydrolysis , Cellulase/metabolism , Cellulase/chemistry , Glucose/chemistry , Solvents/chemistry , Nanoparticles/chemistry
10.
J Chromatogr A ; 1735: 465267, 2024 Oct 25.
Article in English | MEDLINE | ID: mdl-39241404

ABSTRACT

A novel nanofibrous double-layered biosorbent was fabricated by electrospinning polyethersulfone (PES) doped with a natural deep eutectic solvent (DES), composed of choline chloride (ChCl) and caffeic acid (CFA) in a 3:1 molar ratio, onto a bacterial cellulose (BC) substrate. The pristine PES/DES@BC biosorbent was employed in a thin film-solid phase microextraction (TF-SPME) to extract 12 multiclass pesticides from water. Characterization techniques, including ATR-FTIR, FT-NMR, SEM, and nitrogen adsorption/desorption isotherms, confirmed the nanofibrous structure of the electrospun PES-DES and BC biopolymer. The method was validated for matrix effect, specificity, reproducibility, limits of quantification (0.03-0.10 µg/L), and enrichment factor (7-14). Matrix-match calibration linearity ranged from 0.03 to 500 µg/L, with determination coefficients (r²) between 0.9884 and 0.9994. Intra-day and inter-day relative standard deviations (RSDs) were 1.2-3.6 % and 7.0-9.3 %, respectively. The composition of the biosorbent and the fabrication reproducibility across different batches were also thoroughly examined. The accuracy was evaluated by measuring extraction recoveries in six environmental water samples, which ranged from 75 to 105 % (RSDs < 9.0 %). Furthermore, the sustainability of the method was evaluated with the Analytical Eco-Scale and Analytical Greenness metrics. To our knowledge, this study represents the first synthesis and combination of [ChCl:[CFA] DES with PES to create a double-layered nanofiber biosorbent, as well as its application for extracting various pesticide groups from water samples.


Subject(s)
Cellulose , Deep Eutectic Solvents , Nanocomposites , Pesticides , Polymers , Solid Phase Microextraction , Sulfones , Water Pollutants, Chemical , Nanocomposites/chemistry , Cellulose/chemistry , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Polymers/chemistry , Pesticides/analysis , Pesticides/isolation & purification , Deep Eutectic Solvents/chemistry , Reproducibility of Results , Solid Phase Microextraction/methods , Sulfones/chemistry , Limit of Detection , Nanofibers/chemistry , Adsorption , Green Chemistry Technology/methods
11.
Int J Mol Sci ; 25(18)2024 Sep 17.
Article in English | MEDLINE | ID: mdl-39337480

ABSTRACT

Pomegranate (Punica granatum L.) peel is a potential source of bioactive phenolic compounds such as ellagic acid and α- and ß-punicalagin. This work explores the efficiency of natural deep eutectic solvents combined with ultrasound-assisted extraction (UAE) and pressurized liquid extraction (PLE) for their extraction. Five NaDESs were evaluated by employing UAE (25 °C, for 50 min) to determine their total phenolic content (Folin-Ciocalteu assay) and ellagic acid and α- and ß-punicalagin contents (high-performance liquid chromatography (HPLC-DAD)). The NaDES composed of choline chloride (ChCl) and glycerol (Gly) (1:2, molar ratio) was the most efficient in the UAE when compared with the rest of the NaDESs and water extracts. Therefore, ChCl:Gly was further evaluated using PLE at different temperatures (40, 80, 120 and 160 °C). The PLE-NaDES extract obtained at 80 °C for 20 min at 1500 psi exhibited the highest contents of ellagic acid and α- and ß-punicalagin compared to the rest of the temperatures and PLE-water extracts obtained under the same extraction conditions. Combining UAE or PLE with a NaDES emerges as a sustainable alternative for extracting ellagic acid and α- and ß-punicalagin from pomegranate peel.


Subject(s)
Ellagic Acid , Phenols , Plant Extracts , Pomegranate , Pomegranate/chemistry , Phenols/chemistry , Phenols/isolation & purification , Phenols/analysis , Plant Extracts/chemistry , Ellagic Acid/chemistry , Ellagic Acid/isolation & purification , Deep Eutectic Solvents/chemistry , Chromatography, High Pressure Liquid/methods , Hydrolyzable Tannins/chemistry , Hydrolyzable Tannins/isolation & purification , Fruit/chemistry , Solvents/chemistry
12.
Talanta ; 279: 126666, 2024 Nov 01.
Article in English | MEDLINE | ID: mdl-39116727

ABSTRACT

In this work, coacervation in primary amines solutions with hydrophobic natural deep eutectic solvents based on terpenoids and carboxylic acids was demonstrated for the first time. A liquid-phase microextraction approach was developed based on supramolecular solvent formation with primary amine acting as amphiphile and hydrophobic deep eutectic solvent making up mixed vesicles and serving as coacervation agent. Such supramolecular solvents could be used to separate wide range of substances from different aqueous media, such as food products, biological liquids and wastewaters. It is important that both hydrophobic and ionic interactions with supramolecular aggregates take place ensuring synergetic effect and better extraction ability, which is significant in separating relatively polar analytes. Different primary amines and deep eutectic solvents were investigated for liquid-phase microextraction of proof-of-concept amphoteric analyte (enrofloxacin, widely used veterinary fluoroquinolone antibiotic) and its determination by high-performance liquid chromatography with fluorescence detection using Shimadzu LC-20 Prominence chromatograph and RF-20A fluorescence detector. It was found that the supramolecular solvent based on 1-nonylamine, formed after addition of a deep eutectic solvent based on menthol and hexanoic acid (molar ratio of 1:1), provided maximum extraction recovery (85 %) and maximum enrichment factor (34). To characterize the extraction system, the composition of the phases was investigated, and cryo-transmission electron microscopy images were obtained. Vesicular aggregates were observed in the supramolecular solvent. The extraction mechanism was proposed in terms of formation of mixed aggregates to capture the analyte. Limit of detection was found to be 7 µg kg-1, while linear range of 20-250 µg kg-1 was established. Relative standard deviation values were lower than 7 %. Relative bias did not exceed 12 %.


Subject(s)
Amines , Deep Eutectic Solvents , Enrofloxacin , Hydrophobic and Hydrophilic Interactions , Liquid Phase Microextraction , Milk , Enrofloxacin/analysis , Milk/chemistry , Animals , Amines/chemistry , Amines/analysis , Deep Eutectic Solvents/chemistry , Liquid Phase Microextraction/methods , Chromatography, High Pressure Liquid/methods , Menthol/chemistry , Menthol/analysis , Limit of Detection , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/chemistry , Solvents/chemistry , Caprylates/chemistry , Caprylates/analysis , Food Contamination/analysis , Caproates
13.
Int J Biol Macromol ; 277(Pt 3): 134425, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39097065

ABSTRACT

In this study, deep eutectic solvent (DES) prepared from choline chloride, lactic acid, and one of the four polyols (ethylene glycol, glycerol, xylitol, and sorbitol) were compared and assessed for their effectiveness in extracting chitin from lobster shells. Our results revealed that as the number of hydroxyl groups in polyols increased, the hydrogen bond network within the DESs became denser. However, this led to a corresponding increase in viscosity, which impacted the efficiency of chitin extraction. Among all prepared DESs, choline chloride-lactic acid/glycerol (CCLaGly) exhibited superior extractive ability, resulting in the extraction of pure chitin from lobster shells. The purity, crystallinity, and molecular weight of the extracted chitin using CCLaGly DES were comparable to those of chemically-isolated chitin, with purity reaching 94.76 ± 0.33 %, crystallinity at 78.78 %, and a molecular weight of 655 kDa. Additionally, the physicochemical properties of the DES-extracted chitins were characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy. This study conducted a comparative analysis of polyol effects on chitin extraction from lobster shells, thereby opening a promising avenue for the utilization of various crustacean shells in sustainable biomaterial production.


Subject(s)
Animal Shells , Chitin , Deep Eutectic Solvents , Polymers , Chitin/chemistry , Chitin/isolation & purification , Animals , Polymers/chemistry , Animal Shells/chemistry , Deep Eutectic Solvents/chemistry , Viscosity , Molecular Weight , Solvents/chemistry , Spectroscopy, Fourier Transform Infrared , X-Ray Diffraction , Nephropidae/chemistry
14.
Int J Biol Macromol ; 277(Pt 3): 134295, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39098673

ABSTRACT

Complete valorization of lignocellulosic biomass is crucial for bio-based biorefineries to fulfil the circular bioeconomy concept. However, the existence of lignin carbohydrate complexes (LCC) in biomass hinders the simultaneous fractionation of biomass components, such as lignin, hemicellulose and cellulose, for subsequent biorefining processes. This study explores for the first time a novel approach tailored for the deconstruction of sorghum biomass components through efficient breakdown of LCC. Selective targeting of the major LCC linkages binding xylan and lignin was performed using an ultrasound-assisted deep eutectic solvent under mild treatment conditions. This process yielded a maximum cellulose content of 98.3 %, hemicellulose content of 95.2 %, and lignin content of 94.6 %, with the highest purities of 99.43 %, 96.71 %, and 98.12 %, respectively. FTIR, 2D-HSQC NMR and XRD analyses confirmed that most of the structural properties of lignin, hemicellulose, cellulose are retained. The lignocellulosic components were successfully valorised to cellulose, hemicellulose, and lignin nanoparticles with mean sizes of 64.5 ± 6 nm, 72.8 ± 4 nm and 57.2 ± 8 nm respectively, with good thermal stability. The proposed green process enables the complete utilization of agro-residue feedstock for the preparation of biomass-derived nanoparticles, thereby accelerating the economic and industrial prospects of bio-based biorefineries.


Subject(s)
Biomass , Cellulose , Lignin , Nanoparticles , Polysaccharides , Sorghum , Lignin/chemistry , Sorghum/chemistry , Polysaccharides/chemistry , Cellulose/chemistry , Nanoparticles/chemistry , Deep Eutectic Solvents/chemistry , Chemical Fractionation/methods , Green Chemistry Technology
15.
J Sep Sci ; 47(15): e2400275, 2024 Aug.
Article in English | MEDLINE | ID: mdl-39091185

ABSTRACT

In this study, we propose a novel strategy utilizing deep eutectic solvents (DESs) as both the extraction solvent and dispersing liquid, with nanometer zinc oxide (ZnO) serving as the adsorbent. This method incorporates ultrasound-assisted matrix solid phase dispersion (UA-MSPD) for the extraction of six active components (salidroside, echinacoside, acteoside, specnuezhenide, nuezhenoside G13, and oleanolic acid) from Ligustri Lucidi Fructus samples. The extracts were then analyzed using high-performance liquid chromatography equipped with a diode array detector. The effects of various parameters such as dispersant dosage, DESs volume, grinding time, ultrasonication duration, and eluent volume on extraction recovery were investigated and optimized using a central composite design under response surface methodology. The optimized conditions yielded detection limits ranging from 0.003 to 0.01 mg/g and relative standard deviations of 8.7% or lower. Extraction recoveries varied between 93% and 98%. The method demonstrated excellent linearity for the analytes (R2 ≥ 0.9997). The simple, green, and efficient DESs/ZnO-UA-MSPD technique proved to be rapid, accurate, and reliable for extracting and analyzing the six active ingredients in Ligustri Lucidi Fructus samples.


Subject(s)
Ligustrum , Solid Phase Extraction , Ultrasonic Waves , Zinc Oxide , Solid Phase Extraction/methods , Zinc Oxide/chemistry , Ligustrum/chemistry , Deep Eutectic Solvents/chemistry , Chromatography, High Pressure Liquid , Fruit/chemistry , Plant Extracts/chemistry , Plant Extracts/analysis , Particle Size , Solvents/chemistry
16.
Anal Chim Acta ; 1320: 343007, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-39142784

ABSTRACT

BACKGROUND: Personalized medicine is a rapidly revolving field that offers new opportunities for tailoring disease treatment to individual patients. The main idea behind this approach is to carefully select safe and effective medications and treatment plant based on each patient's unique pharmacokinetic profile. Isoniazid is a first-line anti-tuberculosis drug that has interindividual variability in its metabolic processing, leading to significant differences in plasma concentrations among patients receiving equivalent doses. This variability necessitates the creation of individualized treatment regimens as part of personalized medicine to achieve more effective therapy. RESULTS: In this work, a deep eutectic solvent-based liquid-liquid microextraction approach for the separation and determination of isoniazid in human plasma by high-performance liquid chromatography with UV-Vis detection was developed for the first time. A new natural deep eutectic solvent based on thymol as a hydrogen bond donor and 4-methoxybenzaldehyde as a hydrogen bond acceptor was proposed as the extraction solvent. The developed microextraction procedure assumed two simultaneous processes during the mixing of the sample and extraction solvent: the derivatization of the polar analyte in the presence of 4-methoxybenzaldehyde (component of the natural deep eutectic solvent) with the formation of a hydrophobic Schiff base (1); mass transfer of the Schiff base from the sample phase to the extraction solvent phase (2). Under optimal conditions, the limits of detection and quantification were 20 and 60 µg L-1, respectively. The RSD value was <10 %, the extraction recovery was 95 %. SIGNIFICANCE: In this work, the possibility of isoniazid derivatization in the natural deep eutectic solvent phase with the formation of the Schiff base was presented for the first time. The approach provided the separation and preconcentration of polar isoniazid without the use of expensive derivatization agents and solid-phase extraction cartridges. The formation of the Schiff base was confirmed by mass spectrometry.


Subject(s)
Deep Eutectic Solvents , Isoniazid , Liquid Phase Microextraction , Isoniazid/blood , Isoniazid/chemistry , Isoniazid/isolation & purification , Humans , Liquid Phase Microextraction/methods , Deep Eutectic Solvents/chemistry , Chromatography, High Pressure Liquid/methods , Antitubercular Agents/blood , Antitubercular Agents/isolation & purification , Antitubercular Agents/chemistry
17.
Molecules ; 29(15)2024 Jul 25.
Article in English | MEDLINE | ID: mdl-39124900

ABSTRACT

Cellulose and lignin, sourced from biomass, hold potential for innovative bioprocesses and biomaterials. However, traditional fractionation and purification methods often rely on harmful chemicals and high temperatures, making these processes both hazardous and costly. This study introduces a sustainable approach for fractionating acacia wood, focusing on both cellulose and lignin extraction using a deep eutectic solvent (DES) composed of choline chloride (ChCl) and levulinic acid (LA). A design of experiment was employed for the optimization of the most relevant fractionation parameters: time and temperature. In the case of the lignin, both parameters were found to be significant variables in the fractionation process (p-values of 0.0128 and 0.0319 for time and temperature, respectively), with a positive influence. Likewise, in the cellulose case, time and temperature also demonstrated a positive effect, with p-values of 0.0103 and 0.028, respectively. An optimization study was finally conducted to determine the maximum fractionation yield of lignin and cellulose. The optimized conditions were found to be 15% (w/v) of the wood sample in 1:3 ChCl:LA under a treatment temperature of 160 °C for 8 h. The developed method was validated through repeatability and intermediate precision studies, which yielded a coefficient of variation lower than 5%. The recovery and reuse of DES were successfully evaluated, revealing remarkable fractionation yields even after five cycles. This work demonstrates the feasibility of selectively extracting lignin and cellulose from woody biomass using a sustainable solvent, thus paving the way for valorization of invasive species biomass.


Subject(s)
Acacia , Cellulose , Chemical Fractionation , Deep Eutectic Solvents , Lignin , Wood , Lignin/chemistry , Lignin/isolation & purification , Cellulose/chemistry , Acacia/chemistry , Wood/chemistry , Chemical Fractionation/methods , Deep Eutectic Solvents/chemistry , Solvents/chemistry , Temperature , Biomass
18.
Molecules ; 29(15)2024 Aug 02.
Article in English | MEDLINE | ID: mdl-39125075

ABSTRACT

Banana peels, comprising about 35% of the fruit's weight, are often discarded, posing environmental and economic issues. This research focuses on recycling banana peel waste by optimizing advanced extraction techniques, specifically microwave-assisted (MAE) and ultrasound-assisted extraction (UAE), for the isolation of phenolic compounds. A choline chloride-based deep eutectic solvent (DES) with glycerol in a 1:3 ratio with a water content of 30% (w/w) was compared to 30% ethanol. Parameters, including sample-to-solvent ratio (SSR), extraction time, and temperature for MAE or amplitude for UAE, were varied. Extracts were analyzed for hydroxycinnamic acid (HCA) and flavonoid content, and antioxidant activity using FRAP and ABTS assays. DES outperformed ethanol, with HCA content ranging from 180.80 to 765.92 mg/100 g and flavonoid content from 96.70 to 531.08 mg/100 g, accompanied by higher antioxidant activity. Optimal MAE conditions with DES were an SSR of 1:50, a temperature of 60 °C, and a time of 10 min, whereas an SSR of 1:60, time of 5 min, and 75% amplitude were optimal for UAE. The polyphenolic profile of optimized extracts comprised 19 individual compounds belonging to the class of flavonols, flavan-3-ols, and phenolic acids. This study concluded that DESs, with their superior extraction efficiency and environmental benefits, are promising solvents for the extraction of high-value bioactive compounds from banana peels and offer significant potential for the food and pharmaceutical industries.


Subject(s)
Antioxidants , Deep Eutectic Solvents , Musa , Phenols , Plant Extracts , Musa/chemistry , Phenols/chemistry , Phenols/isolation & purification , Phenols/analysis , Antioxidants/chemistry , Antioxidants/isolation & purification , Plant Extracts/chemistry , Plant Extracts/isolation & purification , Deep Eutectic Solvents/chemistry , Flavonoids/chemistry , Flavonoids/isolation & purification , Fruit/chemistry , Microwaves , Green Chemistry Technology/methods , Solvents/chemistry
19.
Int J Mol Sci ; 25(15)2024 Jul 29.
Article in English | MEDLINE | ID: mdl-39125847

ABSTRACT

Lignin, the second most abundant natural polymer, is a by-product of the biorefinery and pulp and paper industries. This study was undertaken to evaluate the properties and estimate the prospects of using lignin as a by-product of the pretreatment of common reed straw (Phragmites australis) with deep eutectic solvents (DESs) of various compositions: choline chloride/oxalic acid (ChCl/OA), choline chloride/lactic acid (ChCl/LA), and choline chloride/monoethanol amine (ChCl/EA). The lignin samples, hereinafter referred to as Lig-OA, Lig-LA, and Lig-EA, were obtained as by-products after optimizing the conditions of reed straw pretreatment with DESs in order to improve the efficiency of subsequent enzymatic hydrolysis. The lignin was studied using gel penetration chromatography, UV-vis, ATR-FTIR, and 1H and 13C NMR spectroscopy; its antioxidant activity was assessed, and the UV-shielding properties of lignin/polyvinyl alcohol composite films were estimated. The DES composition had a significant impact on the structure and properties of the extracted lignin. The lignin's ability to scavenge ABTS+• and DPPH• radicals, as well as the efficiency of UV radiation shielding, decreased as follows: Lig-OA > Lig-LA > Lig-EA. The PVA/Lig-OA and PVA/Lig-LA films with a lignin content of 4% of the weight of PVA block UV radiation in the UVA range by 96% and 87%, respectively, and completely block UV radiation in the UVB range.


Subject(s)
Antioxidants , Deep Eutectic Solvents , Lignin , Poaceae , Ultraviolet Rays , Lignin/chemistry , Antioxidants/chemistry , Antioxidants/pharmacology , Deep Eutectic Solvents/chemistry , Poaceae/chemistry , Green Chemistry Technology/methods , Solvents/chemistry
20.
J Sep Sci ; 47(17): e2400340, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39215580

ABSTRACT

In this work, an easy, safe, simple, and efficient pH-switchable deep eutectic solvents (DESs)-based liquid phase microextraction followed by high-performance liquid chromatography-diode array detector analysis was developed for the determination of 1,3-dimethylamylamine (DMAA). The switchability of the obtained DESs was investigated by changing the pH. Then the best-selected DES was characterized and the application of the selected DES in the extraction of DMAA from sports nutrition and bodybuilding supplements was investigated. The DES synthesized from l-menthol: oleic acid in a molar ratio of 1:2 had the highest efficiency in the extraction of the target compound. Under the optimum conditions, (50 µL of DES, 100 µL of 4 mol/L KOH, 100 µL of 4 mol/L HCl, extraction time of 40 s and without salt addition) the calibration graph was linear in the range of 0.05-100 µg/kg and limit of detection was 0.02 µg/kg. The relative standard deviations including intra-day and inter-day for 10.0 µg/kg of DMAA in real samples were 2.7% (n = 7) and 5.3% (n = 7), respectively. The enrichment factor and percentage extraction recovery of the method were 283 and 85%, respectively. The relative recoveries for DMAA in different samples were in the range of 90%-109%.


Subject(s)
Deep Eutectic Solvents , Dietary Supplements , Chromatography, High Pressure Liquid , Dietary Supplements/analysis , Hydrogen-Ion Concentration , Deep Eutectic Solvents/chemistry , Amines/analysis , Amines/chemistry , Liquid Phase Microextraction
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