Green Solvent System Research Articles

Delamination and Evaluation of Multilayer PE/Al/PET Packaging Waste Separated Using a Hydrophobic Deep Eutectic Solvent.

This research concerns the development and implementation of ground-breaking strategies for improving the sorting, separation, and recycling of common flexible laminate packaging materials. Such packaging laminates incorporate different functional materials in order to achieve the desired mechanical performance and barrier properties. Common components include poly(ethylene) (PE), poly(propylene) (PP), and poly(ethylene terephthalate) (PET), as well as valuable barrier materials such as poly(vinyl alcohol) (PVOH) and aluminium (Al) foils. Although widely used for the protection and preservation of food produce, such packaging materials present significant challenges for established recycling infrastructure and, therefore, to our future ambitions for a circular economy. Experience from the field of ionic liquids (ILs) and deep eutectic solvents (DESs) has been leveraged to develop novel green solvent systems that delaminate multilayer packaging materials to facilitate the separation and recovery of high-purity commodity plastics and aluminium. This research focuses on the development of a hydrophobic DES and the application of a Design of Experiments (DoE) methodology to investigate the effects of process parameters on the delamination of PE/Al/PET laminate packaging films. Key variables including temperature, time, loading, flake size, and perforations were assessed at laboratory scale using a 1 L filter reactor vessel. The results demonstrate that efficient separation of PE, Al, and PET can be achieved with high yields for material and solvent recovery. Recovered plastic films were subsequently characterised via Fourier-transform infra-red (FTIR) spectroscopy, Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) to qualify the quality of plastics for reuse.

Review on Green Bioanalytical Chemistry with Sustainable Approaches in Method Development: Unveiling the Crucial Role of Sustainable Bioanalysis in the Future of Chemistry

Green bioanalytical chemistry, with its focus on incorporating sustainable practices into developing bioanalytical methods, has the potential to significantly reduce the environmental impact of laboratory activities. This approach, while maintaining the high standards required for analytical precision and accuracy, includes key strategies such as reducing hazardous chemicals, optimizing energy use, and implementing waste-reduction practices. This review highlights recent advancements in green bioanalytical chemistry, including green solvent systems, miniaturized techniques, and eco-friendly analytical platforms. We discuss the benefits, such as reduced environmental pollution and improved resource efficiency, challenges, and future perspectives of integrating green principles into bioanalytical method development, emphasizing the balance between sustainability and analytical performance.

Toward sustainable manufacturing of highly efficient and stable semi-transparent perovskite solar cells: The critical role of green solvent properties

Perovskite solar cells, promising a bright future in the energy market, are now being prioritized for high-throughput production to match their remarkable success at the laboratory scale. However, the use of toxic solvents proved to be one of the major constraints on scaling up production. Herein, a green solvent system consist of dimethyl sulfoxide (DMSO) and 1-dodecyl-3-methylimidazolium chloride ([C12MIM]Cl) ionic liquids (ILs) was developed to modulate the crystallization of wide-bandgap (WBG) perovskite films combined with a antisolvent-free process, i.e., nitrogen (N2) quenching method. The [C12MIM]Cl IL promoted the crystallization of WBG perovskite films with large grain sizes, reduced photo-active PbI2, modulated residual strain, prolonged carrier lifetimes as well as improved energy alignment. Consequently, the [C12MIM]Cl-modified single-junction 1.77 eV perovskite solar cells (PSCs) achieved a champion efficiency of 18.75 % with an excellent operational stability, retaining an initial PCE of 93 % after 2000 h of maximum-power-point tacking test. Meanwhile, the positive effect of the [C12MIM]Cl ILs was universal in perovskite with different bandgaps at 1.53, 1.68 and 1.72 eV, respectively. Furthermore, stacking semi-transparent [C12MIM]Cl-modified 1.77 eV WBG PSCs as top cells coupled with 1.27 eV OPV or 1.24 eV Sn-Pb PSC as bottom cells for the 4 T tandem configuration showed impressive PCE of 26.01 % and 27.44 %, respectively. This study opens a new avenue toward the sustainable fabrication of highly efficient and stable perovskite-based semitransparent and tandem solar cells.

A novel temperature-responsive biphasic deep eutectic solvent-based solvent system: Integrated efficient extraction, enrichment and recovery of phytochemicals

The current large-scale use of organic and some toxic reagents hinders the development of plant secondary metabolite extraction and processing industry. Here, a biphasic temperature-responsive solvent system consisting of hydrophilic deep eutectic solvent (choline chloride: levulinic acid) and fatty acid-based hydrophobic deep eutectic solvent is developed. Some characteristics of this intelligent solvent system, including hundreds of synthesis ratios and corresponding switching temperatures, phase ratios, etc., have been comprehensively determined. Subsequently, it is applied to different plant matrices. The extraction efficiencies ranged from 1.006 to 6.807 times higher than those of conventional organic reagents, with separation efficiencies ranging from 60.7 % to 100 %, besides the fact that the hydrophilic components are almost entirely distributed in the lower phase. The recovery of targeted phytochemicals achieves satisfactory results during the simultaneous extraction and enrichment process. Mechanisms of switching, extraction, and enrichment have been elucidated to a certain extent from the point of view of chemical computational simulations. Overall, this new green solvent system is universal and can be applied to a wide range of phytochemicals extraction and separation from plants in a one-pot operating unit. Also, it is almost the greenest of the temperature-responsive solvents studied so far and has superior application prospects.

Flow synthesis of silver nanoparticles using water in supercritical CO2 emulsion

Rapid and continuous synthesis of metal nanoparticles using green solvent system is still a serious challenge for both fundamental and practical research. In this work, we report a new flow process using water in supercritical CO2 (w/scCO2) emulsion and applied it to the synthesis of silver nanoparticles (AgNPs). To investigate the performance of our system, AgNPs were synthesized by batch, flow and w/scCO2 emulsion flow system at 40 ºC while using AgNO3, NaBH(OAc)3, trisodium citrate and Aerosol-OT as precursor, reducer, stabilizer and emulsifier. As a result, we demonstrated that water droplets in w/scCO2 emulsion significantly contribute to a rise in the size controllability and productivity (product yield). Additionally, w/scCO2 emulsion flow process allowed the control of mean size from 4.0 to 36.6 nm and yield from 25% to 65% by changing the CO2 pressure and Aerosol-OT concentration. Furthermore, synthesized AgNPs successfully gave citrate-modified surface with high zeta potential of –54 mV and the transparent water dispersion with unimodal size distribution, showing promising potential to allow various practical applications.

Organosolv Treatment of Red Grape Pomace for Effective Recovery of Antioxidant Polyphenols and Pigments Using a Ternary Glycerol/Ethanol/Water System under Mild Acidic Conditions.

The purpose of this investigation was (i) the development of a novel, green tertiary solvent system, composed of water, ethanol and glycerol, and (ii) the implementation of an organosolv treatment of red grape pomace (RGP) for the efficient production of polyphenol-containing extracts with enhanced antioxidant properties. The treatment developed was performed under mild acidic conditions, imparted by the addition of citric acid, and it was first evaluated on the basis of severity, establishing linear models that described the correlation between treatment performance and combined severity factors. To solicit treatment optimization, response surface methodology was implemented, considering solvent acidity and residence time as the treatment variables. The optimized treatment afforded maximum total polyphenol (166 ± 6 mg GAE g-1 DM), total pigment (4.4 ± 0.2 mg MvE g-1 DM) and total flavanol (31.5 mg CtE g-1 DM) yields and extracts with particularly enhanced antioxidant activity. This might be attributed to specific constituents with high antioxidant potency, such as catechin, determined in the extract using high-performance liquid chromatography. Thus, the treatment developed is proposed as a highly efficient process to generate RGP extracts enriched in polyphenolic compounds, with enhanced antioxidant activity. Such extracts might then be valorized as food additives, to provide antioxidant protection and/or pigmentation.

Green solvent systems for material syntheses and chemical reactions.

It is of great significance to develop environmentally benign, non-volatile and recyclable green solvents for different applications. This feature article overviews the properties of green solvent systems (e.g., ionic liquids, supercritical carbon dioxide, deep eutectic solvents and mixed green solvent systems) and their applications in (1) framework material syntheses, including metal-organic frameworks, covalent organic frameworks and hydrogen-bonded organic frameworks, and (2) CO2 conversion reactions, including photocatalytic and electrocatalytic reduction reactions. Finally, the future perspective for research on green solvent systems is proposed from different aspects.

Utility and greenness appraisal of nuclear magnetic resonance for sustainable simultaneous determination of three 1,4-benzodiazepines and their main impurity 2-amino-5-chlorobenzophenone

A robust, stability-indicating, and eco-friendly proton nuclear magnetic resonance (1H-qNMR) method was developed for the concurrent determination of three 1,4-benzodiazepines (BDZs), namely diazepam (DZP), alprazolam (ALP), and chlordiazepoxide (CDP) and their common impurity, synthesis precursor, and degradation product; 2-amino-5-chlorobenzophenone (ACB). In the present method, a novel approach was developed for composing a green and cost-efficient solvent system as an alternative to the common NMR organic solvents utilizing 0.3 M sodium dodecyl sulfate prepared in deuterated water. The conducted method is characterized by simplicity with no need for sample pretreatment or labeling. Phloroglucinol was used as an internal standard. The chosen signals for the determinations of ALP, CDP, DZP and ACB were at 2.35 ppm (singlet), 2.84 ppm (singlet), 3.11 ppm (singlet), and 6.90 ppm (doublet of doublet), respectively. The proposed method possessed linearity over the concentration range of 0.25–15.0 mg ml−1 for DZP, ALP, CDP and of 0.5–25.0 mg ml−1 for ACB with LOD values of 0.06, 0.03, 0.07 and 0.16 mg ml−1 respectively, and LOQ values of 0.18, 0.09, 0.21 and 0.49 mg ml−1, respectively. Accuracy of the method was evidenced by excellent recovery% (99.57–99.90%) and small standard deviation (≥ 1.10) for the three analyzed drugs. Intra- and inter-day precision were determined with coefficient of variation ranging from 0.12 to 1.14 and from 0.72 to 1.67, respectively. For the studied compounds, appraisal of the method greenness was achieved via four approaches: Analytical Eco-Scale, Green Analytical Procedure Index (GAPI), Analytical greenness metric (AGREE), and RGB Additive Color Model. The results proved that the proposed method has the privilege of being a green analytical method.

Synthesis of 3-Aminoquinazolinones via a SnCl2-Mediated ANRORC-like Reductive Rearrangement of 1,3,4-Oxadiazoles.

Herein, we developed a new SnCl2-mediated ANRORC (addition of nucleophile, ring-opening, and ring-closure)-like rearrangement for the synthesis of 3-amino-2-substituted-quinazolin-4(3H)-one from 2-(2-nitrophenyl)-5-substituted-1,3,4-oxadiazole. The new method is solvent-dependent and features the use of a green solvent system (i.e., ethanol/water), high yields, and simple workup. The reduced product could be exclusively synthesized by changing the solvent to acetonitrile.

Evaluation of polycaprolactone nanofibers’ spinnability using green solvent systems by solution blow spinning (SBS)

Solution blow spinning (SBS) is a promising alternative to produce fibrous matrices for a wide range of applications, such as packaging and biomedical devices. Polycaprolactone (PCL) is a biodegradable polyester commonly used for spinning. The usual choices for producing PCL solutions include chlorinated solvents (CS), such as chloroform. However, the high toxicity of CS makes it difficult for biological and green applications. This work evaluates the influence of two less toxic solvents, acetic acid (AA) and acetone (Acet), and their mixtures (AA/Acet) on the properties of PCL fibers produced by SBS. The results showed that Acet does not cause degradation of the PCL chains, in opposition to AA. Furthermore, adding acetone to the acetic acid tended to preserve the size of PCL chains. It was not possible to produce fibers using PCL in 100% acetone. However, the AA/Acet mixture allowed the efficient production of PCL fibers. The proportion of Acet and AA in the mixture modulated the fiber morphology and orientation, making it possible to use this green solvent system according to the desired application.

Process optimization and characterization of nanocellulose from chestnut shell

Nanocellulose, a unique and promising natural substance extracted from cellulose-based materials, has gained tremendous attention for its use in various applications. Latest studies hypothesized that green extraction techniques reveal high-yield cellulose nanoparticles with lower environmental hazard and also highlighted that selectivity and characteristics of final products are highly dependent upon process parameters. This study aimed to produce nanocellulose powders from the chestnut shell –an agroindustrial waste without pertinent reuse– by acid hydrolysis (conventional), microwave-assisted acid hydrolysis, hydrotropic solvent, and deep eutectic solvent extraction techniques. The effectiveness of process parameters was investigated, and optimum conditions were determined by targeting the highest yields for each method. Additionally, the physico-chemical and microstructural properties of nanocellulose powders produced by each method were analyzed to investigate the product characteristics. The highest yield was obtained by deep eutectic solvent extraction (99.2%) followed by hydrotropic solvent (89.6%), conventional (64.5%), and microwave-assisted (34.1%) extractions. The methods bearing strong acid solvents resulted in a higher crystallinity index (up to 81%). The highest viscosity and absolute zeta potential values were obtained in deep eutectic solvent extraction as 843.6 cp and −23.7 mV, respectively. For all nanocellulose suspensions, the storage modulus (G′) was greater than the loss modulus (G″), indicating a more gel-like behavior. Nanocellulose powders produced by different methods had characteristic Fourier transform Infrared (FTIR) spectrum. The results of X-ray diffractometer (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) evidenced that nanofibrils could be produced via hydrotropic and deep eutectic solvent extraction systems while acid hydrolysis, i.e., conventional and microwave-assisted extraction generate nanocrystals. Obtained results indicated that green solvent systems could be utilized in the production of nanocellulose with many advantages, including efficiency, sustainability, reduced environmental harm, and low cost.

All-biomass cellulose/casein adsorbent fabricated via the “green solvent system” of ionic liquid for the efficient removal of Cu(II), Cd(II) and Pb(II)

All-biomass cellulose/casein adsorbent fabricated via the “green solvent system” of ionic liquid for the efficient removal of Cu(II), Cd(II) and Pb(II)

Supercritical CO2/Deep Eutectic Solvent Biphasic System as a New Green and Sustainable Solvent System for Different Applications: Insights from Molecular Dynamics Simulations.

Deep eutectic solvents (DESs) are one of the most interesting research subjects in green chemistry nowadays. Due to their low toxicity, simple synthesis, and lower prices, they have gradually taken the place of other green solvents such as ionic liquids (ILs) in sustainable processes. However, problems such as high viscosity and high polarity limit the applications of DESs in areas such as extraction, catalysis, and biocatalysis. In this work, we introduce and evaluate the potential application of scCO2/DES for the first time. Molecular dynamics simulations were used to examine the phase behavior, polarity, molecular mobilities, and microstructure of this system. Results show that CO2 molecules can significantly diffuse to the DES phase, while DES components do not appear in the scCO2 phase. The diffused CO2 molecules significantly enhanced the molecular mobility of the DES components. The presence of CO2 molecules changes the DES polarity so that hexane can be solubilized and dispersed in the DES phase. Radial distribution functions show that the solubilized CO2 molecules have negligible effects on the microstructure of DES. It was shown that chloride and urea are the main interaction sites of CO2 in DES. The results of this study show that scCO2/DES as a new class of green and versatile solvents can open a new promising window for research in sustainable chemistry and engineering.

Stable and Continuous Production of Amines via Reductive Amination in a Green Switchable Solvent System with Efficient Water Removal

Stable and Continuous Production of Amines via Reductive Amination in a Green Switchable Solvent System with Efficient Water Removal

Nanofibrous hybrid scaffolds based on PCL-borosilicate system by a green sol-gel process

Tissue regeneration is yet a critical issue, and to mimic the natural extracellular matrix (ECM) innovative scaffolds need to be developed to ensure the functional and safe repair of the damaged organs or tissues. Hybrid biomaterials based on the combination of a biodegradable polymer and bioactive glasses (BGs) are potential candidates for tissue engineering (TE), since they exhibit tailored physical, biological, and mechanical properties, as well as controlled degradation behavior. Thus, the main purpose of this research was to develop by electrospinning (ES) a hybrid nanofibrous membrane composed of a synthetic polymeric matrix (PCL) and a boron and calcium silicate glass, formed via in situ sol-gel, and based on a non-aqueous and green fabrication route. Formic acid (FA) and glacial acetic acid (AA) were used as green solvents to dissolve the PCL. Different compositions were prepared: neat PCL and PCL/SiO2–B2O3–CaO with different sol-gel aging times and green solvent systems. All prepared hybrid solutions, except the composition with only AA, were spinnable. Structural features of the hybrids were assessed by ATR-FTIR spectroscopy, which confirmed the presence of siloxane (Si–O–Si) bonds of silica and carbonyl (CO) bonds characteristic of PCL polymer as well as intermolecular hydrogen-bonding interactions between the carbonyls of PCL and the silanol hydroxyls (Si–OH) of silica networks. Boron (B–O–B) and borosiloxane (B–O–Si) bonds were not visible due to the overlapping of PCL bands in the spectra. Only the solid state 11B NMR technique allowed to find peaks assigned to trigonal BO3 and tetrahedral BO4 groups, which evidence the boron linkages to silica. Thermal analysis showed a change in the crystallinity of PCL with the incorporation of inorganic domains, confirming the formation of chemical interactions between the polymer and the inorganic part. Microstructure and chemical analysis, by SEM/EDS, showed a homogenous distribution of Ca and Si elements into the fibers, as well as an increase of the fiber diameter with the incorporation of boron and calcium silicate glass in the PCL. The developed compositions of PCL/boron and calcium-containing silicate were feasible to electrospin into fibrous meshes, proving its potential for further design of multicomponent nanofibrous microstructures closer to extra cellular matrix architectures.

Guesstimate of thymoquinone diversity in Nigella sativa L. genotypes and elite varieties collected from Indian states using HPTLC technique.

Thymoquinone is a valuable metabolite derived from the Nigella sativa L. seeds and has a variety of therapeutic properties. Thymoquinone was estimated using n-hexane:ethyl acetate (8:2, v/v) green solvent system and computed at a wavelength of 254 nm using the high-performance thin-layer chromatography densitometry method in distinct varieties and genotypes congregated from different geographical regions. Genotype Ajmer Nigella-13 has the paramount thymoquinone content (247.60 µg/100 mg seed) followed by Ajmer Nigella 19 (244.5 µg/100 mg seed), while the lowest amount of thymoquinone was recorded in the genotype Ajmer Nigella-6 (42.88 µg/100 mg seed). The hierarchical cluster analysis found that the collected genotypes and elite varieties were classified into four broad clusters, and the identified chemotypes with elevated thymoquinone proportion were positioned in cluster D. Significant genotypic variation in thymoquinone content is available, that can be used in exploiting pharmaceutical applications of N. sativa L. as well as a breeding programme for specific metabolite improvement perspective.

Ultrasound-Assisted Deep Eutectic Solvent Extraction of Polysaccharides from Anji White Tea: Characterization and Comparison with the Conventional Method.

Deep eutectic solvent as a new green and safe solvent system has attracted more and more attention in recent years. In this study, three deep eutectic solvents (DES) were combined with ultrasound irradiation to extract tea polysaccharides (TPs) from Anji white tea, which was compared with conventional hot water extraction (HW). The physicochemical, structural, and biological properties of TPs extracted by ultrasound-assisted DES and hot water (HWP) were further investigated. Results showed that the DES system composed of choline chloride and 1,6-hexanediol (CH) with the molar ratio of 1:2 exhibited the optimal extraction yield (19.18%) and in vitro antioxidant activities for TPs (CHP). Furthermore, compared to the HWP, the CHP had a higher extraction yield and total carbohydrate content and a lower molecular weight. Monosaccharide composition analysis displayed that the molecular structure of CHP exhibited more arabinose but less glucose, mannose, galacturonic acid, and glucuronic acid than HWP. Little difference was observed in the preliminary structural characteristics between HWP and CHP from Fourier transform infrared analysis. Besides, CHP possessed better α-glucosidase inhibitory and hypoglycemic activity in L6 cells than HWP. Therefore, the ultrasound-assisted DES extraction method can be a promising strategy for extracting TPs with excellent bioactivities for future applications in functional foods.

Application of a novel and green temperature-responsive deep eutectic solvent system to simultaneously extract and separate different polar active phytochemicals from Schisandra chinensis (Turcz.) Baill

In the present study, a novel and green temperature-responsive deep eutectic solvent (TRDES) system was developed and applied for the simultaneous extraction and separation of different polar active phytochemicals from Schisandra chinensis (Turcz.) Baill. The TRDES, consisting of amino alcohols and phenolic compounds, was chosen as the switching medium, and an upper critical solution temperature (UCST) type switchable solvent was obtained by adding an inorganic salt solution. The switchable phase diagram was plotted based on the relationship between the phase change temperature, the concentration and the amount of sodium chloride solution. Under optimal parameters, the yields with TRDES for different polar active phytochemicals (lignanoids and polysaccharides) from the dried fruit of Schisandra chinensis (DFSC) were 1.62 ∼ 1.17-fold and 1.39-fold to those with conventional solvents. Also, the TRDES system was still effective on extraction of DFSC lignanoids and polysaccharides after four cycles of extraction. The separated polysaccharides and lignanoids both had strong antioxidant activities with IC50 values of 1.92 mg/ mL and 0.10 mg/ mL against 2,2′-Azinobis(3-ethylbenzothiazoline-6-sulfonic acid)(ABTS), respectively. The extraction mechanism of TRDES was postulated by Density functional theory (DFT) calculations the hydrogen bonding in TRDES was the main factor to the higher extraction yield. This temperature-responsive deep eutectic solvent could be widely used for the efficient extraction and separation of multi-polar components. As a green and recyclable solvents, TRDES has great potential for the lower cost production from plants.

Perovskite Films Doped with Polyoxometalate and Ionic Liquid Assisted Crystallization for Efficient Photodetectors

AbstractThe dependence of perovskite‐based photovoltaic devices on toxic solvents limits their applications. Therefore, we added polyoxometalates into ionic liquids, as the green solvent and polyoxometalates synergistically improve the performance of devices. Firstly, methylammonium formate (MAFa) as solvent delayed the crystallization process of perovskite thin films, thus obtained an extended crystal domain, and the photocurrent of the device was increased from 35.51 μA to 63.18 μA. Secondly, introducing PW12 into this green solvent system, the matched energy level and good electron transmission rate promoted the separation of photogenerated excitons and accelerated the transmission of photogenerated electrons in perovskite. After dual adjustment of MAFa and PW12, the photocurrent of the champion device reached 95.99 μA (about 2.7 times of the original device), the unpacked devices can still maintain 80 % of initial value after being placed under environmental conditions for 700 h.

Green Electrospinning of Biodegradable Cellulose Acetate Nanofibrous Membranes with Tunable Porosity

The electrospinning of polymer nanofibers has received significant attention owing to their high surface-area-to-volume ratio, high porosity, adjustable pore size and texture, and highly interconnected porous structure. In particular, the electrospinning of biodegradable cellulose acetate (CA) nanofibers has sparked interest in diverse applications, including drug delivery systems, scaffolding for tissue engineering, air filtration, and affinity membrane systems. However, the electrospinning process has been mostly performed using toxic and hazardous solvents and additives. We developed electrospun CA nanofibers using a green solvent system comprising dimethyl carbonate and cyclopentanone. The use of green additives, namely, tetrabutylammonium bromide salts and sophorolipid-based biosurfactants, obtained from honey yeast, substantially improved the spinnability of the CA solution. Moreover, the nanofiber diameter and porous texture were tunable by adjusting the solvent ratio. Pore generation was induced using volatile dimethyl carbonate, which quickly evaporated from the fiber jet. Molecular dynamics simulations demonstrated that the electrospinning process can be divided into three stages. The addition of the biosurfactant facilitated the evaporation process and improved the uniformity of the nanofibers. Furthermore, the nanofibers can be degraded using esterase and cellulase enzymes. To summarize, the electrospinning of ultrafine CA porous nanofibers with tunable morphology was achieved using green solvents and additives.