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The development of semiconducting polymers with good processability in green solvents and competitive electrical performance is essential for realizing sustainable large-scale manufacturing and commercialization of organic electronics. A major obstacle is the processability-performance dichotomy that is dictated by the lack of ideal building blocks with balanced polarity, solubility, electronic structures, and molecular conformation. Herein, through the integration of donor, quinoid and acceptor units, an unprecedented building block, namely TQBT, is introduced for constructing a serial of conjugated polymers. The TQBT, distinct in non-symmetric structure and high dipole moment, imparts enhanced solubility in anisole-a green solvent-to the polymer TQBT-T. Furthermore, PTQBT-T possess a highly rigid and planar backbone owing to the nearly coplanar geometry and quinoidal nature of TQBT, resulting in strong aggregation in solution and localized aggregates in film. Remarkably, PTQBT-T films spuncast from anisole exhibit a hole mobility of 2.30 cm2 V-1 s-1, which is record high for green solvent-processable semiconducting polymers via spin-coating, together with commendable operational and storage stability. The hybrid building block emerges as a pioneering electroactive unit, shedding light on future design strategies in high-performance semiconducting polymers compatible with green processing and marking a significant stride towards ecofriendly organic electronics.

Herein, we report an efficient strategy towards the synthesis of amino acid substituted isoquinoline derivatives via reaction of unprotected amino acid/amino acid ester/amino acid based drugs with 2‐(2‐oxo‐2‐aryl/alkylethyl)benzonitrile under metal‐free conditions. The developed protocol is highly simple and shows functional group tolerance to provide corresponding novel amino acid substituted isoquinolines in aqueous medium. The applicability of the reaction is an easier modification of well‐known drugs and successfully extended to gram‐scale synthesis. [ABSTRACT FROM AUTHOR]

Polymeric mixed ionic–electronic conductors hold great potential for advancing high‐performance organic electronics due to their exceptional electrical conductivity achieved through ion–electron coupling. However, the widespread adoption of these conductors faces obstacles due to their reliance on environmentally harmful solvents during processing and the potential performance degradation under various conditions. In this study, a practical solution to these challenges is proposed by incorporating monomers with ionic liquid‐behaving pendant groups into conjugated polymers. The copolymerization of these charged monomers not only improves solubility in environmentally friendly solvents but also imparts long‐term stability against humidity, high temperatures, and mechanical deformation. The immobilized ion species foster highly selective interactions of these polymers with nitrogen dioxide, paving the way for the development of stretchable sensing devices capable of functioning at exceptionally high temperatures. [ABSTRACT FROM AUTHOR]

AbstractIn recent years, driven by increasing consumer demand for natural and healthy convenient foods, the food industry has been shifting from synthetic to natural products. This shift is also reflected in the growing popularity of non-conventional extraction methods for pigments, which are favored for sustainability and environment-friendliness compared to conventional processes. This review aims to investigate the extraction of carotenoids from a variety of natural sources, including marine sources like fungus, microalgae, and crustaceans, as well as widely studied plants like tomatoes and carrots. Additionally, it delves into the recovery of valuable carotenoids from waste products like pomace and peels, highlighting the nutritional and environmental benefits. The review also emphasizes the role of green solvents such limonene, vegetable oils, ionic liquids, supercritical fluids, and natural deep eutectic solvents in effective and ecologically friendly carotenoid extraction. These technologies support the ideas of a circular and sustainable economy in addition to having a smaller negative impact on the environment. Overall, the present study highlights the crucial importance of green extraction technologies in achieving the dual goals of sustainability and public safety. [ABSTRACT FROM AUTHOR]

Despite the remarkable advances in the field of perovskite photovoltaics, the use of toxic solvents for their fabrication poses a significant challenge to their scale‐up and commercialization. The vast majority of studies rely on using the highly hazardous N, N‐Dimethylformamide (DMF), with green alternatives remaining scarce. In this work, the use of glycerol formal (Gly‐F) is reported as a green solvent for fabricating quasi‐2D (n = 5) perovskite solar cells. Quasi‐2D perovskite films processed from Gly‐F exhibit a high degree of uniformity and a compact microstructure. When integrated into solar cells, the green solvent‐processed films reach a promising power conversion efficiency of 14.53%. This performance is lower than that of DMF‐based perovskites, most likely due to the presence of laterally oriented low n perovskite phases. Interestingly, while the performance of DMF‐based devices is rather irreproducible, the performance of Gly‐F‐based devices is robust and consistent. These results demonstrate the potential of Gly‐F‐ as a promising green alternative to DMF. [ABSTRACT FROM AUTHOR]

Solvents can significantly influence chemical reactions in condensed phases. Their critical properties are increasingly recognized in various research domains such as organic synthesis and biomass valorization. However, in semiconductor photocatalysis, solvents are primarily viewed as mediums for dissolving and diffusing substances, with their potential beneficial effects on photocatalytic conversions often overlooked. Additionally, common photocatalysis solvents like acetonitrile (ACN) pose serious safety and environmental concerns. In this study, we demonstrate that novel and safe green solvents, such as γ‐valerolactone (GVL), can significantly enhance the performance of semiconductor photocatalysis for C−H bond activation. Non‐specific solvent‐solute interactions are the primary contributors to increased photocatalytic activity in the self‐coupling of benzylic compounds. Specifically, GVL′s large dielectric constant and high refractive index lower the energy barrier for the rate‐determining C−H bond activation step, facilitating a faster coupling reaction. The versatility of GVL is further demonstrated in reactions with multiple reagents and in various oxidation and reduction photocatalytic systems beyond classic C−H bond activation. This work not only pioneers the use of green solvents but also provides comprehensive insights for proper solvent selection in semiconductor photocatalysis. [ABSTRACT FROM AUTHOR]

Polyhydroxybutyrate (PHB) is a potential biopolymer and can replace petroleum-based plastic. PHB accumulated by bacteria needs a supply of carbon source whereas cyanobacteria are capable of synthesizing PHB by carbon fixation using sunlight energy. Since PHB is an intracellular product the polymer recovery cost is about 50 % of production cost. Apart from these, cyanobacterial pigments also affect the purity and recovery yield. In the present study, Chlorogloea fritschii TISTR 8527 was chosen as a PHB cell factory which accumulated 28 % of biopolymer. The hypochlorite-chloroform dispersion method could remove the pigments along with PHB extraction with 95.51 ± 3.164 % of the recovery in a single step. In addition to this, PHB extraction was performed with various halogenated solvents and green non-halogenated solvents with hypochlorite pretreatment. Selected solvents were unable to recover more than 90 % of polymer yield due to unsuitable operating conditions. Besides this, the green solvent dimethyl carbonate (DMC) was employed for PHB recovery with prior pigment removal from biomass using chilled methanol. DMC was capable of 83.34 ± 0.76 % biopolymer recovery with a purity of 75 %. PHB recovered using DMC has improved thermal and material characteristics. [ABSTRACT FROM AUTHOR]

The metal-free direct oxidative cross-dehydrogenative C–H bond amination of imidazopyridines with pyrazole in water as solvent has been developed under K2 S2 O8-promoted mild conditions. This strategy was applied to variable imidazoheterocycles to give amination products in moderate to good yields. The described protocol also offers scale-up synthesis for the construction of C–N bonds, which makes it suitable for the synthesis of biologically active compounds and pharmaceuticals. [ABSTRACT FROM AUTHOR]

This work aimed to obtain a phytochemical extract from jambolan leaf using a hydroethanolic solvent and ultrasound-assisted extraction. For this purpose, an experimental design was applied to analyze the effect of process variables related to temperature (30–60 °C), time (10–30 min), and solvent to leaf ratio (5–15 mL g−1), on the extraction mass yield (EMY) and on the yield of phenolic compounds (PCY). The effect of extractor solvent, AE (absolute ethanol), 75E (75% v·v−1 ethanol) and 50E (50% v·v−1), on the chemical characterization of the extracts, antidiabetic and antimicrobial activity, and cell viability, were also evaluated. The application of the highest values of process variables resulted in obtaining the maximum of the response variables (EMY = 9.94 wt% and PCY = 13.01 mg GAE g−1 leaf). A higher content of phenolic compounds and flavonoids was obtained with 50E, which is mainly composed of sinapic, vanillic, trans-caffeic, and quinic acids, which were responsible for the greatest antioxidant potential, antibacterial activity (against Staphylococcus aureus and Pseudomonas aeruginosa), and inhibition of α-amylase. On the other hand, the use of AE allowed us to obtain extracts with higher concentrations of squalene, α-tocopherol, β-sitosterol, and friedelin. From cell viability tests, the extracts are not considered toxic at the concentration tested (100 µg mg−1). [ABSTRACT FROM AUTHOR]

Extraction of lipids and high-value products from highly wet microalgae requires significant energy for the drying pretreatment. In this study, we examined the direct extraction of lipids, β-carotene, and polyphenolic compounds from wet Dunaliella salina using liquefied dimethyl ether (DME), which is effective in lipid extraction for biofuel production. The amount of DME-extracted β-carotene was 7.0 mg/g, which was higher than that obtained from the chloroform–methanol extraction. Moreover, the total phenolic content extracted with DME and its antioxidant capacity were slightly higher than those extracted with chloroform–methanol. DME removed almost all the water and extracted 29.2 wt% of total lipids and 9.7 wt% of fatty acids. More lipids were extracted from wet samples by liquefied DME than by chloroform–methanol extraction. The C/N ratio of lipids extracted with DME was 112.0, higher than that of chloroform–methanol. The high C/N ratio suggests that nitrogen-containing phosphatidylcholines may be less easily extracted by liquefied DME and may be highly selective. However, the ratio of saturated fatty acids was 34.8%, lower than that of chloroform–methanol. Na+ and Mg2+ in the culture medium were not extracted using DME. Thus, using the extract with DME has both advantages and disadvantages compared to using the extract with chloroform–methanol; however, it has satisfactory extraction properties. DME is expected to be an environment-friendly alternative solvent because it does not require drying, which is necessary for conventional extraction solvents. [ABSTRACT FROM AUTHOR]

Although encouraging progress in spin‐coated small‐area organic solar cells (OSCs), reducing efficiency loss caused by differences in film uniformity and morphology when up‐scaled to large‐area modules through meniscus‐guided coating is an important but unsolved issue. In this work, in‐depth research is conducted on the influence of both liquid and solid additives on the film uniformity and morphology of active layer in blade‐coated PM6:L8‐BO binary system. The study reveals that high boiling point liquid additives like 1,8‐diiodooctane (DIO) used in blade‐coating not only delay the volatilization of the solvent but also trigger the Marangoni flow in the same direction as capillary flow, causing excessive aggregation of acceptors, therefore destroying device performance. On the contrary, the solid additive 2‐Iododiphenyl ether (IDPE), which is first reported in this work, can preserve the mechanism for improving device performance while effectively suppressing the excessive aggregation of acceptors during the film‐forming process in blade‐coating from halogen‐free solvent of toluene, resulting in highly homogeneous large‐area active layer films. Consequently, organic solar modules with an impressive efficiency of 15.34% with a total module area of 18.90 cm2 via blade‐coating based on PM6:L8‐BO are achieved. This study not only provides a deep understanding on the effect of liquid and solid additives during blade‐coating from the perspective of fluid mechanisms but also gives a pathway for the development of green solvent printed high‐efficiency OSCs. [ABSTRACT FROM AUTHOR]

AbstractCobalt is beneficial for human activity but has adverse effects when discharged in large quantities. Therefore, its precise and accurate quantification in samples is of importance. Here, a natural deep eutectic solvent (NADES), composed of camphor (H-bond acceptor) and menthol (H-bond donor), has been used for the preconcentration of Co(II) from water samples before determination by a spectrophotometer at 398 nm. The 8-hydroxyquinoline-Co(II) complex was transferred to the NADES using air-assisted dispersive liquid-liquid microextraction (AA-DLLME). The extraction efficiency was enhanced through fine tuning of various parameters, including pH, NADES volume, and quantity of dispersant. Similarly, the centrifugation rate and time, quantity of the complexing agent, matrix effects, and salt concentration were also evaluated. Under the optimized conditions, an enrichment factor of 37.5 and a preconcentration factor of 37.5 were obtained. The limits of detection (LOD) and quantification (LOQ) were 0.44 µg/L and 1.47 µg/L, respectively. For seven replicates of 50 µg/L Co(II), the relative standard deviation was 3.2%. The developed method was employed for the determination of Co(II) in water samples, with quantitative recovery values from 94.5 to 98.5%. [ABSTRACT FROM AUTHOR]

In recent years, in an effort to reach Net Zero Emissions, there has been growing interest by various academic and industry communities to develop chemicals and industrial processes that are circular, sustainable and green. We report the rapid, simple and effective surface modification of a porous metal oxide with organic dyes using supercritical carbon dioxide (scCO2). Titanium dioxide (TiO2) photoanodes were coated in very short times, under mild conditions and the excess dye recovered afterwards for reuse. The process obviates the need for conventional toxic solvents, the generation of unwanted waste streams, and more importantly, we see an unexpected device performance enhancement of 212 and 163 % for TerCOOTMS, 2 a and TerCN/COOTBDMS, 4 dyes, respectively, when compared to the conventional solvent deposition method. [ABSTRACT FROM AUTHOR]

This study was planned to create an alternative use for orange peel, which is one of the most important fruit wastes within the scope of waste utilization. In the study, firstly, orange peel extracts were prepared by ultrasonic assisted extraction using different types of deep eutectic solvents in the green solvent category that can be alternative to organic solvents and the bioactive compound contents of these extracts were evaluated. As a result, it was determined that deep eutectic solvents were statistically effective in providing the highest total flavonoid compound and antioxidant activity values. In addition, when the individual phenolic compound profile was examined, the most dominant component was hesperidin and the highest value was reached with choline chloride:glycerol (1:2) combination. In conclusion, it was determined that deep eutectic solvents can be an alternative to organic solvents in the extraction of phytochemical compounds from orange peel. [ABSTRACT FROM AUTHOR]

Enormous advances have been made in the synthesis of metal nanoparticles (NPs) affording a high degree of control over their size, shape, and composition. In recent years, a growing effort has been dedicated to incorporating principles of green chemistry in different aspects of NPs, ranging from reagents/solvents to their fate in the environment. In this report, we focus on the use of Cyrene (dihydrolevoglucosenone) as an alternative green solvent for the synthesis of metal NPs. We begin with the synthesis of Ag NPs, given their prominence in the literature. Through control reactions, we show that Cyrene has a dual role of solvent and reducing agent. Additionally, the conversion yield for the Ag NPs synthesis was studied with respect to temperature and the Ag precursor. We then expand on the synthetic methodology to access Pd, Pt, and Bi NPs. The functionality of the synthesized NPs is assessed by employing them as electrocatalysts for furfural reduction and the hydrogen evolution reaction. We envision the use of Cyrene as a green solvent can be extended toward the synthesis of NPs of other metals and classes of materials. [ABSTRACT FROM AUTHOR]

Vine shoots hold promise as a biomass source for fermentable sugars with efficient fractionation and conversion processes. The study explores vine shoots as a biomass source for fermentable sugars through pretreatment with two deep eutectic solvents mixtures: choline chloride:lactic acid 1:5 (ChCl:LA) and choline chloride:ethylene glycol 1:2 (ChCl:EG). Pretreatment conditions, such as temperature/time, solid/liquid ratio, and biomass particle size, were studied. Chemical composition, recovery yields, delignification extent, and carbohydrate conversion were evaluated, including the influence of washing solvents. Temperature and particle size notably affected hemicellulose and lignin dissolution, especially with ChCl:LA. Pretreatment yielded enriched cellulose substrates, with high carbohydrate conversion rates up to 75.2% for cellulose and 99.9% for xylan with ChCl:LA, and 54.6% for cellulose and 60.2% for xylan with ChCl:EG. A 50% acetone/water mixture increased the delignification ratios to 31.5%. The results underscore the potential of this pretreatment for vine shoot fractionation, particularly at 30% solid load, while acknowledging the need for further process enhancement. [ABSTRACT FROM AUTHOR]

Lignocellulosic biomass, the most abundant natural resource on earth, can be used for cellulosic ethanol production but requires a pretreatment to improve enzyme access to the polymeric sugars while obtaining value from the other components. γ‐Valerolactone (GVL) is a promising candidate for biomass pretreatment since it is renewable and bio‐based. In the present work, the effect of a pretreatment based on GVL on the enzymatic saccharification of white birch was evaluated at a laboratory scale and the importance of the washing procedure for the subsequent saccharification was demonstrated. Both the saccharification yield and the production of cellulosic ethanol were higher using a noncommercial enzyme crude from Talaromyces amestolkiae than with the commercial cocktail Cellic CTec2 from Novozymes. Furthermore, the production of extracellular cellulases by T. amestolkiae has been optimized in 2 L bioreactors, with improvements ranging from 40% to 75%. Finally, it was corroborated by isoelectric focus that optimization of cellulase secretion by T. amestolkiae did not affect the pattern production of the main β‐glucosidases and endoglucanases secreted by this fungus. [ABSTRACT FROM AUTHOR]

A method was developed for the simultaneous extraction of herbicides such as 2,4 D, MCPA, ametryn, chlorothalonil, and bromacil in water and vegetable samples by emulsification liquid-liquid microextraction with fatty acids based hydrophobic deep eutectic solvents (DES). The DES were synthesised by mixing several fatty acids ratios that functioned as both the hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). Using the DES as the microextraction solvent, several vital parameters were optimised, including the type and volume of hydrophobic DES, pH of the sample, sonication time, and type and volume of emulsifier. Then, the extracted herbicides were back-extracted into phosphoric acid solution (0.05 M). The detection limits were in the range of 0.01–2.5 ng mL−1, the quantification limits were in the range of 0.03–8.3 ng mL−1, and recoveries were in the range of 73.1–98.8% with RSD <10%. The greenness assessment using Analytical Eco-Scale and AGREE (Analytical GREEnness Metric Approach System) exhibited that the emulsification liquid-liquid microextraction method using DES can be considered as simple, practical, and environmentally friendly. [ABSTRACT FROM AUTHOR]

This paper reports process development for the extraction of silica from paddy straw pretreated with green solvent and its characterization. Paddy straw pretreated with ethyl lactate resulted in a maximum reduction of total solids (11.78%), volatile solids (1.66%), cellulose (4.38%), hemicellulose (28.00%) and lignin (9.64%), while the increase in ash and silica content by 7.18 and 37.30%, respectively. Silica was extracted from 1% pretreated paddy straw using base dissolution and acid precipitation methods and was optimized by response surface methodology (RSM) using three parameters, viz. slurry concentration, and NaOH and HCl normalities to improve the silica yield. Maximum silica yield of 1.57 g per 2.5 g paddy straw ash (PSA) with 62.8% recovery was achieved under the optimized conditions of 2.50% slurry concentration, 0.55 N NaOH and 1.50 N HCl. Physico-chemical characterization by Fourier-transform infrared spectroscopy confirmed the purity of extracted silica particles by IR peak patterns. Field emission scanning electron microscopy showed an agglomerate form of 50–200 nm amorphous silica. Inductively coupled plasma atomic emission spectroscopy of residual ash inferred its potential as fertilizer in the fields. Hence, green solvent pretreated silica extraction from paddy straw improved the commercial value of underutilized paddy straw and reduced environmental pollution. [ABSTRACT FROM AUTHOR]

Inkjet printing has emerged as a promising technique for the fabrication of halide perovskite (HP) thin films, as it enables precise and controlled deposition of the perovskite ink on a variety of substrates. One main advantage of inkjet printing for the fabrication of HP thin films is its ability to produce uniform films with controlled thickness and high coverage, which is critical for achieving high‐performance devices. Additionally, inkjet printing allows for the deposition of patterned thin films, enabling the fabrication of complex device architectures such as light‐emitting diodes (LEDs). In this work, flexible LEDs based on inkjet printed Pb‐free HP thiophene‐ethylammonium tin iodide (TEA2SnI4) are produced that has gained attention as a potential alternative to Pb‐based HPs in optoelectronic devices due to its lower toxicity, environmental impact, and high performance. The role of ink solutions is compared using pure solvents: toxic dimethyl formamide (DMF) and more eco‐friendly dimethyl sulfoxide (DMSO). Red‐emitting devices (λmax = 633 nm) exhibit, in ambient conditions, a maximum external quantum efficiency (EQEmax) of 0.5% with a related brightness of 21 cd m−2 at 54 mA cm−2 for DMSO‐based LEDs. The environmental impacts of films prepared with DMSO‐based solvents ensure only 40% of the impact caused by DMF. [ABSTRACT FROM AUTHOR]

Researchers worldwide have increasingly focused on ionic liquids (ILs) in recent decades due to their distinctive properties and wide range of uses. Researchers are working on creating novel ILs and enhancing their characteristics to broaden their use across many industries. ILs are significant due to their versatility across various applications, and their utilization should take into account aspects such as cost, toxicity, and availability. Due to their unique properties, they have been extensively used as a green catalyst system in the synthesis of pyrazole derivatives. Pyrazole derivatives is privileged scaffolds among aza‐heterocycles owing to its various applications in drug discovery and materialistic program. A big task of green chemistry in organic synthesis has been fulfilled to the organic chemists towards the formation of valuable pyrazole‐based frameworks. This review explores the diverse applications of ILs in organic synthesis, specifically highlighting literature from 2004 to 2023 on the synthesis of pyrazole and its derivatives using IL‐assisted strategies. Specifically, it covers the synthesis of substituted pyrazoles, pyrazolo‐pyrans, quinolino‐triazolo‐triazepines, pyrazolo‐pyrimidines, and pyrazolo‐quinolinones. Also, reveals a role of IL as a catalyst and solvent on the synthesis of pyrazole derivatives. [ABSTRACT FROM AUTHOR]

In order to contribute to the demanded sustainability transparent poly(methyl methacrylate) (PMMA) composites with cellulose nanocrystals (CNC) up to high shares of 50 wt% were prepared by in situ radical polymerization in green solvent Cyrene. The weight average molecular weights of PMMA were in the range from 144,000 to 160,000 g mol−1 and the dispersity was in the range of 1.49 to 1.89 with high conversion of monomer to polymer. The DSC thermal analysis showed that the glass transition temperature of pure PMMA was at 99°C while in composites increased from 103°C up to 129°C with the increase of CNC from 1 wt% to 50 wt%. TGA shows that the addition of CNC does not have a significant effect on the thermal stability of PMMA. In composites Young's modulus increases with the increasing CNC ratio and composites with 50 wt% of CNC showed more than twice the modulus of the PMMA matrix. The SEM images indicate uniform distribution of CNC in polymer matrix. The transparent and semitransparent PMMA/cellulose composites of improved sustainability with higher modulus of elasticity and glass transition temperature can be used as lightweight materials for a wide range of technical and everyday applications as well as optical lenses or acoustic lenses for ultrasound transducers and other devices. Highlights: Cellulose nanocrystals/PMMA composites fabricated by a green in situ process.Synthesized PMMA matrices have high molecular weights.Improved elastic modulus and glass transition temperature were achieved.Prioritizing eco‐friendly chemicals for a greener production approach. [ABSTRACT FROM AUTHOR]

Green solvent processing of perovskite light‐emitting diodes (PeLEDs) is a necessity for their future commercialization. However, the almost insoluble nature of perovskites in most green solvents strongly impedes the progress of green solvent‐processed PeLEDs. Here, a novel green solvent triethylene glycol (TEG) is used as the processing solvent for perovskites. TEG has better solubility for perovskite precursors than most reported green solvents. Moreover, it is found that the low vapor pressure of TEG solvent and stable precursor solution render a much wider time window for the so‐called antisolvent treatment than that of perovskite precursor solution in commonly dimethyl sulfoxide. High‐quality perovskite film can be readily synthesized with the antisolvent treatment at a time window of 70–100 s, and the resultant green PeLEDs demonstrate nearly identical light‐emitting efficiencies. Together with further interface modification, the optimized green PeLEDs processed with TEG exhibit an external quantum efficiency of 20.4% and a maximal luminance over 38000 cd m−2. It is the first successful attempt to fabricate high‐efficiency PeLEDs utilizing green solvent and is enlightening for the development of high‐performance PeLEDs prepared with eco‐friendly solvents. [ABSTRACT FROM AUTHOR]

A base-induced synthesis of 2-(4-(2-(phenylthio)ethyl)piperazinyl) acetonitriles by reaction of disulfides, 1-(chloromethyl)-4-aza-1-azonia bicyclo[2.2.2]octane chloride and trimethylsilyl cyanide is reported. The scope of the method is demonstrated with 30 examples. The reaction mechanism research indicates that the three-component reaction would be a SN2 reaction. The products exhibit good activities towards advanced synthesis of aqueous soluble acyl-CoA: cholesterol O-acyltransferase-1 (ACAT-1) inhibitors. Our work is superior as it uses less-odor disulfides as carbon sources and EtOH as solvent in a water and dioxygen insensitive reaction system, followed by a simple purification process. [ABSTRACT FROM AUTHOR]

A Molybdate intercalated copper–aluminium hydrotalcite (CAM) material was synthesised using a simple co-precipitation technique, employing varying amounts of molybdate anions. Powder XRD, FT-IR, and TEM studies revealed the presence of molybdate species in the interlayer spaces and the formation of layered hydrotalcite structures. The resultant CAM materials have been explored for the hydrogenation of 5-hydroxymethyl furan using water as a green solvent in liquid-phase conditions under a hydrogen atmosphere. The catalyst showed around 60% conversion with the selective formation of 2,5-bishydroxymethyl furan (BHMF). The activity remains intact for five cycles. The increase in reaction temperature enhanced the conversion level to 80%, with the cost of a decrease in the selectivity of BHMF to 74%. The uniform dispersion of copper-molybdenum and strong interaction in the presence of a hydrogen atmosphere favoured better activity. [ABSTRACT FROM AUTHOR]

[Display omitted] It has been a challenge to prepared polyether block amide (PEBA) fibrous membrane via solution electrospinning. The only few reported methods though involved hazardous solvents and surfactants which were against the principle of green chemistry. In this work, uniform fibrous membrane of PEBA was successfully fabricated by solution electrospinning with a bio-based solvent dihydrolevoglucosenone (Cyrene). To further improve the mechanical strength and adsorption performance of the PEBA membrane, a hierarchical magnesium hydrogen phosphate (MgHPO 4 ·1.2H 2 O, MHP) was synthesized to blend evenly into the PEBA matrix. A Janus MHP/PEBA membrane with one side of hydrophobic surface and the other side of hydrophilic surface was subsequently prepared, which exhibited fast adsorption, high capacity, good selectivity and reusability towards ibuprofen, acetaminophen, carbamazepine and triclosan. In addition, the Janus membrane showed high removal efficiency of the above contaminants in secondary wastewater effluent with good long term stability. It demonstrated that this Janus MHP/PEBA membrane had a good potential in practical wastewater treatment. [ABSTRACT FROM AUTHOR]

Lycopene is usually extracted from the by‐product of the tomato industry using organic solvents (OS) in combination with a physical technique. An emerging physical technique is high‐pressure processing (HPP). This study aims to find a method by applying a green solvent (edible vegetable oils) in an HPP‐assisted solid–liquid extraction. Three dosages of tomato by‐product (10%, 20%, and 40%, w/v) were tested using OS, sunflower oil (RSO), and extra‐virgin olive oil (EVOO). Lycopene recovery increased with the ratio of by‐product to oil, particularly when using EVOO. In another stage of the study, consumers evaluated EVOO that contained two doses of tomato by‐product (10% and 20%, w/v). Consumers preferred the EVOO from 10% tomato by‐product ratio over that with 20%. Additionally, 83.8% of consumers stated that enriched oil could be deemed beneficial for health. The proposed method considers the fundamental principles of the circular economy and practical industrial scenario to recover lycopene from tomato by‐product. [ABSTRACT FROM AUTHOR]

Purple yam (Dioscorea trifida) has high agricultural productivity in the Amazon region but has not been much investigated. Multivariate strategies were employed to optimize the method to obtain a food extract rich in functional compounds. The optimal conditions showed that the combination of 0.2 g of dried purple yam with 15 mL of citric acid (1%) under agitation in a water bath at 36 °C for 4 min yields an extract with a high content of peonidin-3-O-glucoside-5-O-glucoside, peonidin-3-O-feruloylglycosideum-5-O-glycosideum, peonidin-3-Op-coumaroylglycosideum-5-O-glycoside, quinic acid, apigenin 8-C-xyloside-6-C-glycoside (vicenin 3), quinic acid, apigenin 6-C-xyloside-8-C-glycoside (vicenin 1), and isorhamnetin-O-dihexoside. Our extract also presented 56.91 ± 0.76 mg 100 g−1 of total anthocyanins, 417.05 ± 11.37 mg 100 g−1 total carotenoids, and 493.09 ± 6.38 mg GAE 100 g−1 of total phenolic compounds. In a Galleria mellonella, in vivo model consumption safety was for up to 150 g by 70 kg of body weight. In addition, it inhibited the growth of Gram-negative bacteria (Salmonella typhimurium and Escherichia coli). The simple, fast, and ecofriendly extraction conditions, combined with the biological effects of our extract, gives us a great potential for its application in food or packaging technologies. [ABSTRACT FROM AUTHOR]

In the present study, twin-column recycling chromatography has been employed for the purification of a Cannabis extract by using a green solvent, ethanol, as the mobile phase. In particular, the complete removal of the psychoactive tetrahydrocannabinol (THC) from a Cannabis extract rich in cannabidiol (CBD) was achieved under continuous conditions. The performance of the method, in terms of compound purity, recovery, productivity and solvent consumption, was compared to that of traditional batch operations showing the potential of the twin-column recycling approach. The employment of a theoretical model to predict the band profiles of the two compounds during the recycling process has facilitated method development, thus further contributing to process sustainability by avoiding trial and error attempts or at least decreasing the number of steps significantly. [ABSTRACT FROM AUTHOR]

The preservation of stone materials faces significant challenges due to biological deterioration, compromising the visual appearance and structural integrity of artifacts. Current cleaning treatments use toxic chemical biocides, with a high impact on the environment and human health. Research is turning to eco-friendly alternatives, such as Deep Eutectic Solvents (DESs), which offer a promising combination of biocidal properties and eco-friendly, as well as features such as biodegradability, non-flammability and non-volatility. This study defines the efficacy of Choline Chloride-based DESs reported in the literature as biocides in a real case study on an outdoor exposed magmatic effusive rock at the University of Calabria. Several analytical techniques were used to define DESs biocidal efficacy, monitoring their action for 6 months. This study contributes to the evidence of DESs' ability to keep treated surfaces clean, thus promoting the long-term preservation of materials. Macroscopic and microscopic observations, spectrocolorimetry, bioluminometry and FTIR spectroscopy have highlighted the significant potential of DESs as sustainable biocidal solvents for the preservation of stone materials exposed outdoors. [ABSTRACT FROM AUTHOR]

Butia capitata endocarp (BCE) is a biomass residue with the potential to produce a wide variety of bio-products. The processing of BCE in a sequential process of subcritical water hydrolysis (SWH) and hydrothermal liquefaction (HTL) was investigated to obtain fermentable sugars, platform chemicals, bio-oil, and biochar. The SWH was evaluated at 230 and 260 °C and solvent: feed mass ratios (R) of 10 and 20 for the production of fermentable sugars and platform chemicals. The solid residue from SWH was sequentially submitted to the HTL at 330 and 360 °C for bio-oil and biochar production. The results were analyzed by comparing the sequential (SWH/HTL) and individual (HTL only) processes. The highest yields of fermentable sugars (5.26 g/ 100 g BCE) were obtained for SWH at 260 °C and R-20 with higher contents of xylose (2.64 g/100 g BCE) and cellobiose (1.75 g/100 g BCE). The highest yields of platform chemicals (2.44 g/100 g BCE) were obtained for SWH at 260 °C and R-10 with higher contents of acetic acid (1.78 g/100 g BCE) and furfural (0.54 g/100 g BCE). The highest yield of bio-oil (25.30 g/100 g BCE) occurred in HTL individual process at 360 °C and R-20. Sequential process SWH/HTL showed a decrease in bio-oil yield but maintained a similar biochar yield compared to HTL, in addition to the production of fermentable sugars and platform chemicals. [ABSTRACT FROM AUTHOR]

A metal‐free three‐component reaction for the direct synthesis of α‐sulfonamide phosphonates involving sulfonamide derivatives, benzaldehyde derivatives, and diethyl phosphite, has been achieved with high yields using ethanol as a green solvent. This efficient method reduces reaction time and minimizes the use of excess reagents. Hitherto, no reports have been found in the literature for the direct synthesis of α‐sulfonamide phosphonates from the readily available aldehydes, diethyl phosphite, and sulfonamides, emphasizing the novelty and significance of this work. [ABSTRACT FROM AUTHOR]

Vegetable oils are rich in health-beneficial compounds, including fatty acids, phenolic compounds, natural antioxidants, and fat-soluble vitamins. However, oil extraction methods can influence their composition. This study aims to understand the chemical basis for developing a green process to extract oils from two Andean seeds, cañihua (Chenopodium pallidicaule) and tarwi (Lupinus mutabilis). Ethanol, considered a green solvent, is compared to petroleum ether used at the laboratory level and hexane used at the industrial scale for extracting oils. The extraction efficiency is assessed in terms of yield, fatty acids profile, polar and neutral lipids, tocopherols, phenolic compounds, and antioxidant capacity. The chemical composition of edible commercial oils, such as sunflower, rapeseed, and olive oils, was used as a reference. Hexane had the highest extraction yield, followed by petroleum ether and ethanol. However, the oils extracted with ethanol having yields of tarwi 15.5% and cañihua 5.8%, w/w showed the significatively superior content of tocopherols (α, γ, and δ); phenolic compounds; and antioxidant capacity. In addition, ethanol-extracted (EE) oils have higher levels of polar lipids, such as phosphatidylcholine and phosphatidylinositol, than those extracted with the other solvents. Remarkably, EE oils presented comparable or slightly higher levels of monounsaturated fatty acids than those extracted with hexane. Finally, compared to the commercial oils, tarwi and cañihua EE oils showed lower but acceptable levels of oleic, linoleic and palmitic acids and a wider variety of fatty acids (10 and 13, respectively). The composition of tarwi and cañahua oils extracted with ethanol includes compounds associated with nutritional and health benefits, providing a sustainable alternative for oil production. [ABSTRACT FROM AUTHOR]

Organometallic lead halide perovskite powders have gained widespread attention for their intriguing properties, showcasing remarkable performance in the optoelectronic applications. In this study, formamidinium lead iodide (α‐FAPbI3) microcrystals (MCs) is synthesized using retrograde solubility‐driven crystallization. Additionally, methylammonium lead bromide (MAPbBr3) and cesium lead iodide (δ‐CsPbI3) MCs are prepared through a sonochemical process, employing low‐grade PbX2 (X = I & Br) precursors and an eco‐friendly green solvent (γ‐Valerolactone). The study encompasses an analysis of the structural, optical, thermal, elemental, and morphological characteristics of FAPbI3, MAPbBr3, and CsPbI3 MCs. Upon analysing phase stability, a phase transition in FAPbI3 MCs is observed after 2 weeks. To address this issue, a powder‐based mechanochemical method is employed to synthesize stable mixed cation perovskite powders (MCPs) by subjecting FAPbI3 and MAPbBr3 MCs with varying concentrations of CsPbI3. Furthermore, the performance of mixed cation perovskites are examined using the Solar Cell Capacitance Simulator (SCAPS‐1D) software. The impact of cesium incorporation in the photovoltaic characteristics is elucidated. All mixed cation absorbers exhibited optimal device performance with a thickness ranging between 0.6–1.5 µm. It's worth noting that the MCPs exhibit impressive ambient stability, remaining structurally intact and retaining their properties without significant degradation for 70 days of ambient exposure. [ABSTRACT FROM AUTHOR]

Research on the preparation of diallyl sulfides and selenides is always an important challenge among chemists because these compounds are of high biological, pharmaceutical, industrial and chemical importance. For this purpose, in this attractive and highly efficient approach, we wish to report that copper (I) chloride immobilized on magnetic nanoparticles modified with benzothiazole–pyrimidine ligand (Fe3O4@BTH-Pyr-CuCl) is a novel and efficient magnetically recoverable catalyst for C–S and C–Se bonds formation through reaction of a category of heterocyclic compounds with aryl iodides, sulfur and selenium sources. The structure of Fe3O4@BTH-Pyr-CuCl nanocatalyst was well identified with FT-IR, SEM, TEM, EDX, elemental mapping, TGA, XRD, VSM and ICP-OES techniques. The recycling tests confirmed that the Fe3O4@BTH-Pyr-CuCl nanocatalyst was reused for 6 times without considerable reduction in its activity. This method is almost better than other methods reported in the literature for C–S and C–Se coupling of heterocycles for the following reasons, such as the use of an environmentally friendly solvent, high yields of products, the use of a catalyst that can be separated and reused and the performance of the reaction in a shorter time, presentation of well-analysis for catalyst and full NMR for products. [ABSTRACT FROM AUTHOR]

The inorganic cesium lead bromide (CsPbBr3) perovskite solar cell (PSC) is considered as an attractive option for new solar cells due to its outstanding stability. Preparing CsPbBr3 PSCs with H2O can effectively save costs and reduce the harm of toxic solvents to the environment. However, the poor contact property of the PbBr2 layer to the CsBr/H2O solution and the ability of water to dissolve the CsPbBr3 phase has a significant impact on the performance of the CsPbBr3 devices. In this article, isobutyramide is introduced into the PbBr2 film in the first step to improve the wettability of the PbBr2 film to CsBr/H2O solution, followed by spin‐coating of the 150 mg mL−1 CsBr/H2O solution on the PbBr2 film. Using this strategy, the fabricated PSCs with the architecture of FTO/compact‐TiO2/mesoporous‐TiO2/CsPbBr3 film/carbon demonstrate outstanding performance with a maximum efficiency of 9.59%. Furthermore, after 45 days of storage at ambient temperatures, the unencapsulated device retains more than 96% of its original efficiency. Therefore, this work provides a good demonstration for the preparation of high‐efficiency and eco‐friendly CsPbBr3 PSCs. [ABSTRACT FROM AUTHOR]

[Display omitted] Over the last few decades, significant research efforts have been devoted to developing new cleaning systems aimed at preserving cultural heritage. One of the main objectives is to selectively remove aged or undesirable coatings from painted surfaces while preventing the cleaning solvent from permeating and engaging with the pictorial layers. In this work, we propose the use of electrospun polyamide 6,6 nonwovens in conjunction with a green solvent (dimethyl carbonate). By adjusting the electrospinning parameters, we produced three distinct nonwovens with varying average fiber diameters, ranging from 0.4 μm to 2 μm. These samples were characterized and tested for their efficacy in removing dammar varnish from painted surfaces. In particular, the cleaning process was monitored using macroscale PL (photoluminescence) imaging in real-time, while post-application examination of the mats was performed through scanning electron microscopy. The solvent evaporation rate from the different nonwovens was evaluated using gravimetric analysis and Proton Transfer Reaction- Time-of-Flight. It was observed that the application of the nonwovens with small or intermediate pore sizes for the removal of the terpenic varnish resulted in the swollen resin being absorbed into the mats, showcasing a peel-off effect. Thus, this protocol eliminates the need for further potentially detrimental removal procedures involving cotton swabs. The experimental data suggests that the peel-off effect relates to the microporosity of the mats, which enhances the capillary rise of the swollen varnish. Furthermore, the application of these systems to historical paintings underwent preliminary validation using a real painting from the 20th century. [ABSTRACT FROM AUTHOR]

Reactant solubility, which dictates achievable concentrations, and the stability of reaction intermediates (excited states), solvents modulate the potential energy landscape and influence reaction rates. Consequently, solvent selection is pivotal in optimizing process productivity, economic feasibility, and environmental footprint. At present, organic synthesis pivots around the idea of sustainability. In particular, PEG‐400, a popular solvent and phase transfer catalyst, is considered greener as it can be reused several times without significant loss in its catalytic activity, which checks the box regarding sustainability. This review highlights the emerging potential of Polyethylene Glycol 400 (PEG‐400) as a dual‐threat agent in sustainable organic synthesis. We explore its efficacy as a catalyst, promoting various reactions under mild conditions and often eliminating the need for traditional metal catalysts. Additionally, PEG‐400's role as a green solvent is addressed, emphasizing its biodegradability, low toxicity, and ability to facilitate reactions without hazardous Volatile Organic Compounds (VOCs). The review examines recent research on PEG‐400 mediated reactions, showcasing its effectiveness in diverse transformations, thus exploring the potential of PEG 400 as a facilitator for heterocycle synthesis in both multicomponent reactions and stepwise approaches. It identifies exciting research directions that promise to expand the boundaries of polymer‐based solvents in heterocyclic chemistry. [ABSTRACT FROM AUTHOR]

Hexafluoropropylene oxide (HFPO) is a versatile fluorochemical widely used in the synthesis of various fluorinated compounds and fluorinated polymers. In this paper, we report on the successful synthesis of HFPO via the epoxidation of hexafluoropropylene (HFP) with NaOCl in a two-phase solvent system. Among the organic phase solvents tested, hydrofluoroethers such as C4F9OCH3, C4F9OC2H5, and C7F15OC2H5 showed high HFPO yields, indicating their potential to replace conventional CFCl2CF2Cl (CFC-113), which is ozone depleting and global warming chemical. When the reaction was carried out for 20 min at room temperature, the C4F9OCH3—water two-phase system produced HFPO with over 40% yield and over 70% selectivity. To optimize the reaction conditions, various reaction parameters were investigated, including the effects of NaOH and phase transition catalysts. Analysis of the by-products using 19F and 13C NMR and X-ray diffraction (XRD) showed that HFP/HFPO decomposes during oxidation to F¯, CO2, oxalate, trifluoroacetate, etc. Density functional theory (DFT) calculations elucidated the reaction pathway of this epoxidation: with a lower E-barrier of 12.8 kcal/mol, the nucleophilic attack of OCl¯ on the β-carbon of HFP is preferable to the α-carbon pathway. [ABSTRACT FROM AUTHOR]

ABSTRACT Lignocellulosic biomass, the most abundant natural resource on earth, can be used for cellulosic ethanol production but requires a pretreatment to improve enzyme access to the polymeric sugars while obtaining value from the other components. γ‐Valerolactone (GVL) is a promising candidate for biomass pretreatment since it is renewable and bio‐based. In the present work, the effect of a pretreatment based on GVL on the enzymatic saccharification of white birch was evaluated at a laboratory scale and the importance of the washing procedure for the subsequent saccharification was demonstrated. Both the saccharification yield and the production of cellulosic ethanol were higher using a noncommercial enzyme crude from Talaromyces amestolkiae than with the commercial cocktail Cellic CTec2 from Novozymes. Furthermore, the production of extracellular cellulases by T. amestolkiae has been optimized in 2 L bioreactors, with improvements ranging from 40% to 75%. Finally, it was corroborated by isoelectric focus that optimization of cellulase secretion by T. amestolkiae did not affect the pattern production of the main β‐glucosidases and endoglucanases secreted by this fungus.

Ionic liquids (ILs) have many beneficial properties that are extensively used in various fields. Despite their utility, the phytotoxic aspects of ILs are poorly known. This is especially true at the transcriptomic level and the role of nitric oxide (NO) in this process. Herein, we studied the mechanism by which endogenous NO reduces the toxicity of ILs in Arabidopsis. We examined the effects of two imidazolium-based ILs (IILs) on three Arabidopsis lines, each characterized by distinct endogenous NO levels, using a combination of physiological and transcriptomics methods. IILs impaired seed germination, seedling development, chlorophyll content, and redox homeostasis in Arabidopsis. Notably, 1,3-dibutyl imidazole bromide had greater toxicity than 1-butyl-3-methylimidazolium chloride. Nox1, a mutant with an elevated NO level, had enhanced resistance, while nia1nia2, a mutant with a diminished NO level, had increased susceptibility compared to the wild type. RNA sequencing results suggested that NO mitigates IILs-induced phytotoxicity by modulating the metabolism of chlorophyll and secondary metabolites, and by bolstering the antioxidant defense system. These findings illustrate the complex molecular networks that respond to IIL stress and reveal the potential of endogenous NO as a mitigating factor in plant stress physiology.

The application of bio-based solvents for living radical polymerization has been a hot topic in recent year. In this article, γ-valerolactone (GVL), a bio-based solvent as green media for ARGET atom transfer radical polymerization (ATRP) of styrene (St) were investigated. We first conducted polymerization of St in γ-valerolactone using copper(ii) bromide as the catalyst, tris(2-pyridylmethyl) amine as the ligand, and only sodium ascorbate as reducing agent. The polymerization achieved moderate conversion; however, the controllability of polymerization was not very good, providing a polymer with a broad molecular weight distribution (M w/M n > 1.30). When sodium carbonate is introduced, excellent results were obtained providing high yields and low M w/M n values under very low catalyst usage (∼5 ppm). 1H NMR spectroscopy, chain extension, and MALDI–MS experiments confirmed the final polymer chains with high fidelity. The use of GVL solvent opens a new route for the easy synthesis of PS through ARGET ATRP with low catalyst usage conditions.

ABSTRACTTriethyl phosphate (TEP) is a new member of the Green Solid-Phase Peptide Synthesis (GSPPS) toolbox. TEP shows almost no toxicity and no carcinogenic or mutagenic properties. It degrades, giving the rather innocuous phosphoric acid and ethanol. TEP has a low viscosity, which makes it appealing for solid-phase peptide synthesis (SPPS), where the reagents delivered by the solvent should penetrate the polymeric matrix. TEP dissolves most Fmoc-amino acids and key coupling reagents and additives. The use of TEP has allowed the SPPS of several model peptides using the most conventional polystyrene resin at room temperature, while other green solvents required more sophisticated resins and/or elevated temperatures. In conclusion, TEP is an excellent contender to become the green solvent of choice.

The utilization of two-dimensional (2D) materials in optoelectronic devices has witnessed a surge. Production of 2D ultrathin molybdenum disulfide (MoS2) nanosheets without the use of toxic precursors and without altering the phase of the material is still a task. We developed a cost-effective liquid-phase exfoliation method that is free of additives, utilizing ultrasound to produce a significant amount of nearly single-layered MoS2 nanosheets by employing isopropyl alcohol and deionized water as a cosolvent. This work addresses the deficiencies in the current state-of-the-art studies by exploring the mechanism governing ultrasonic cavitation, resulting in MoS2 nanosheets. Various sonication durations were altered to investigate the relationship between the duration of sonication and the dimensionality of the resulting nanosheets. The findings revealed that prolonged sonication durations yielded bilayered and trilayered nanosheets. The reduction in layer thickness was confirmed by Raman modes as the sonication time increased. Size-dependent optical studies indicated that the optical properties have enhanced as the sonication time increased. An open-aperture Z-scan investigation was conducted to explore the size-dependent nonlinear optical features of MoS2 nanosheets, employing a 532 nm neodymium-doped yttrium aluminum garnet pulsed laser in a nanosecond pulsed regime. The optical limiting performance of the nanosheets sonicated at various time intervals was accessed and it was observed that as the nanosheets' thickness decreases, the optical limiting behavior improves. Due to two-photon absorption, MoS2 nanosheets display optical limiting behaviors through reverse saturable absorption. Optical limiting thresholds as low as 2.98 × 1012 W/m2 are attained. This significant enhancement suggests that these ultrathin MoS2 nanosheets are suitable for applications in laser shielding. [ABSTRACT FROM AUTHOR]

The green transition requires new, clean, inexpensive, and sustainable strategies to prepare controllable bimetallic and multimetallic nanostructures. Cu−Ag nanostructures, for example, are promising bimetallic catalysts for different electrocatalytic reactions such as carbon monoxide and carbon dioxide reduction. In this work, we present the one‐step preparation method of electrodeposited Cu−Ag with tunable composition and morphology from choline chloride plus urea deep eutectic solvent (DES), a non‐toxic and green DES. We have assessed how different electrodeposition parameters affect the morphology and composition of our nanostructures. We combine electrochemical methods with ex‐situ scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), and X‐ray photoelectron spectroscopy (XPS) to characterize the nanostructures. We have estimated the electrochemically active surface area (ECSA) and roughness factor (R) by lead underpotential deposition (UPD). The copper/silver ratio in the electrodeposited nanostructures is highly sensitive to the applied potential, bath composition, and loading. We observed that silver‐rich nanostructures were less adherent whereas the increase in copper content led to more stable and homogenous films with disperse rounded nanostructures with tiny spikes. These spikes were more stable when the deposition rate was fast enough and the molar ratio of Cu and Ag was no greater than approximately two to one. [ABSTRACT FROM AUTHOR]