Search Results (56)

The aim of this work was to prepare a large set of variously substituted 3-aminophthalates starting from substituted 3-acylamino-2H-pyran-2-ones acting as dienes in Diels–Alder reactions with dialkyl acetylenedicarboxylates having the role of dienophiles. These thermally allowed [4+2] cycloadditions were taking place with normal electron demand due to rather electron-deficient dienophiles and relatively electron-rich dienes; however, they still required quite harsh reaction conditions: heating in closed vessels at 190 °C for up to 17 h was sufficient in most cases (albeit for a few reactions the time needed was up to 58 h) to achieve conversions above 95%. Such conditions, unfortunately, necessitated the use of a larger excess of dienophiles (as undesired polymerization takes place concomitantly); nevertheless, the straightforward isolation procedures enabled access to the target compounds in moderate to high yields (average yield 56%). All products were characterized by standard analytical and spectroscopic methods. With the goal of changing the reaction conditions to be more environmentally friendly, we investigated the effect of various solvents (water, n-butanol, butyl acetate, xylene, para-cymene, n-nonane, etc.) and the temperature applied (130–190 °C) on the conversion. We found that higher temperatures are necessary in most cases (except for the most reactive 2H-pyran-2-ones) regardless of the solvent used. Relative reactivity was determined for both sets of reactants and the experimentally obtained data show good agreement with the computational results. Full article

Bacterial cellulose (BC) is a highly pure and crystalline cellulose produced via bacterial fermentation. However, due to its chemical structure made of strong hydrogen bonds and its high molecular weight, BC can neither be melted nor dissolved by common solvents. Therefore, processing BC implies the use of very strong, often toxic and dangerous chemicals. In this study, we proved a green method to produce electrospun BC fibers by testing different ionic liquids (ILs), namely, 1-butyl-3-methylimidazolium acetate (BmimAc), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium dicyanamide (EmimDCA), either individually or as binary mixtures. Moreover, γ-valerolactone (GVL) was tested as a co-solvent derived from renewable sources to replace dimethyl sulfoxide (DMSO), aimed at making the viscosity of the cellulose solutions suitable for electrospinning. A BmimAc and BmimAc/EmimTFSI (1:1 w/w) mixture could dissolve BC up to 3 w%. GVL was successfully applied in combination with BmimAc as an alternative to DMSO. By optimizing the electrospinning parameters, meshes of continuous BC fibers, with average diameters ~0.5 μm, were produced, showing well-defined pore structures and higher water absorption capacity than pristine BC. The results demonstrated that BC could be dissolved and electrospun via a BmimAc/GVL solvent system, obtaining ultrafine fibers with defined morphology, thus suggesting possible greener methods for cellulose processing. Full article

Water contamination by heavy metals, including radionuclides, is a major threat to human health and the environment. New methods for their removal are therefore needed. Adsorption is currently a common method for wastewater treatment. It depends on the physical and chemical interactions between heavy metal ions and adsorbents. The main characteristics of suitable adsorption methods are (i) a high adsorption efficiency and ability to remove different types of ions, (ii) a high retention time and cycle stability of adsorbents, and (iii) availability. Chitin is a commercially available biopolymer from marine waste that has several favourable properties: availability, low cost, high biocompatibility, biodegradability, and effective adsorption properties for metal ions. However, the processing of chitin into stable structures, such as chitin-based composites, is difficult due to its high chemical stability and extremely low solubility in most solvents. The central working hypothesis of the present work is that powdered α-chitin can be dissolved in the ionic liquid 1-butyl-3-methylimidazolium acetate and cross-linked with its monomer, N-acetyl-D-glucosamine, in a Maillard-like or caramelisation reaction to produce chitin-based composites. It is further hypothesised that such composites can be used as biosorbents for heavy metal ions. Eu(III) is chosen here as a non-radioactive representative and analogue for other f-elements. Full article

In the process of ginger deep processing, a lot of waste is generated which is rich in biopolymers and active ingredients such as cellulose, starch, gingerol, and gingerol, but its low utilization rate leads to waste of resources. In this study, ginger waste residue, cellulose, and bioactive substances were spun into fiber materials by wet electrospinning technology with 1-butyl-3-methylimidazole acetate ([Bmim]Ac) as solvent. Fiber plasticization and [Bmim]Ac removal were achieved by dynamic deionized water coagulation bath. Scanning electron microscopy (SEM) and tensile strength analysis showed that the obtained GC-1 and GC-2 films have a non-uniform diameter, with a clear fiber structure and strong tensile strength. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) confirmed that cellulose transforms from type I to type II crystal structure, and [Bmim]Ac is effectively removed. The inhibition rate of 6-Shogaol-impregnated GC film against Escherichia coli and Staphylococcus aureus was 99%. The experiment of strawberry preservation verified the potential of GC film in food preservation. In this study, the high-value utilization of ginger waste in food packaging was realized by preparing antibacterial electrospun fiber films. Full article

Gynura divaricata (L.) DC is a long-used medicinal and edible plant in China folk. Its hyperglycemic effects have garnered increasing public attention in recent years. This study revealed that the ethyl acetate (EtOAc) and butanol (BuOH) partition fractions of G. divaricata crude extract exhibited significantly higher α-glucosidase inhibition activity and enhanced glucose uptake ability compared to other fractions. Guided by the hypoglycemic bioassay, these two fractions were subjected to isolation of active compounds using high-speed countercurrent chromatography (HSCCC). A two-phase solvent system composed of hexane-methyl tert-butyl ether (MtBE)-methanol-0.1% TFA water was employed for the separation of the EtOAc fraction by conventional HSCCC through a gradient elution strategy. Five major compounds were obtained and identified as chlorogenic acid (1), 3,4-dicaffeoylquinic acid (2), 3,5-dicaffeoylquinic acid (3), 4,5-dicaffeoylquinic acid (4), and kaempferol-3-O-β-D-glucopyranoside (5) by ESI-MS, ¹HNMR, and ¹³CNMR. The chlorogenic acid and the three dicaffeoylquinic acids were found to display higher inhibitory activities against α-glucosidase compared to the flavonoid. Considering their acidic nature, pH-zone-refining CCC (PHZCCC) was then applied for further scale-up separation using a solvent system MtBE: n-butanol: acetonitrile: water with trifluoroacetic acid (TFA) as a retainer and ammonium hydroxide (NH₄OH) as an eluter. A significantly higher yield of chlorogenic acid was obtained from the BuOH fraction by PZRCCC. Molecular docking between the caffeoylquinic acids and α-glucosidase confirmed their hypoglycemic activities. This study demonstrates that CCC is a powerful tool for preparative separation of active constituents in natural products. This research presents a novel and effective method for the preparative isolation of hypoglycemic compounds from Gynura divaricata. Full article

N,N′-Dialkylimidazolium-based ionic liquids are capable of completely dissolving lignocellulosic biomass at elevated temperatures and are considered as promising green solvents for future biorefining technologies. However, the obtained ionic liquid lignin preparations may contain up to several percent nitrogen. This indicates strong interactions between the biopolymer and the IL cation, the nature of which has not yet been clarified. The present study investigates mechanisms and pathways of the formation of nitrogen-containing lignin compounds. To achieve this goal, eight monomeric lignin-related phenols bearing different functional groups (ketone, aldehyde, hydroxyl, carbon–carbon double bonds) were treated with 1-butyl-3-methylimidazolium acetate (BmimOAc) under typical conditions of IL-assisted lignocellulose fractionation (80–150 °C). A number of the resulting products were tentatively identified, for all the studied model compounds, by two-dimensional NMR spectroscopy and high-performance liquid chromatography—high-resolution mass spectrometry. They all possess covalently bonded Bmim residues and occur through the nucleophilic addition of an N-heterocyclic carbene (deprotonated Bmim cation) to electron-deficient groups. The reactivity of lignin functional groups in their interaction with Bmim is greatly affected by the temperature and dissolved oxygen. IL’s thermal degradation products act as additional reactive species toward lignin, further complicating the range of products formed. The obtained results made it possible to answer the question posed in this article’s title and to assert that N,N′-dialkylimidazolium-based ILs act as active reagents with respect to lignin during the dissolution of lignocellulose. Full article

An overview of solvent replacement strategies shows that there is great progress in green chemistry for replacing hazardous di-polar aprotic solvents, such as N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), and 1,4-dioxane (DI), used in processing active industrial ingredients (APIs). In synthetic chemistry, alcohols, carbonates, ethers, eucalyptol, glycols, furans, ketones, cycloalkanones, lactones, pyrrolidinone or solvent mixtures, 2-methyl tetrahydrofuran in methanol, HCl in cyclopentyl methyl ether, or trifluoroacetic acid in propylene carbonate or surfactant water (no organic solvents) are suggested replacement solvents. For the replacement of dichloromethane (DCM) used in chromatography, ethyl acetate ethanol or 2-propanol in heptanes, with or without acetic acid or ammonium hydroxide additives, are suggested, along with methanol acetic acid in ethyl acetate or methyl tert-butyl ether, ethyl acetate in ethanol in cyclohexane, CO₂-ethyl acetate, CO₂-methanol, CO₂-acetone, and CO₂-isopropanol. Supercritical CO₂ (scCO₂) can be used to replace many organic solvents used in processing materials from natural sources. Vegetable, drupe, legume, and seed oils used as co-extractants (mixed with substrate before extraction) can be used to replace the typical organic co-solvents (ethanol, acetone) used in scCO₂ extraction. Mixed solvents consisting of a hydrogen bond donor (HBD) solvent and a hydrogen bond acceptor (HBA) are not addressed in GSK or CHEM21 solvent replacement guides. Published data for 100 water-soluble and water-insoluble APIs in mono-solvents show polarity ranges appropriate for the processing of APIs with mixed solvents. When water is used, possible HBA candidate solvents are acetone, acetic acid, acetonitrile, ethanol, methanol, 2-methyl tetrahydrofuran, 2,2,5,5-tetramethyloxolane, dimethylisosorbide, Cyrene, Cygnet 0.0, or diformylxylose. When alcohol is used, possible HBA candidates are cyclopentanone, esters, lactone, eucalytol, MeSesamol, or diformylxylose. HBA—HBA mixed solvents, such as Cyrene—Cygnet 0.0, could provide interesting new combinations. Solubility parameters, Reichardt polarity, Kamlet—Taft parameters, and linear solvation energy relationships provide practical ways for identifying mixed solvents applicable to API systems. Full article

Lactide is one of the most popular and promising monomers for the synthesis of biocompatible and biodegradable polylactide and its copolymers. The goal of this work was to carry out a full cycle of polylactide production from lactic acid. Process conditions and ratios of reagents were optimized, and the key properties of the synthesized polymers were investigated. The influence of synthesis conditions and the molecular weight of lactic acid oligomers on the yield of lactide was studied. Lactide polymerization was first carried out in a 500 mL flask and then scaled up and carried out in a 2000 mL laboratory reactor setup with a combined extruder. Initially, the lactic acid solution was concentrated to remove free water; then, the oligomerization and synthesis of lactide were carried out in one flask in the presence of various concentrations of tin octoate catalyst at temperatures from 150 to 210 °C. The yield of lactide was 67–69%. The resulting raw lactide was purified by recrystallization in solvents. The yield of lactide after recrystallization in butyl acetate (selected as the optimal solvent for laboratory purification) was 41.4%. Further, the polymerization of lactide was carried out in a reactor unit at a tin octoate catalyst concentration of 500 ppm. Conversion was 95%; Mw = 228 kDa; and PDI = 1.94. The resulting products were studied by differential scanning calorimetry, NMR spectroscopy and gel permeation chromatography. The resulting polylactide in the form of pellets was obtained using an extruder and a pelletizer. Full article

CO₂ capture, applied in CO₂ separation from natural gas or in CO₂/N₂ separation from power plant flue gas streams, is of great importance for technical, economic, and environmental reasons. The latter seems important because CO₂, as a greenhouse gas, is considered the main contributor to global warming. Using polymeric membranes for CO₂ separation presents several advantages, such as low energy demand, small equipment volume, and the absence of liquid waste. In this study, two ionic liquids (ILs) were used for the preparation of cellulose acetate (CA)–IL blend membranes for potential CO₂ capture applications, namely, 1-butyl-3-methylimidazolium hydrogen sulfate ($[{\mathrm{Bmim}}^{+}]$[${\mathsf{H}\mathrm{SO}}_4^{-}$]) and choline glycine ($[{\mathrm{Ch}}^{+}]\left[{\mathrm{Gly}}^{-}\right]$), as they present adequate CO₂ dissolution ability. The first IL is commercially available, whereas the latter was synthesized by a novel route. Several composite membranes were prepared through the solvent casting technique and characterized by a variety of methods, including thermogravimetry, calorimetry, FTIR spectroscopy, and X-ray diffraction. The CO₂ sorption in the composite membranes was experimentally measured using the mass loss analysis (MLA) technique. The results showed that the ILs strongly interacted with the C=O groups of CA, which exhibited high affinity with CO₂. In the case of $[{\mathrm{Bmim}}^{+}]$[${\mathsf{H}\mathrm{SO}}_4^{-}$], a reduction in the available sites that allow strong intermolecular interactions with CO₂ resulted in a decrease in CO₂ sorption compared to that of pure CA. In the case of $[{\mathrm{Ch}}^{+}]\left[{\mathrm{Gly}}^{-}\right]$, the reduction was balanced out by the presence of specific groups in the IL, which presented high affinity with CO₂. Thus, the CA-$[{\mathrm{Ch}}^{+}]\left[{\mathrm{Gly}}^{-}\right]$ blend membranes exhibited increased CO₂ sorption capability, in addition to other advantages such as non-toxicity and low cost. Full article

Eruca sativa is a commonly used edible plant in Italian cuisine. E. sativa 70% ethanol extract (ES) was fractionated with five organic solvents, including n-hexane (EHex), chloroform (ECHCl₃), ethyl acetate (EEA), n-butyl alcohol (EBuOH), and water (EDW). Ethyl acetate fraction (EEA) had the highest antioxidant activity, which was correlated with the total polyphenol and flavonoid content. ES and EEA acted as PPAR-α ligands by PPAR-α competitive binding assay. EEA significantly increased cornified envelope formation as a keratinocyte terminal differentiation marker in HaCaT cells. Further, it significantly reduced nitric oxide and pro-inflammatory cytokines (IL-6 and TNF-α) in lipopolysaccharide-stimulated RAW 264.7 cells. The main flavonol forms detected in high amounts from EEA are mono-and di-glycoside of each aglycone. The main flavonol form of EEA is the mono-glycoside of each aglycone detected, and the most abundant flavonol mono-glycoside is kaempferol 3-glucoside 7.4%, followed by quercetin-3-glucoside 2.3% and isorhamnetin 3-glucoside 1.4%. Flavonol mono-glycosides were shown to be a potent PPAR-α ligand using molecular docking simulation and showed the inhibition of nitric oxide. These results suggest that the flavonol composition of E. sativa is suitable for use in improving skin barrier function and inflammation in skin disorders, such as atopic dermatitis. Full article

Acidic deep eutectic solvents (DESs) have been considered desirable extractants and catalysts for desulfurization. However, their hydrogen bond donors (HBDs) are usually sole organic acids, which are not conducive to efficient green catalysis. Herein, a novel inorganic–organic dual-acid DES (DADES) was reported for efficient extractive and oxidative desulfurization. Benefiting from the physical interaction among the three components in a DADES, a transparent homogeneous liquid can be obtained even though inorganic acid (boric acid, BA) and organic acid (acetic acid, AA) can be immiscible. Furthermore, the dual-acid HBD can increase the acidity of the DADES and reduce its viscosity, accelerating its mass transfer efficiency and enhancing its catalytic activity. With 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) as the hydrogen bond acceptor, [Bmim]Cl/BA/0.3AA effectively activated hydrogen peroxide and achieved sulfur removal of 96.6% at 40 °C. Furthermore, the universality of the synergistic effect in various DADESs was confirmed by the modulation of the types of organic acids. This study not only motivates the construction of more intriguing novel DESs based on the DADES concept but also highlights their potential in clean fuel production. Full article

Slippery coatings, such as the slippery liquid-infused porous surface (SLIPS), have gained significant attention for their potential applications in anti-icing and anti-fouling. However, they lack durability when subjected to mechanical impact. In this study, we have developed a robust slippery coating by blending polyurethane acrylate (PUA) with methyltriethoxysilane (MTES) and perfluoropolyether (PFPE) in the solvent of butyl acetate. The resulting mixture is homogeneous and allows for uniform coating on various substrates using a drop coating process followed by drying at 160 °C for 3 h. The cured coating exhibits excellent water repellency (contact angle of ~108° and sliding angle of ~8°), high transparency (average visible transmittance of ~90%), exceptional adherence to the substrate (5B rating according to ASTMD 3359), and remarkable hardness (4H on the pencil hardness scale). Moreover, the coating is quite flexible and can be folded without affecting its wettability. The robustness of the coating is evident in its ability to maintain a sliding angle below 25° even when subjected to abrasion, water jetting, high temperature, and UV irradiation. Due to its excellent nonwetting properties, the coating can be employed in anti-icing, anti-graffiti, and anti-sticking applications. It effectively reduces ice adhesion on aluminum substrates from approximately 217 kPa to 12 kPa. Even after 20 cycles of icing and de-icing, there is only a slight increase in ice adhesion, stabilizing at 40 kPa. The coating can resist graffiti for up to 400 cycles of writing with an oily marker pen and erasing with a tissue. Additionally, the coating allows for easy removal of 3M tape thereon without leaving any residue. Full article

For the synthesis of ionogels containing microcrystalline cellulose (MCC) and Na-bentonite (Na-Bent), ionic liquid (IL) 1-butyl-3-methylimidazolium acetate was used as an MCC solvent. Characterization and research of the physicochemical properties of the synthesized materials were carried out using methods such as SEM, WAXS, thermal analysis, FTIR, conductometry, and viscometry. WAXS analysis showed an increase in the interlayer distance of Na-bentonite in composites due to the intercalation of IL molecules. Based on the data on the characteristic temperatures of thermal degradation, enhanced thermal stability of triple IL/Na-Bent/MCC ionogels was revealed compared to that for cellulose-free systems. It was found that the electrical conductivity of both triple IL/Na-Bent/MCC and binary IL/MCC ionogels was non-monotonous. The data obtained can be used in the formation of multifunctional coatings with enhanced thermal stability. Full article

This study aims to solve the icing problem of wind turbine blades in low-temperature environments and to improve the power generation efficiency of wind turbines. In this study, modified TiO₂ particles (500 nm), butyl acetate solvent, polyaspartic acid ester polyurea (PAE polyurea), and Crestron N75 curing agent were mixed and sprayed on the epoxy resin board surface. Static icing test, dynamic icing test, wear resistance test, and icing adhesion strength test studies were carried out to evaluate the anti-icing performance of the coating as well as its mechanical stability. The results showed that the mechanical stability and anti-icing performance of the coating were relatively optimal when the ratio of modified TiO₂ particles to PAE polyurea was 1.5. Under this ratio, the static contact angle of the coating was 161.4°, and the rolling angle was 4.7°. The main reason for the superhydrophobic performance after 250 wear cycles was that the TiO₂ particles were encapsulated by PAE polyurea. The static contact angle of the coating was still greater than 150° after eight icing–de-icing cycles. This paper provides a simple method to prepare a robust superhydrophobic coating and promotes the application of superhydrophobic coatings in the field of passive anti-icing of wind turbine blades. Full article

High-performance counter-current chromatography (HPCCC) was used as a tool for the isolation and fractionation of phenolic compounds (PCs) in extracts from wine lees (WL) and grape pomace (GP). The biphasic solvent systems applied for HPCCC separation were n-butanol:methyl tert-butyl ether:acetonitrile:water (3:1:1:5) with 0.1% trifluoroacetic acid (TFA) and n-hexane:ethyl acetate:methanol:water (1:5:1:5). After refining the ethanol:water extracts of GP and WL by-products by ethyl acetate extraction, the latter system yielded an enriched fraction of the minor family of flavonols. Recoveries of 112.9 and 105.9 mg of purified flavonols (myricetin, quercetin, isorhamnetin, and kaempferol) in GP and WL, respectively, from 500 mg of ethyl acetate extract (equivalent to 10 g of by-product) were obtained. The HPCCC fractionation and concentration capabilities were also exploited for the characterization and tentative identification of constitutive PCs by ultra-high performance liquid chromatography-mass spectrometry (UHPLC-MS). In addition to the isolation of the enriched flavonol fraction, a total of 57 PCs in both matrixes were identified, 12 of which were reported for the first time in WL and/or GP. The application of HPCCC to GP and WL extracts may be a powerful approach to isolate large amounts of minor PCs. The composition of the isolated fraction demonstrated quantitative differences in the individual compound composition of GP and WL, supporting the potential exploitation of these matrixes as sources of specific flavonols for technological applications. Full article