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1.
J Biotechnol ; 391: 106-116, 2024 Aug 10.
Article in English | MEDLINE | ID: mdl-38871028

ABSTRACT

Icaritin, a hydrolysate from total flavonoids of Epimedii (TFE), which has better anti-hepatoma activity than its glycosylated form. In this work, immobilized enzymes 4LP-Tpebgl3@Na-Y and DtRha@ES-107 were used to hydrolyze TFE to prepare icaritin. Five different hydrophobic deep eutectic solvents (HDES) were prepared and the most ideal HDES was successfully selected, which was composed of dodecyl alcohol and thymol with the molar ratio of 2:1. The relative enzyme activity of 4LP-Tpebgl3@Na-Y and DtRha@ES-107 was about 102.4 % and 112.5 %, respectively. In addition, the thermal and binding stability of 4LP-Tpebgl3@Na-Y and DtRha@ES-107 in HDES was not affected negatively. In the biphasic system composed of 50 % (v/v) HDES and Na2HPO4-citric acid buffer (50 mM, pH 5.5), 4LP-Tpebgl3@Na-Y (1.0 U/mL) and TFE (1 g/L) were reacted at 80 °C for 1 h, and then reacted with DtRha@ES-107 (20 U/mL) at 80 °C for 2 h. Finally, TFE was completely converted to 301.8 mg/L icaritin (0.82 mM). After 10 cycles, 4LP-Tpebgl3@Na-Y/DtRha@ES-107 still maintained 84.1 % original activity. In this study, we developed an efficient methodology for icaritin preparation through the integration of enzymatic catalysis and adsorption separation, presenting a viable approach for large-scale, cost-effective production of icaritin.


Subject(s)
Biotransformation , Enzymes, Immobilized , Flavonoids , Hydrophobic and Hydrophilic Interactions , Flavonoids/metabolism , Flavonoids/chemistry , Enzymes, Immobilized/metabolism , Enzymes, Immobilized/chemistry , Deep Eutectic Solvents/chemistry , Deep Eutectic Solvents/metabolism , Epimedium/chemistry , Epimedium/metabolism , Hydrolysis , Solvents/chemistry
2.
Mar Drugs ; 22(6)2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38921592

ABSTRACT

The growing demand for phycobiliproteins from microalgae generates a significant volume of by-products, such as extraction cakes. These cakes are enriched with products of interest for the cosmetics market, namely free fatty acids, particularly polyunsaturated (PUFA). In this work, two cakes, one of spirulina and one of Porphyridium cruentum, were valorized using innovative natural hydrophobic deep eutectic solvents (NaDES) based on alkanediols. The most promising NaDES, as determined by physicochemical properties and screening, are mixtures of alkanediols and fatty acids. These include the mixtures of 1,3-propanediol and octanoic acid (1:5, mol/mol) and 1,3-propanediol and octanoic and decanoic acid (1:3:1, mol/mol). Two extractive processes were implemented: ultrasound-assisted extraction and an innovative mechanical process involving dual asymmetric centrifugation. The second process resulted in the production of extracts significantly enriched in PUFA, ranging from 65 to 220 mg/g dry matter with the two cakes. The extracts and NaDES demonstrated good safety with respect to epidermal keratinocyte viability (>80% at 200 µg/mL). The study of their impact on commensal and pathogenic cutaneous bacteria demonstrated significant effects on the viability of Staphylococcus aureus and Staphylococcus epidermidis (>50% decrease at 200 µg/mL) while preserving Corynebacterium xerosis and Cutibacterium acnes. These results highlight the potential of valorizing these co-products using alkanediol-based NaDES, in a strategy combining an active vector (NaDES) and a growth regulator extract, for the management of cutaneous dysbiosis involving staphylococci.


Subject(s)
Fatty Acids, Nonesterified , Spirulina , Spirulina/chemistry , Humans , Deep Eutectic Solvents/chemistry , Microalgae/chemistry , Keratinocytes/drug effects , Cosmetics/chemistry , Dermatologic Agents/pharmacology , Dermatologic Agents/chemistry , Aquatic Organisms
3.
J Mater Chem B ; 12(25): 6102-6116, 2024 Jun 27.
Article in English | MEDLINE | ID: mdl-38836422

ABSTRACT

Physical eutectogels as a newly emerging type of conductive gel have gained extensive interest for the next generation multifunctional electronic devices. Nevertheless, some obstacles, including weak mechanical performance, low self-adhesive strength, lack of self-healing capacity, and low conductivity, hinder their practical use in wearable strain sensors. Herein, lignin as a green filler and a multifunctional hydrogen bond donor was directly dissolved in a deep eutectic solvent (DES) composed of acrylic acid (AA) and choline chloride, and lignin-reinforced physical eutectogels (DESL) were obtained by the polymerization of AA. Due to the unique features of lignin and DES, the prepared DESL eutectogels exhibit good transparency, UV shielding capacity, excellent mechanical performance, outstanding self-adhesiveness, superior self-healing properties, and high conductivity. Based on the aforementioned integrated functions, a wearable strain sensor displaying a wide working range (0-1500%), high sensitivity (GF = 18.15), rapid responsiveness, and excellent stability and durability (1000 cycles) and capable of detecting diverse human motions was fabricated. Additionally, by combining DESL sensors with a deep learning technique, a gesture recognition system with accuracy as high as 98.8% was achieved. Overall, this work provides an innovative idea for constructing multifunction-integrated physical eutectogels for application in wearable electronics.


Subject(s)
Deep Learning , Wearable Electronic Devices , Humans , Gels/chemistry , Lignin/chemistry , Acrylates/chemistry , Electric Conductivity , Choline/chemistry , Particle Size , Deep Eutectic Solvents/chemistry
4.
Int J Biol Macromol ; 273(Pt 1): 133046, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38857726

ABSTRACT

Chitin-glucan complex (CGC) is an emerging novel prebiotic with numerous physiological activities in amelioration of clinical manifestations. In the present work, natural deep eutectic solvent (NADES), ultrasonication, and submerged fermentation using probiotic microorganisms were deployed for the extraction of CGC from Shiitake fruiting bodies. CGC obtained through non-ultrasonication assisted fermentation employing Lactiplantibacillus plantarum exhibited maximum polysaccharide yield (27.86 ± 0.82 % w/w). However, based on antioxidant potential, NADES combination of urea: glycerol (1:1 M ratio) was selected for further characterization. The rheological behavior of CGC under optimized conditions showed shear thinning property in both 0.1 M NaCl and salt-free solution. FTIR, 1H-(1D), and 2D 1H1H Homonuclear NMR spectra displayed distinctive patterns associated with ß-glycosidic linkage and ß-d-glucopyranose sugar moiety. XRD profiles of CGC exhibited characteristic peaks at 2θ = 23°, 25°, and 28° with corresponding hkl values of (220), (101), and (130) lattice planes, respectively. Enhanced radical scavenging activities were noticed due to the triple helical structure and anionic nature of CGC. CGC exhibited potential prebiotic activity (prebiotic score 118-134 %) and short chain fatty acids liberation (maximum 9.99 ± 0.41 mM by Lactobacillus delbrueckii). Simulated static in-vitro digestion demonstrated that CGC withstands acidic environment of gastric phase, which indicated its suitability for use as a prebiotic in nutraceutical-enriched food products.


Subject(s)
Chitin , Deep Eutectic Solvents , Fruiting Bodies, Fungal , Glucans , Prebiotics , Shiitake Mushrooms , Glucans/chemistry , Glucans/isolation & purification , Fruiting Bodies, Fungal/chemistry , Chitin/chemistry , Chitin/isolation & purification , Shiitake Mushrooms/chemistry , Deep Eutectic Solvents/chemistry , Antioxidants/chemistry , Antioxidants/pharmacology , Fermentation , Lactobacillus plantarum/metabolism
5.
Int J Biol Macromol ; 273(Pt 2): 133007, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38857729

ABSTRACT

Heteroatom-doped porous carbon-based materials with high surface area compared to their metal-based homologs are considered environmentally friendly and ideal catalysts for organic reactions. In this paper, a new method for the convenient fabrication, cost-effective, and high efficiency of nitrogen/selenium co-doped porous carbon-based catalysis (marked as N/SePC-T) was designed. The N/SePC-T catalysts were created from the direct pyrolysis of a eutectic solvent containing choline chloride/urea as the nitrogen-rich carbon source, selenium dioxide as a source of heteroatom and chitosan as a secondary carbon source in different temperatures (T). The efficacy of the carbonization temperature on the pore structure, morphology, and catalytic activity of the N/SePC-T materials was investigated and displayed, the N/SePC-900 (having a surface area of 562.01 m2/g and total pore volume of 0.2351 cm3 g-1) has the best performance. The morphology, structure, and physicochemical properties of N/SePC-900 were characterized using various analyses including XRD, TEM, TGA, FE-SEM, EDX, FT-IR, XPS, and Raman. The optimized N/SePC-900 catalyst indicated excellent catalytic performance in the oxidation of benzylalcohols to corresponding aldehydes in very mild conditions.


Subject(s)
Alcohols , Carbon , Chitosan , Deep Eutectic Solvents , Nitrogen , Oxidation-Reduction , Selenium , Chitosan/chemistry , Catalysis , Porosity , Carbon/chemistry , Nitrogen/chemistry , Alcohols/chemistry , Selenium/chemistry , Deep Eutectic Solvents/chemistry , Green Chemistry Technology , Solvents/chemistry
6.
J Environ Manage ; 363: 121350, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38850901

ABSTRACT

Conventional methods of metal recovery involving solvents have raised environmental concerns. To address these concerns and promote sustainable resource recovery, we explored the use of deep eutectic solvents (DES) and chelating agents (CA) as more environmentally friendly alternatives. Goethite and blast oxide slag dust (BOS-D) from heap piles at their respective sites and characterised via ICP-MS. The greatest extraction of critical metals was from goethite, removing 38% of all metals compared to 21% from the blast oxide slag. Among the tested CA, nitrilotriacetic acid (NTA) was the most effective, while for DES, choline chloride ethylene glycol (ChCl-EG) demonstrated superior performance in extracting metals from both blast oxide slag dust and goethite. The study further highlighted the selectivity for transition metals and metalloids was influenced by the carboxyl groups of DES. Alkaline metals and rare earth lanthanides extractions were favoured with DES due to improved mass transfer and increased denticity, respectively. In comparison to ethylenediaminetetraacetic acid (EDTA), typically used for metal extraction, CA and DES showed comparable extraction efficiency for Fe, Cu, Pb, Li, Al, Mn, and Ni. Using these greener chelators and solvents for metal extraction show significant promise in enhancing the sustainability of solvometallurgy. Additional conditions e.g., temperature and agitation combined with a cascading leaching process could further enhance metal extraction potential.


Subject(s)
Chelating Agents , Edetic Acid , Metals , Chelating Agents/chemistry , Edetic Acid/chemistry , Metals/chemistry , Deep Eutectic Solvents/chemistry , Solvents/chemistry
7.
Molecules ; 29(11)2024 May 21.
Article in English | MEDLINE | ID: mdl-38893285

ABSTRACT

In the study, natural deep eutectic solvents (NADESs) were used as alternatives to traditional chemical solvents for the extraction of polyphenols from Elaeagnus angustifolia L. Nine NADESs were tested for the first time and compared with ethanol and water (traditional solvents) regarding the extraction of phenolic compounds from E. angustifolia L. These solvents were particularly effective at extracting polyphenols, whose low water solubility usually requires high amounts of organic solvents. The solvent based on choline chloride and malonic acid provided optimal results and was selected for further optimization. The effects of material-to-liquid ratio, ultrasound time, and ultrasound temperature on the extraction efficiency were studied through single-factor experiments. These parameters were optimized by Box-Behnken design using response surface methodology. The optimal conditions identified were 49.86 g/mL of material-to-liquid ratio, 31.10 min of ultrasound time, and 62.35 °C of ultrasound temperature, resulting in a high yield of 140.30 ± 0.19 mg/g. The results indicated that the NADES extraction technique provided a higher yield than the conventional extraction process. The antioxidant activity of the extract of polyphenols from E. angustifolia L. was determined, and UPLC-IMS-QTOF-MS was used to analyze the phenolic compounds in it. The results revealed that the scavenging ability of 1,1-diphenyl-2-picryl-hydrazil and 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulphonate) extracted by NADES was higher than that of polyphenols extracted by water and ethanol. Furthermore, a total of 24 phenolic compounds were identified in the extract. To the best of our knowledge, this is the first study in which a green and efficient NADES extraction method has been used to extract bioactive polyphenols from E. angustifolia L., which could provide potential value in pharmaceuticals, cosmetics, and food additives.


Subject(s)
Antioxidants , Elaeagnaceae , Plant Extracts , Polyphenols , Polyphenols/chemistry , Polyphenols/isolation & purification , Plant Extracts/chemistry , Antioxidants/chemistry , Antioxidants/pharmacology , Antioxidants/isolation & purification , Elaeagnaceae/chemistry , Deep Eutectic Solvents/chemistry , Green Chemistry Technology , Solvents/chemistry
8.
Molecules ; 29(11)2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38893476

ABSTRACT

Saffron (Crocus sativus) floral by-products are a source of phenolic compounds that can be recovered and used in the nutraceutical, pharmaceutical, or cosmetic industries. This study aimed to evaluate the phenolic compounds' extraction using green extraction techniques (GETs) in saffron floral by-products and to explore the influence of selected extraction techniques on the phytochemical composition of the extracts. Specifically, ultrasound-assisted extraction (UAE), subcritical water extraction (SWE), and deep eutectic solvents extraction (DESE) were used. Phenolic compounds were identified with (HR) LC-ESI-QTOF MS/MS analysis, and the quantitative analysis was performed with HPLC-PDA. Concerning the extraction techniques, UAE showed the highest amount for both anthocyanins and flavonoids with 50:50% v/v ethanol/water as solvent (93.43 ± 4.67 mg/g of dry plant, dp). Among SWE, extraction with 96% ethanol and t = 125 °C gave the best quantitative results. The 16 different solvent mixtures used for the DESE showed the highest amount of flavonoids (110.95 ± 5.55-73.25 ± 3.66 mg/g dp), while anthocyanins were better extracted with choline chloride:butane-1,4-diol (16.0 ± 0.80 mg/g dp). Consequently, GETs can be employed to extract the bioactive compounds from saffron floral by-products, implementing recycling and reduction of waste and fitting into the broader circular economy discussion.


Subject(s)
Crocus , Flowers , Phenols , Plant Extracts , Water , Crocus/chemistry , Phenols/chemistry , Phenols/isolation & purification , Phenols/analysis , Plant Extracts/chemistry , Water/chemistry , Flowers/chemistry , Deep Eutectic Solvents/chemistry , Solvents/chemistry , Chromatography, High Pressure Liquid/methods , Flavonoids/isolation & purification , Flavonoids/chemistry , Flavonoids/analysis , Anthocyanins/isolation & purification , Anthocyanins/chemistry , Anthocyanins/analysis , Tandem Mass Spectrometry , Ultrasonic Waves
9.
Molecules ; 29(11)2024 Jun 02.
Article in English | MEDLINE | ID: mdl-38893491

ABSTRACT

This paper explores the emerging subject of extracting tannins from various plant sources using deep eutectic solvents (DESs). Tannins are widely used in the food and feed industries as they have outstanding antioxidant qualities and greatly enhance the flavor and nutritional content of a wide range of food products. Organic solvents are frequently used in traditional extraction techniques, which raises questions about their safety for human health and the environment. DESs present a prospective substitute because of their low toxicity, adaptability, and environmental friendliness. The fundamental ideas supporting the application of DESs in the extraction of tannins from a range of plant-based materials frequently used in daily life are all well covered in this paper. Furthermore, this paper covers the impact of extraction parameters on the yield of extracted tannins, as well as possible obstacles and directions for future research in this emerging subject. This includes challenges such as high viscosity, intricated recovery of compounds, thermal degradation, and the occurrence of esterification. An extensive summary of the diversity, structure, biosynthesis, distribution, and roles of tannins in plants is given in this paper. Additionally, this paper thoroughly examines various bioactivities of tannins and their metabolites.


Subject(s)
Deep Eutectic Solvents , Tannins , Tannins/chemistry , Tannins/isolation & purification , Deep Eutectic Solvents/chemistry , Plant Extracts/chemistry , Antioxidants/chemistry , Antioxidants/pharmacology , Plants/chemistry , Plants/metabolism , Solvents/chemistry
10.
Sci Rep ; 14(1): 13613, 2024 06 13.
Article in English | MEDLINE | ID: mdl-38871855

ABSTRACT

Propolis extracts have been used in traditional medicines since ages due to its advantageous complex chemical composition. However, the antibacterial and antifungal activity of poplar propolis extracts prepared in Natural Deep Eutectic Solvent (NADES) are seldom studied. This study investigates suitable alternate for ethanol as a solvent for extraction for Polish poplar propolis. It also attempts to identify suitable extraction condition for the efficient transfer of compounds from propolis to the solvents. The extraction efficiency of NADES extracts was assessed in terms of total phenolic content, antioxidant activity and antimicrobial activity. The chemical composition of the extracts was analysed using UHPLC-DAD-QqTOF-MS. Four extracts, prepared in Propylene Glycol, Choline Chloride:Propylene Glycol (1:3), Choline Chloride:Propylene Glycol (1:4) and Choline Chloride:Glycerol (1:2), demonstrated activity and properties similar to ethanolic extract and extraction at 50 °C was found the most suitable for propolis. HPLC analysis confirmed that the chemical cocktail extracted by these solvents from propolis were identical with minor variations in their concentration as compared to its ethanolic extract. Thus, extracts of propolis at 50 °C in Propylene Glycol, Choline Chloride:Propylene Glycol (1:3) and Choline Chloride:Propylene Glycol (1:4) can be alternates for ethanolic extracts.


Subject(s)
Anti-Bacterial Agents , Antifungal Agents , Propolis , Propolis/chemistry , Propolis/pharmacology , Antifungal Agents/pharmacology , Antifungal Agents/chemistry , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Microbial Sensitivity Tests , Chromatography, High Pressure Liquid , Plant Extracts/chemistry , Plant Extracts/pharmacology , Antioxidants/pharmacology , Antioxidants/chemistry , Propylene Glycol/chemistry , Solvents/chemistry , Choline/chemistry , Deep Eutectic Solvents/chemistry , Phenols/chemistry , Phenols/pharmacology
11.
Mikrochim Acta ; 191(7): 425, 2024 06 27.
Article in English | MEDLINE | ID: mdl-38926184

ABSTRACT

A solvothermal synthesis of ultrasmall cerium oxide nanoparticles (USCeOxNPs) with an average size of 0.73 ± 0.07 nm using deep eutectic solvent (DES) as a stabilizing medium at a temperature of 90 ºC is reported. Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) were used to morphologically characterize the USCeOxNPs. These revealed approximately spherical shapes with emission lines characteristic of cerium. Selected area electron diffraction (SAED) was used to determine the crystalline structure of the cerium oxide nanoparticles (CeO2NPs), revealing the presence of crystalline cubic structures. The USCeOxNPs-DES/CB film was characterized by scanning electron microscopy (SEM), which demonstrated the spherical characteristic of CB with layers slightly covered by DES residues. DES was characterized by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR), indicating its formation through hydrogen bonds between the precursors. An electrochemical sensor for dopamine (DA) determination in biological fluids was developed using the USCeOxNPs together with carbon black (CB). An enhanced current response was observed on DA voltammetric determination, and this can be attributed to the USCeOxNPs. This sensor displayed linear responses for DA in the range 5.0 × 10-7 mol L-1 to 3.2 × 10-4 mol L-1, with a limit of detection of 80 nmol L-1. Besides detectability, excellent performances were verified for repeatability and anti-interference. The sensor based on USCeOxNPs synthesized in DES in a simpler and environmentally friendly way was successfully applied to determine DA in biological matrix.


Subject(s)
Cerium , Dopamine , Electrochemical Techniques , Cerium/chemistry , Dopamine/analysis , Dopamine/blood , Electrochemical Techniques/methods , Humans , Deep Eutectic Solvents/chemistry , Nanoparticles/chemistry , Limit of Detection , Metal Nanoparticles/chemistry , Particle Size
12.
Int J Mol Sci ; 25(12)2024 Jun 18.
Article in English | MEDLINE | ID: mdl-38928384

ABSTRACT

Atenolol, one of the top five best-selling drugs in the world today used to treat angina and hypertension, and to reduce the risk of death after a heart attack, faces challenges in current synthetic methods to address inefficiencies and environmental concerns. The traditional synthesis of this drug involves a process that generates a large amount of waste and other by-products that need disposal. This study presents a one-pot DES-based sustainable protocol for synthesizing atenolol. The use of the DES allowed the entire process to be conducted with no need for additional bases or catalysts, in short reaction times, under mild conditions, and avoiding chromatographic purification. The overall yield of atenolol was 95%. The scalability of the process to gram-scale production was successfully demonstrated, emphasizing its potential in industrial applications. Finally, the 'greenness' evaluation, performed using the First Pass CHEM21 Metrics Toolkit, highlighted the superiority in terms of the atom economy, the reaction mass efficiency, and the overall process mass intensity of the DES-based synthesis compared with the already existing methods.


Subject(s)
Atenolol , Deep Eutectic Solvents , Atenolol/chemistry , Deep Eutectic Solvents/chemistry , Green Chemistry Technology/methods
13.
Molecules ; 29(12)2024 Jun 11.
Article in English | MEDLINE | ID: mdl-38930830

ABSTRACT

The objective of this research was to optimize the natural deep eutectic solvent (NADES) extraction process from sour cherry kernels (Prunus cerasus L.). For polyphenol isolation, conventional solid-liquid extraction was employed using different concentrations of ethanol (0, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 96%), as well as the innovative NADES extraction technique. In the initial phase of the research, a screening of 10 different NADESs was conducted, while extraction was carried out under constant parameters (50 °C, 1:20 w/w, 60 min). NADES 4, composed of lactic acid and glucose in a molar ratio of 5:1, exhibited the highest efficiency in the polyphenol isolation. In the subsequent phase of the research, response surface methodology (RSM) was utilized to optimize the extraction process. Three independent variables, namely temperature, extraction time, and solid-liquid (S/L) ratio, were examined at three different levels. The extracted samples were analyzed for total phenol (TP) and antioxidant activity using the DPPH, ABTS, and FRAP assays. ANOVA and descriptive statistics (R2 and CV) were performed to fit the applied model. According to RSM, the optimal extraction conditions were determined as follows: temperature of 70 °C, extraction time of 161 min, and S/L ratio of 1:25 w/w.


Subject(s)
Antioxidants , Deep Eutectic Solvents , Polyphenols , Prunus avium , Polyphenols/chemistry , Polyphenols/isolation & purification , Prunus avium/chemistry , Antioxidants/chemistry , Antioxidants/pharmacology , Deep Eutectic Solvents/chemistry , Plant Extracts/chemistry , Solvents/chemistry
14.
J Chromatogr A ; 1727: 464999, 2024 Jul 19.
Article in English | MEDLINE | ID: mdl-38788403

ABSTRACT

A reliable and greener alternative to the usual extraction methods is reported for the determination of pesticide residues in soybeans. This novel approach combines the classical QuEChERS extraction method with a DLLME (dispersive liquid-liquid microextraction) step, utilizing a deep eutectic solvent (DES) - camphor: hexanoic acid (1:1 molar ratio) - as the microextraction solvent. This DES has never been employed in pesticide analysis by gas chromatography-mass spectrometry of complex matrices like soybeans. A Plackett-Burman screening design was employed to optimize sample preparation variables of QuEChERS (amount of sodium chloride and magnesium sulfate, and amount of PSA and C18 sorbents) and DLLME (pH of medium, amount of sodium chloride, and volume of microextraction solvent). This design allowed for a systematic evaluation of the impact of each parameter on the method's performance. The optimized method was evaluated using a certified reference material and commercial samples of soybeans. The method exhibited high accuracy and precision for most of the analytes under study, demonstrating its applicability for pesticide residue analysis in soybeans. To assess the greenness and practicality of the developed method, the Analytical Greenness (AGREE) and Blue Applicability Grade Index (BAGI) metric systems were employed, respectively. Overall, the proposed QuEChERS-DLLME method using a DES solvent is a reliable and greener alternative to conventional extraction methods for the determination of pesticide residues in soybeans. Its high performance, coupled with its environmental friendliness, makes it a promising tool for food safety analysis.


Subject(s)
Gas Chromatography-Mass Spectrometry , Glycine max , Liquid Phase Microextraction , Pesticide Residues , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Glycine max/chemistry , Gas Chromatography-Mass Spectrometry/methods , Liquid Phase Microextraction/methods , Deep Eutectic Solvents/chemistry , Limit of Detection , Reproducibility of Results
15.
Water Res ; 257: 121654, 2024 Jun 15.
Article in English | MEDLINE | ID: mdl-38701552

ABSTRACT

Volatile fatty acids (VFAs) derived from arrested anaerobic digestion (AD) can be recovered as a valuable commodity for value-added synthesis. However, separating VFAs from digestate with complex constituents and a high-water content is an energy-prohibitive process. This study developed an innovative technology to overcome this barrier by integrating deep eutectic solvents (DESs) with an omniphobic membrane into a membrane contactor for efficient extraction of anhydrous VFAs with low energy consumption. A kinetic model was developed to elucidate the mechanistic differences between this novel omniphobic membrane-enabled DES extraction and the previous hydrophobic membrane-enabled NaOH extraction. Experimental results and mechanistic modeling suggested that VFA extraction by the DES is a reversible adsorption process facilitating subsequent VFA separation via anhydrous distillation. High vapor pressure of shorter-chain VFAs and low Nernst distribution coefficients of longer-chain VFAs contributed to DES-driven extraction, which could enable continuous and in-situ recovery and conversion of VFAs from AD streams.


Subject(s)
Fatty Acids, Volatile , Hydrophobic and Hydrophilic Interactions , Membranes, Artificial , Deep Eutectic Solvents/chemistry , Solvents/chemistry , Kinetics , Anaerobiosis
16.
Molecules ; 29(10)2024 May 14.
Article in English | MEDLINE | ID: mdl-38792157

ABSTRACT

Deep eutectic solvents (DESs) are commonly used in pharmaceutical applications as excellent solubilizers of active substances. This study investigated the tuning of ibuprofen and ketoprofen solubility utilizing DESs containing choline chloride or betaine as hydrogen bond acceptors and various polyols (ethylene glycol, diethylene glycol, triethylene glycol, glycerol, 1,2-propanediol, 1,3-butanediol) as hydrogen bond donors. Experimental solubility data were collected for all DES systems. A machine learning model was developed using COSMO-RS molecular descriptors to predict solubility. All studied DESs exhibited a cosolvency effect, increasing drug solubility at modest concentrations of water. The model accurately predicted solubility for ibuprofen, ketoprofen, and related analogs (flurbiprofen, felbinac, phenylacetic acid, diphenylacetic acid). A machine learning approach utilizing COSMO-RS descriptors enables the rational design and solubility prediction of DES formulations for improved pharmaceutical applications.


Subject(s)
Deep Eutectic Solvents , Ibuprofen , Ketoprofen , Machine Learning , Solubility , Ketoprofen/chemistry , Ibuprofen/chemistry , Deep Eutectic Solvents/chemistry , Cyclooxygenase Inhibitors/chemistry , Hydrogen Bonding , Solvents/chemistry
17.
Int J Biol Macromol ; 270(Pt 2): 132245, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38729477

ABSTRACT

This study investigates the use of nanodiamonds (ND) as a promising carrier for enzyme immobilization and compares the effectiveness of immobilized and native enzymes. Three different enzyme types were tested, of which Rhizopus niveus lipase (RNL) exhibited the highest relative activity, up to 350 %. Under optimized conditions (1 h, pH 7.0, 40 °C), the immobilized ND-RNL showed a maximum specific activity of 0.765 U mg-1, significantly higher than native RNL (0.505 U mg-1). This study highlights a notable enhancement in immobilized lipase; furthermore, the enzyme can be recycled in the presence of a natural deep eutectic solvent (NADES), retaining 76 % of its initial activity. This aids in preserving the native conformation of the protein throughout the reusability process. A test on brine shrimp revealed that even at low concentrations, ND-RNL had minimal toxicity, indicating its low cytotoxicity. The in silico molecular dynamics simulations performed in this study offer valuable insights into the mechanism of interactions between RNL and ND, demonstrating that RNL immobilization onto NDs enhances its efficiency and stability. All told, these findings highlight the immense potential of ND-immobilized RNL as an excellent candidate for biological applications and showcase the promise of further research in this field.


Subject(s)
Deep Eutectic Solvents , Enzymes, Immobilized , Lipase , Nanodiamonds , Lipase/chemistry , Lipase/metabolism , Enzymes, Immobilized/chemistry , Enzymes, Immobilized/metabolism , Nanodiamonds/chemistry , Deep Eutectic Solvents/chemistry , Molecular Dynamics Simulation , Enzyme Stability , Animals , Hydrogen-Ion Concentration , Rhizopus/enzymology , Temperature , Artemia/drug effects , Solvents/chemistry
18.
Ecotoxicol Environ Saf ; 280: 116528, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38820821

ABSTRACT

Effective removal of organic UV filters from aquatic environmental compartments and swimming waters is very important because these substances are hazardous to humans and wildlife at low concentrations and act as endocrine disruptors. Therefore, the aim of the present article is to determine the extraction efficiencies of hydrophobic deep eutectic solvents (HDES) for the selected UV filters based on benzophenone structure (benzophenone, 2,4-dihydroxybenzophenone, 2,2´,4,4´-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2´-dihydroxy-4-methoxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone) from aqueous matrices. For this purpose, six HDESs based on dl-menthol in combination with caprylic, decanoic and lauric acid are prepared and compared with referent terpene solvents such as terpineol and linalool. The effect of various parameters such as HDES composition, volume ratio, frequency and shaking time are studied. The highest extraction efficiency is shown by HDES of menthol:caprylic acid (1:1) composition at the aqueous:organic phase volume ratio of 1:1, shaking frequency of 1500 rpm and shaking time of 15 min. The achieved extraction efficiencies are higher than 99.6 % for all benzophenones studied in the purification of stagnant pond water, swimming pool water and river water samples. After a simple and fast sample treatment, the residual levels of benzophenones in the waters are controlled by a newly developed sensitive HPLC-MS/MS method with LOQs in the range of 0.7 - 5.0 ng/mL.


Subject(s)
Benzophenones , Deep Eutectic Solvents , Hydrophobic and Hydrophilic Interactions , Sunscreening Agents , Water Pollutants, Chemical , Water Purification , Benzophenones/chemistry , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Sunscreening Agents/chemistry , Sunscreening Agents/toxicity , Water Purification/methods , Deep Eutectic Solvents/chemistry , Menthol/chemistry , Caprylates/chemistry
19.
Anal Methods ; 16(22): 3551-3561, 2024 Jun 06.
Article in English | MEDLINE | ID: mdl-38780040

ABSTRACT

Tetracycline (TC) as a broad-spectrum antibiotic, is widely used in the prevention and treatment of various bacterial diseases. However, its abuse in the livestock industry may lead to interference in human microecology, thereby causing various side effects. In this study, deep eutectic solvents (DESs) were synthesized using L-(-)-threonine (L-(-)-Thr) and cerium nitrate hexahydrate (Ce(NO3)3·6H2O), and later lanthanum nitrate hexahydrate (La(NO3)3·6H2O) was doped to synthesize La-Ce hybrid nanorods. These nanorods can be used for the determination of TC with high sensitivity and selectivity by the colorimetric method. This approach has a linear response to TC between 0.05 µM and 10 µM, with a detection limit of 0.016 µM. In this system, good dispersion provides the substance with a distinct peroxidase activity, which is used to create a colorimetric sensor for detecting TC. Mechanism studies show that the superoxide radical generated by the La-Ce nanomembrane plays a key role in peroxidase catalysis. Finally, the practicality of the method was verified by the determination of TC in food products (milk, pork and honey), which demonstrated that a good recovery rate can be obtained (91.4-102%).


Subject(s)
Cerium , Colorimetry , Lanthanum , Milk , Nanotubes , Tetracycline , Colorimetry/methods , Nanotubes/chemistry , Lanthanum/chemistry , Cerium/chemistry , Tetracycline/analysis , Tetracycline/chemistry , Milk/chemistry , Animals , Honey/analysis , Deep Eutectic Solvents/chemistry , Food Analysis/methods , Limit of Detection , Food Contamination/analysis , Anti-Bacterial Agents/analysis , Swine
20.
Carbohydr Polym ; 338: 122199, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-38763725

ABSTRACT

Deep eutectic solvents (DES) emerge as promising alternatives to conventional solvents, offering outstanding extraction capabilities, low toxicity, eco-friendliness, straightforward synthesis procedures, broad applicability, and impressive recyclability. DES are synthesized by combining two or more components through various synthesis procedures, such as heat-assisted mixing/stirring, grinding, freeze drying, and evaporation. Polysaccharides, as abundant natural materials, are highly valued for their biocompatibility, biodegradability, and sustainability. These versatile biopolymers can be derived from various natural sources such as plants, algae, animals, or microorganisms using diverse extraction techniques. This review explores the synthesis procedures of DES, their physicochemical properties, characterization analysis, and their application in polysaccharide extraction. The extraction optimization strategies, parameters affecting DES-based polysaccharide extraction, and separation mechanisms are comprehensively discussed. Additionally, this review provides insights into recently developed molecular guides for DES screening and the utilization of artificial neural networks for optimizing DES-based extraction processes. DES serve as excellent extraction media for polysaccharides from different sources, preserving their functional features. They are utilized both as extraction solvents and as supporting media to enhance the extraction abilities of other solvents. Continued research aims to improve DES-based extraction methods and achieve selective, energy-efficient processes to meet the demands of this expanding field.


Subject(s)
Deep Eutectic Solvents , Polysaccharides , Polysaccharides/chemistry , Polysaccharides/isolation & purification , Deep Eutectic Solvents/chemistry , Biological Products/chemistry , Biological Products/isolation & purification , Animals , Solvents/chemistry , Chemical Fractionation/methods , Plants/chemistry
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