Search Results (22)

Amid global energy crises and environmental pollution, the valorization of renewable biomass resources like corn stover lignin is crucial. This review systematically examines the innovative application of switchable solvents (CO₂-responsive, thermo-responsive, pH-responsive) for extracting lignin from corn stover and its subsequent pyrolysis into bio-oil. We critically analyze the extraction mechanisms, key process parameters (e.g., solvent type, temperature, solid-to-liquid ratio), and their intricate effects on lignin yield and purity. Furthermore, we delve into the pyrolysis kinetics, product distribution influenced by conditions (temperature, atmosphere, catalysts), and comprehensive characterization of the resulting bio-oil. This review highlights the broad application prospects of pyrolysis oil in energy, chemical feedstocks, and niche markets, while frankly addressing current challenges: high costs, product quality issues, and technological immaturity. Finally, we propose future directions focusing on green solvent design, process intensification, multi-technique characterization protocols, and the imperative for integrated lifecycle and techno-economic assessments to guide sustainable industrialization. Full article

Deep eutectic solvents (DESs) have emerged as sustainable and tunable alternatives to conventional solvents for the extraction of polysaccharides. This review presents a structure-informed framework linking DES composition to polysaccharide solubility, emphasizing the differential responsiveness of amorphous, interfacial, and crystalline domains. Amorphous polysaccharides are efficiently extracted under mild DES conditions, while crystalline polymers often require stronger hydrogen bond acceptors or thermal/mechanical activation. Beyond dissolution, DESs modulate key properties of the extracted polysaccharides, including molecular weight, monomer composition, and bioactivity. Comparative analysis highlights how acidic, basic, or metal-coordinating DESs selectively target distinct polymer classes. Emerging innovations, such as in situ DES formation, mechanochemical systems, and switchable solvents, enhance efficiency and reduce downstream processing demands. Furthermore, the integration of machine learning and COSMO-RS modeling enables predictive solvent design, reducing reliance on empirical screening. By combining mechanistic insight, compositional tailoring, and computational tools, this review provides a scientifically grounded perspective for advancing DES-mediated extraction processes and enabling structure-preserving, application-oriented recovery of polysaccharides in food, pharmaceutical, and biorefinery domains. Full article

Multilayer flexible packaging wastes (MFPWs) consist of complex materials composed of multiple plastic films, which are often laminated with aluminum foil, and they constitute a large portion of packaging waste. The use of several polymeric layers is essential to achieve the desired technical and mechanical performance of the packaging; however, this makes layer separation and recycling challenging. Currently, this type of waste is predominantly incinerated or landfilled; non-industrial recycling processes have recently been developed, but they mostly rely on traditional solvent-based treatments, which can be problematic. We present a versatile process for recycling MFPWs using switchable hydrophilicity solvents (SHSs). By treating waste with SHSs through a temperature-controlled process, we efficiently recovered the polymeric layers as sorted transparent films, effectively removing all additives while preserving the original properties of the polymers. Aluminum was recovered as well. N,N-dimethylcyclohexylamine was the best solvent for the delamination of the 26 different packaging materials tested, containing polypropylene, polyethylene, polyethylene terephthalate, and aluminum. The main advantage of this method is the straightforward recovery of the different components that can be efficiently delaminated and easily removed from the solvent, even from highly variable input material. Moreover, by exploiting the CO₂-triggered switchable behavior of the solvent, its purification and recovery can be achieved, maintaining its delamination efficacy over several cycles. Full article

Lignin, the most abundant natural aromatic polymer, holds considerable promise for applications in various industries. The primary obstacle to the valorization of lignin into useful materials is its low molecular weight and diminished chemical reactivity, attributable to its intricate structure. This study aimed to treat lignocellulosic biomass using a switchable solvent (DBU–HexOH/H₂O) derived from the non-nucleophilic superbase 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU), which efficiently separates and extracts lignin from poplar wood. Additionally, it sought to characterize fundamental properties of the extracted switchable solvent lignin (SSL) and propose a mechanism for its separation. In comparison to milled wood lignin, SSL exhibits a greater molecular weight, superior homogeneity, and enhanced stability. The SSL sample was analyzed using spectroscopies including infrared spectroscopy, nuclear magnetic resonance, and X-ray photoelectron spectroscopy. The findings indicated that the structure of SSL was preserved, with the switchable solvent primarily cleaving the C–C and α-O-4 bonds, resulting in a low hydroxyl content, an elevated H/C ratio, and a reduced O/C ratio. The SSL was successfully prepared to lignin nanoparticles (LNPs) with size range of 531–955 nm. This paper presents a technique for processing lignocellulosic biomass using a switchable solvent, highlighting advancements in lignin’s structure and enhancing its use in the chemical sector. Full article

2, 6-diisopropylaniline (2, 6-DIPA) is a crucial non-intentionally organic additive that allows the assessment of the production processes, formulation qualities, and performance variations in biodegradable mulching film. Moreover, its release into the environment may have certain effects on human health. Hence, this study developed simultaneous heating hydrolysis–extraction and amine switchable hydrophilic solvent vortex-assisted homogeneous liquid–liquid microextraction for the gas chromatography–mass spectrometry analysis of the 2, 6-DIPA additive and its corresponding isocyanates in poly(butylene adipate-co-terephthalate) (PBAT) biodegradable agricultural mulching films. The heating hydrolysis–extraction conditions and factors influencing the efficiency of homogeneous liquid–liquid microextraction, such as the type and volume of amine, homogeneous-phase and phase separation transition pH, and extraction time were investigated and optimized. The optimum heating hydrolysis–extraction conditions were found to be a H₂SO₄ concentration of 2.5 M, heating temperature of 87.8 °C, and hydrolysis–extraction time of 3.0 h. As a switchable hydrophilic solvent, dipropylamine does not require a dispersant. Vortex assistance is helpful to speed up the extraction. Under the optimum experimental conditions, this method exhibits a better linearity (0.0144~7.200 μg mL⁻¹ with R = 0.9986), low limit of detection and quantification (0.0033 μg g⁻¹ and 0.0103 μg g⁻¹), high extraction recovery (92.5~105.4%), desirable intra- and inter-day precision (relative standard deviation less than 4.1% and 4.7%), and high enrichment factor (90.9). Finally, this method was successfully applied to detect the content of the additive 2, 6-DIPA in PBAT biodegradable agricultural mulching films, thus facilitating production process monitoring or safety assessments. Full article

A study on the synergistic extraction of Eu(III) ions with a series of chelating ligands and determination of the process parameters is presented by employing ionic liquids and typical organic diluents. The investigations of the liquid–liquid extraction, commonly applied in the separation science of 4f and 5f-ions acidic chelating compounds, 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP), 4-benzoyl-3-phenyl-5-isoxazolone (HPBI), and 2-thenoyltrifluoroacetone (HTTA) alone and in combination with two synergistic agents, meso-hexamethylpropyleneamine oxime (S2: HM-PAO) and its bis-imine precursor (S1: pre-HM-PAO), are presented. The interaction between the two extractants (acidic/neutral) in deuterochloroform was studied using ¹H, ¹³C, and ¹H-¹H NOESY experiments. Several conclusions are given highlighting the role of the ionic diluent in complexation processes and selectivity with an employment of the two synergistic agents for various metal s-, p-, d-, and f-cations in the Periodic table, with almost 25 metal ions. The objective was to optimize a system for 4f-ions solvent extraction based on the new oxime molecules with β-diketone/isoxazolone/pyrazolone partnership. As detailed above, slight enhancements of extraction efficiencies were obtained either by using basic synergistic agents such as HM-PAO and/or using pre-HM-PAO. A competitive solvent extraction test of nearly 18 f-ions by various ligands (HTTA, S1, S2, and HPBI) and the two mixtures HTTA−S1 and HTTA−S2 diluted in ILs or organic diluents was also conducted in order to evaluate the switchable diluent impact. Additionally, electron paramagnetic resonance (EPR) spectroscopy was used to study the established chemical species with Cu²⁺ cations in the obtained organic extracts involving the two synergistic molecules. Full article

Deep eutectic solvents (DESs) are promising for lignin dissolution and extraction. However, they usually possess high polarity and are difficult to recycle. To overcome this drawback, a variety of switchable ionic liquids (SILs) composed of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and alcohols was synthesized and screened. According to the thermodynamic modeling suggestions, the selected DBU–HexOH SIL was coupled with hydrogen-bond donors to form switchable-DES (SDES) systems with moderated viscosity, conductivity, and pH while maintaining switchability. The SDESs produced a well-improved lignin and lignin model compound solubility compared with those of SILs; charging CO₂ into SDES (SDES_CO2) caused a further increase in solubility. The solubility (25 °C) of syringic acid, ferulic acid, and milled wood lignin in SDES_CO2 reached 230.57, 452.17, and 279.12 mg/g, respectively. Such SDES-dissolved lignin can be regenerated using acetone as an anti-solvent. The SDES-regenerated lignin exhibited a well-preserved structure with no noticeable chemical modifications. Furthermore, the SDES_CO2 lignin possessed a higher molecular weight (Mw = 10,340 g/mol; Mn = 7672 g/mol), improved uniformity (polydispersity index = 1.35), and a higher guaiacyl lignin unit content compared with the original milled wood lignin. The SDES system proposed in the present work could benefit the fractionation of lignin compounds and facilitate downstream industrial processes. Full article

The exploitation of shale gas resources brings in abundant hazardous oil-based drilling cuttings (ODBCs). Herein, N, N-Dimethylcyclohexylamine (DMCHA) acted as the CO₂ switchable hydrophilic solvents (SHSs), and the OBDCs treated with DMCHA were studied, especially priority pollutant migration and produced wastewater assessment during the extraction process. The petroleum hydrocarbon content of OBDCs decreased from 10.73 to 0.84 wt% after the DMCHA extraction was conducted at a DMCHA/OBDCs liquid–solid ratio of 20:1, 35 °C, and 200 rpm for 30 min. Using the CO₂ switchability of SHSs, the petroleum hydrocarbon and DMCHA were recovered. There was wastewater, which was produced after recovering DMCHA, and the produced wastewater assessment showed that chemical oxygen demand, 5-day biochemical oxygen demand, total nitrogen, total organic carbon, and petroleum were 561.00, 238.00, 40.60, 309.00, and 0.27 mg/L, respectively. Meanwhile, phenols (0.0031 mg/L), naphthalene (0.0000129 mg/L), phenanthrene (0.000059 mg/L), anthracene (0.000058 mg/L), as well as heavy metal ions such as Cu (0.01 mg/L) could be detected in the produced wastewater. As a result, a priority pollutant migration mechanism from ODBCs to the produced wastewater was proposed. This would be helpful for the better management policy making of the ODBCs treated by using CO₂ SHSs and the produced wastewater. Full article

Cellulose-grafte-poly(L-lactide) (C-g-PLLA) copolymers synthesized in a CO₂-switchable solvent are proposed for use as effective compatibilizers for the preparation of cellulose–PLLA composites with enhanced interfacial compatibility. The effect of the molar substitution (MS_PLLA) of the grafted PLLA side chain in the C-g-PLLA copolymer and the feeding amount of this copolymer on the mechanical and thermal properties and hydrophilicity of the composites was investigated. The composites had a largely increased impact strength with the incorporation of the compatibilizer. With the increasing of MS_PLLA and the feeding amount of the copolymer, the resulting composites had an increased impact strength. When 5 wt% C-g-PLLA with MS_PLLA of 4.46 was used as a compatibilizer, the obtained composite containing 20 wt% cellulose presented an impact strength equal to that obtained for the neat PLLA. The composites had a slightly decreased melting temperature and thermal decomposition temperature, but increased hydrophilicity due to the incorporation of the compatibilizer. This work suggests an effective method to improve the interfacial compatibility between cellulose and PLLA for the fabrication of fully bio-based composites with high performance. Full article

Highly crystalline, organic-solvent-dispersible titanium dioxide (TiO₂) nanorods (NRs) present promising chemicophysical properties in many diverse applications. In this paper, based on a modified procedure from literature, TiO₂ NRs were synthesized via a ligand-assisted nonhydrolytic sol-gel route using oleic acid as the solvent, reagent, and ligand and titanium (IV) isopropoxide as the titanium precursor. This procedure produced monodisperse TiO₂ NRs, as well as some semi-spherical titania nanocrystals (NCs) that could be removed by size-selective precipitation. X-ray diffraction and selected area electron diffraction results showed that the nanorods were anatase, while the semipheres also contained the TiO₂(B) phase. By taking samples during the particle growth, it was found that the average length of the initially grown NRs decreased during the synthesis. Possible reasons for this unusual growth path, partially based on high-resolution transmission electron microscopy (HRTEM) observations during the growth, were discussed. The dispersion of anatase TiO₂ nanorods was capable of spontaneous formation of lyotropic liquid crystals on the TEM grid and in bulk. Considering high colloidal stability together with the large optical birefringence displayed by these high refractive index liquid crystalline domains, we believe these TiO₂ NRs dispersions are promising candidates for application in transparent and switchable optics. Full article

Herein, we report on the metal-free, one-pot synthesis of industrially important dimethyl carbonate (DMC) from molecular CO₂ under ambient conditions. In this process, initially the CO₂ was chemisorbed through the formation of a switchable ionic liquid (SIL), [DBUH] [CH₃CO₃], by the interaction of CO₂ with an equivalent mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol. The obtained SIL further reacted with methyl iodide (CH₃I) to form DMC. The synthesis was carried out in both dimethyl sulfoxide (DMSO) and methanol. Methanol is preferred, as it not only served as a reagent and solvent in CO₂ capture and DMC synthesis, but it also assisted in controlling the side reactions between chemical species such as CH₃I and [DBUH]⁺ cation and increased the yield of DMC. Hence, the use of methanol avoided the loss of captured CO₂ and favored the formation of DMC with high selectivity. Under the applied reaction conditions, 89% of the captured CO₂ was converted to DMC. DBU was obtained, achieving 86% recovery of its salts formed during the synthesis. Most importantly, in this report we describe a simple and renewable solvent-based process for a metal-free approach to DMC synthesis under industrially feasible reaction conditions. Full article

The properties of polymer-based nanocomposites strongly depend on the fillers added and their dispersion on the matrix. Proposing a simple method that can control these variables is essential to obtain nanocomposites with enhanced properties. In this study, cellulose triacetate based nanocomposites modified with sol-gel synthesised vanadium oxide nanoparticles (V₂O₅) and poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-b-PPO-b-PEO or EPE) triblock copolymer were obtained by two methods: solvent casting (SC, drying at ambient conditions) and solvent vapour annealing (SVA, drying under solvent vapour atmosphere). Nanocomposites were characterised by Fourier-transform infrared spectroscopy (FTIR) and UV-vis spectroscopy. Nanocomposites presented green colour and high transparency, improving the SVA method the surface finish of the films. Moreover, V₂O₅ nanoparticles provided switchable photochromic properties, changing the film colour from green to pale blue when exposed to UV radiation. Nanocomposites with EPE triblock copolymer presented a more noticeable colour change. As for the speed of the recovery process to the initial state, it increased with the addition of EPE and the sol-gel content. Thus, it was proved that the SVA preparation method was more appropriate that the SC, as well as corroborate that the EPE triblock copolymer and the sol-gel content affected the properties of developed CTA nanocomposites. Full article

Achieving remotely controlled, reversibly reconfigurable assemblies of plasmonic nanoparticles is a prerequisite for the development of future photonic technologies. Here, we obtained a series of gold-nanoparticle-based materials which exhibit long-range order, and which are controlled with light or thermal stimuli. The influence of the metallic core size and organic shell composition on the switchability is considered, with emphasis on achieving light-responsive behavior at room temperature and high yield production of nanoparticles. The latter translates to a wide size distribution of metallic cores but does not prevent their assembly into various, switchable 3D and 2D long-range ordered structures. These results provide clear guidelines as to the impact of size, size distribution, and organic shell composition on self-assembly, thus enhancing the smart design process of multi-responsive nanomaterials in a condensed state, hardly attainable by other self-assembly methods which usually require solvents. Full article

In the present work, the effectiveness of switchable hydrophobicity solvents (SHSs) as extraction solvent (N,N-Dimethylcyclohexylamine (DMCA), N,N-Diethylethanamine (TEA), and N,N-Benzyldimethylamine (DMBA)) for a variety of emerging pollutants was evaluated. Different pharmaceutical products (nonsteroidal anti-inflammatory drugs (NSAIDs), hormones, and triclosan) were selected as target analytes, covering a range of hydrophobicity (LogP) of 3.1 to 5.2. The optimized procedure was used for the determination of the target pharmaceutical analytes in wastewater samples as model analytical problem. Absolute extraction recoveries were in the range of 51% to 103%. The presented method permits the determination of the target analytes at the low ng mL⁻¹ level, ranging from 0.8 to 5.9 (except for Triclosan, 106 ng mL⁻¹) with good precision (relative standard deviation lower than 6%) using high-pressure liquid chromatography (HPLC) combined with ultraviolet (DAD) and fluorescence (FLR) detection. The microextraction alternative resulted in a fast, simple, and green method for a wide variety of analytes in environmental water sample. The results suggest that this type of solvent turns out to be a great alternative for the determination of different analytes in relatively complex water samples. Full article

Switchable luminescent bioprobes whose emission can be turned on as a function of specific enzymatic activity are emerging as important tools in chemical biology. We report a promising platform for the development of label-free and continuous enzymatic assays in high-throughput mode based on the reversible solvent-induced self-assembly of a neutral dinuclear Pt(II) complex. To demonstrate the utility of this strategy, the switchable luminescence of a dinuclear Pt(II) complex was utilized in developing an experimentally simple, fast (10 min), low cost, and label-free turn-on luminescence assay for the endonuclease enzyme DNAse I. The complex displays a near-IR (NIR) aggregation-induced emission at 785 nm in aqueous solution that is completely quenched upon binding to G-quadruplex DNA from the human c-myc oncogene. Luminescence is restored upon DNA degradation elicited by exposure to DNAse I. Correlation between near-IR luminescence intensity and DNAse I concentration in human serum samples allows for fast and label-free detection of DNAse I down to 0.002 U/mL. The Pt(II) complex/DNA assembly is also effective for identification of DNAse I inhibitors, and assays can be performed in multiwell plates compatible with high-throughput screening. The combination of sensitivity, speed, convenience, and cost render this method superior to all other reported luminescence-based DNAse I assays. The versatile response of the Pt(II) complex to DNA structures promises broad potential applications in developing real-time and label-free assays for other nucleases as well as enzymes that regulate DNA topology. Full article