Search Results (278)

The utilization and chemical transformation of carbon dioxide remains a pressing problem in modern chemistry. Numerous experimental and theoretical studies have focused on the interaction of CO₂ with amines. In this work, quantum chemical density functional theory (DFT) calculations of equilibrium geometries, energies, electronic and vibrational characteristics of CO₂-sensitive mono-, di-, tris-hydroxyamidines and their associates were carried out by the B3LYP/6-31G(d, p) method. The harmonic vibrational frequencies were scaled and compared with the experimental FTIR spectra for supporting wavenumber assignments. Natural bond orbital (NBO) analysis of the atomic charges and charge delocalization was employed to investigate the nature of hydrogen bonding in hydroxyamidine associates. We also used the intrinsically polarizable continuum model (IEFPCM), and the DFT-D3 method was applied to account for dispersion effects during associate formation. Using the 6-311+G(2d, p) basis set for tris-hydroxyamidine, and its adducts, a comparative analysis of the experimental and calculated ¹H NMR spectra was performed. Here, we considered non-trivial sites of carbon dioxide absorption and hydroxyamidine protonation, which, to our knowledge, have hardly been considered by other authors. Present DFT results agree rather well with the experimental data and support new insight into the formation of the PIL structure. Full article

High-ash coal slime water, characterized by its stable colloidal suspension of fine kaolinite particles, poses a significant challenge in the coal preparation industry because it is hard to achieve efficient solid–liquid separation. While traditional coagulants and flocculants often suffer from limited bridging capabilities and distinct pH sensitivity, novel molecular architectures offer potential solutions. In this study, a star-shaped inorganic–organic hybrid flocculant (Al-PAM) was synthesized via in situ polymerization. Its flocculation performance and interfacial adsorption mechanism on the specifically targeted aluminol basal plane of kaolinite were systematically investigated and compared with Polyaluminum Chloride (PAC), Non-ionic Polyacrylamide (NPAM), and their combination (PAC + NPAM). Settling tests revealed that Al-PAM exhibited superior performance at a significantly lower dosage (10 mg∙L⁻¹) compared to the PAC + NPAM binary reagent system. It achieved a rapid initial settling velocity and reduced the supernatant turbidity to 48.45 NTU, while maintaining a near-neutral pH favorable for water recycling. Furthermore, Quartz Crystal Microbalance with Dissipation (QCM-D) monitoring confirmed that Al-PAM forms a thick, viscoelastic, and irreversible adsorption layer on the Al₂O₃ substrate. The dissipation shifts (ΔD) revealed that the star-shaped architecture promotes distinct bridging and electrostatic adsorption, overcoming the limitation of linear polymers. This work elucidates the specific contribution of the alumina-surface interaction with flocculants and proposes an efficient strategy for treating refractory coal slime water. Full article

Insulin injection remains the best therapy for diabetes mellitus, but subcutaneous injection continues to pose challenges, including patient discomfort, poor compliance and fluctuating plasma glucose profiles. Recently, transdermal insulin delivery has emerged as a non-invasive strategy that bypasses gastrointestinal degradation and first-pass hepatic metabolism, thereby increasing insulin bioavailability and enhancing patient acceptance. Recent developments in nanomedicine have facilitated the development of transdermal patches with enhanced drug encapsulation, uptake and controlled release. Nanostructured lipid carriers, polymeric nanocomposites, liposomes and SLNs have demonstrated a five-fold enhancement of transdermal flux and an extended insulin effect in preclinical models. The addition of ionic liquids and polymeric nanogels leads to an additional increase in insulin aqueous solubility and permeation, resulting from the temporary regulation of stratum corneum lipid organization. Bright and stimuli-responsive patches with glucose oxidase or phenylboronic acid functional groups enable regulated insulin delivery in response to changes in blood glucose, demonstrating near-normoglycemia for up to 48 h in animal testing. Nanocomposite systems assisted by microneedles have also been advanced to the early clinical phase, offering enhanced reproducibility of their pharmacokinetics and a low risk of dermal irritation. Despite these encouraging results, several translational challenges remain, such as biocompatibility, repeatability in the production of nanocarriers, long-term stability of formulations and regulatory standardization. This review examines the physicochemical design principles, materials innovations and permeation mechanism of nanomedicine-engineered insulin patches, the current state of preclinical and clinical advancements, challenges in production and future perspectives in viable patient-focused transdermal insulin delivery. Full article

Polymer blends are an essential category of materials formed by physically combining two or more polymers. The plasticizing process is advantageous for brittle or rigid polymer systems that need improved flexibility or ductility. The increasing demand for environmentally friendly and high-performance polymeric materials has spurred research into alternative plasticization methods. The use of ionic liquids as non-volatile plasticizers in polymer blends is owing to their outstanding properties. In this short review, several ionic liquids employed in polymer blends and some polymers used in blends with ionic liquids are listed. Additionally, the plasticizing effects of ionic liquids on the properties of polymer blends are concisely elucidated. This review also provides a brief overview of the potential applications of polymer blends plasticized with ionic liquids. In summary, many studies reveal that ionic liquid-based plasticization impacts the structural, thermal, conductive, and mechanical properties of polymer blends. The potential applications of polymer blends plasticized with ionic liquids cover various fields, including energy systems, packaging, electronics, and soft robotics. Full article

This study reports the synthesis and catalytic evaluation of a series of imidazolium-based polymeric ionic liquids (PILs) for the cycloaddition of CO₂ to epichlorohydrin (ECH). The synthesized catalysts include homopolymers, poly(3-hydroxyethyl-1-vinylimidazole chloride) (p[HVIm][Cl]) and poly(3-carboxymethyl-1-vinylimidazole chloride) (p[CMVIm][Cl]), and their block copolymers with polystyrene, synthesized for the first time, pS-b-p[HVIm][Cl] and pS-b-p[CMVIm][Cl]. Structural characterization by NMR, IR spectroscopy, and gel permeation chromatography confirmed the successful synthesis. The block copolymers exhibited a low polydispersity index (PDI 1.1–1.2), which is indicative of homogeneous chain lengths and the propensity to form ordered nanostructures, whereas the homopolymers showed higher PDI (2.4–2.9). Catalytic testing at 90 °C and 1 MPa CO₂ for 4 h revealed a clear activity trend: p[CMVIm][Cl] < p[HVIm][Cl] < pS-b-p[CMVIm][Cl] < pS-b-p[HVIm][Cl], with conversions exceeding 75% for all catalysts and a maximum of 82.69% for pS-b-p[HVIm][Cl]. These results demonstrate that the catalytic performance of PILs is governed by a synergistic interplay between the local chemical functionality of the ionic moiety and the overall polymer architecture. Based on these results, the synthesized polymeric ionic liquids, particularly pS-b-p[HVIm][Cl], demonstrate strong potential for creating multifunctional materials. Their ability to self-assemble into ordered nanostructures with distinct hydrophobic and hydrophilic domains provides a foundational architecture for combined gas separation and catalysis. The observed “micellar catalytic effect”, which enhances local reagent concentration near active sites, could be leveraged in a membrane reactor to simultaneously capture and convert CO₂ directly within the membrane. This integrated “separation–reaction” approach represents a promising strategy for advancing circular carbon economy technologies. Full article

Nanofluid development is facing the challenge of instability despite the significant body of research dedicated to developing new nanoparticle-enhanced fluids. Numerous combinations of fluids and particles have been studied; however, the research on surfactants is rather limited, and the results are scattered. This paper is dedicated to the study of two regular polymeric surfactants (PVP and PSS) as well as two polyethylene glycols and one ionic liquid as possible alternatives. The results of a coordinated experiment are followed by a discussion of the density, thermal conductivity, thermal effusivity and viscosity of several samples with the same amount of titanium oxide nanoparticles dispersed in water and different mass concentrations of surfactants (2, 4 and 6%wt.). The results indicated that both the thermal properties and viscosity are negatively affected by the addition of surfactant, which is a drawback. The viscosity remains within a reasonable variation (i.e., between a 0.7 and 1.5% increase) for concentrations of PEG 200, PEG 400 and PSS up to 2%wt. Also, the addition of titania nanoparticles increases the water thermal conductivity by 1.8%, while the addition of surfactant decreases the overall values by around 5%. This disadvantage is amplified when also considering the foam creation, characteristic of all regular surfactants, that limits their real-life applications in turbulent flow. Full article

The aza-Michael reaction is a fundamental transformation for carbon–nitrogen bond formation, providing efficient access to β-amino carbonyl compounds, nitriles, and related nitrogen-containing building blocks of broad importance in medicinal chemistry and organic synthesis. Over the past two decades, ionic liquids (ILs) have attracted considerable attention as alternative reaction media, promoters, and catalysts for aza-Michael reactions, owing to their distinctive physicochemical properties and tunable structures. This review presents a comprehensive and critical overview of ionic-liquid-mediated aza-Michael reactions, emphasizing the evolution of IL design from early imidazolium-based systems to modern task-specific, supported, and bio-derived ionic liquids. Conventional room-temperature ionic liquids are discussed as non-innocent solvents capable of stabilizing charged intermediates and enhancing electrophilicity, thereby enabling catalyst-free or metal-assisted aza-Michael additions. Subsequent sections focus on task-specific ionic liquids incorporating Brønsted acidic, basic, hydrogen-bond-donating, or bifunctional motifs, highlighting how rational structural design translates into improved activity, selectivity, and substrate scope. Particular attention is devoted to guanidine-, DABCO-, and DBU-based ionic liquids, where mechanistic studies reveal cooperative activation modes rather than simple acid–base catalysis. Recent advances in supported and polymeric ionic liquids are also reviewed, demonstrating effective strategies to combine IL-like reactivity with enhanced recyclability and operational simplicity. Overall, this review clarifies the diverse roles of ionic liquids in aza-Michael chemistry and outlines current challenges and future perspectives toward more sustainable and efficient C–N bond-forming methodologies. Full article

Plastic streams dominated by polyethylene (PE) including PE HD/MD (High Density/Medium Density) and PE LD/LLD (Low Density/Linear Low Density), polypropylene (PP), and polyvinyl chloride (PVC) across Europe demand a design framework that links synthesis with end of life reactivity, supporting circular economic goals and European Union waste management targets. This work integrates polymerization derived chain architecture and depolymerization mechanisms to guide selective valorization of commercial plastic wastes in the European context. Catalytic topologies such as Bronsted or Lewis acidity, framework aluminum siting, micro and mesoporosity, initiators, and strategies for process termination are evaluated under relevant variables including temperature, heating rate, vapor residence time, and pressure as encountered in industrial practice throughout Europe. The analysis demonstrates that polymer chain architecture constrains reaction pathways and attainable product profiles, while additives, catalyst residues, and contaminants in real waste streams can shift radical populations and observed selectivity under otherwise similar operating windows. For example, strong Bronsted acidity and shape selective micropores favor the formation of C₂ to C₄ olefins and Benzene, Toluene, and Xylene (BTX) aromatics, while weaker acidity and hierarchical porosity help preserve chain length, resulting in paraffinic oils and waxes. Increasing mesopore content shortens contact times and limits undesired secondary cracking. The use of suitable initiators lowers the energy threshold and broadens processing options, whereas diffusion management and surface passivation help reduce catalyst deactivation. In the case of PVC, continuous hydrogen chloride removal and the use of basic or redox co catalysts or ionic liquids reduce the dehydrochlorination temperature and improve fraction purity. Staged dechlorination followed by subsequent residue cracking is essential to obtain high quality output and prevent the release of harmful by products within European Union approved processes. Framing process design as a sequence that connects chain architecture, degradation chemistry, and operating windows supports mechanistically informed selection of catalysts, severity, and residence time, while recognizing that reported selectivity varies strongly with reactor configuration and feed heterogeneity and that focused comparative studies are required to validate quantitative structure to selectivity links. In European post consumer sorting chains, PS and PC are frequently handled as separate fractions or appear in residues with distinct processing routes, therefore they are not included in the polymer set analyzed here. Polystyrene and polycarbonate are outside the scope of this review because they are commonly handled as separate fractions and are typically optimized toward different product slates than the gas, oil, and wax focused pathways emphasized here. Full article

This study presents a methanol-assisted pathway that converts hydroxyl-containing amidine into a polymeric ionic liquid (PIL) through direct CO₂ fixation, followed by its transformation into a cross-linked ionic polymer (CL-IP). Methanol plays a crucial role in this process, acting as both a structural and electronic mediator. Its strong hydrogen-bonding interactions with amidine activate the molecule toward CO₂ capture and promote the formation of ionic intermediates. Spectroscopic analyses (FTIR, ¹H and ¹³C NMR) revealed the emergence of amidinium and alkyl-carbonate groups, while viscosity and mass measurements indicated progressive polymerization during CO₂ absorption. Density functional theory calculations confirmed the stabilizing effect of methanol and the reduced HOMO–LUMO gap, which facilitates PIL formation. The subsequent condensation of the PIL with glutaraldehyde produced a dense three-dimensional cross-linked network (CL-IP), as verified by FTIR, XPS, SEM, and TGA analyses. These results highlight a straightforward and sustainable strategy for constructing hydrogen-bond-mediated ionic polymers capable of tunable CO₂ capture and potential application in environmentally compatible materials. Full article

In this work, the properties of polymer composites filled with carbon fillers were investigated. The subject of the research was polymeric materials prepared from styrene-butadiene rubber (KER 1500) commonly used in rubber processing, using a conventional sulfur-containing curing system. Two different carbon fillers were applied, namely furnace carbon black (N550) and graphene nanoplatelets (XG G300). These fillers were modified in bulk (during rubber compound preparation) with 4-methyl-1-butylpyridinium bromide (BmPyBr). Modifier would interact with filler’s surface through, e.g., π–π interactions between its pyridine ring and surface of the fillers. The paper highlights the different tendency of the polymer to interact with filler particles of different shapes and sizes, as well as the interactions between filler particles in the presence of an ionic liquid. The rheometric properties of rubber compounds as well as cross-linking density and mechanical properties of SBR composites were studied. Additionally, rheological and viscoelastic properties at the service temperature and the damping properties as a function of deformation of the obtained materials were examined. Full article

Conductive hydrogels are ideal for flexible strain sensors, yet their practical use is often limited by water evaporation, signal hysteresis, and structural instability, which impair linearity, durability, and long-term reliability. To overcome these challenges, we developed a robust multiple-network hydrogel composed of poly(vinyl alcohol) (PVA), polyacrylic acid (PAA), in situ polymerized polyaniline (PANi), and the ionic liquid [EMIM][TFSI]. The resulting composite exhibits an exceptional linear piezoresistive response across its entire working range—from rest to fracture strain of 290%—together with high conductivity (0.68 S/cm), fast response/recovery (0.34 s/0.35 s), and a maximum gauge factor of 2.78. Mechanically robust (tensile strength ≈ 3.7 MPa, modulus ≈ 1.3 MPa), the hydrogel also demonstrates outstanding cyclic durability, withstanding over 12,000 stretching–relaxation cycles, and markedly improved dehydration resistance, retaining about 60% of its mass after 3 days at room temperature. This work provides a holistic material solution for developing high-performance, reliable strain sensors suitable for wearable electronics and soft robotics. Full article

Solid-state batteries (SSBs) are regarded as one of the most promising next-generation energy storage technologies due to their high energy density and improved safety. To achieve this goal, the development of solid-state electrolytes with high ionic conductivity and low interfacial resistance is essential. In recent years, composite polymer electrolytes (CPEs) have garnered extensive attention due to their ability to combine the intrinsic flexibility of polymers with the enhanced ionic conductivity and mechanical robustness provided by inorganic fillers. Metal–organic frameworks (MOFs), characterized by tunable pore structures, high surface areas, and excellent thermal and mechanical stability, are considered ideal fillers for constructing MOF–polymer composite electrolytes (MPCEs). This review summarizes the performance enhancement mechanisms of MPCEs and strategies for electrode–electrolyte interface stability. First, the primary preparation methods of MPCEs are introduced. Subsequently, the roles of MOFs in regulating ionic transport, suppressing dendrite growth, improving electrochemical stability, and optimizing the solid electrolyte interphase (SEI) layer are discussed. In addition, various interface engineering strategies are highlighted, including in situ polymerization of the polymer matrix, in situ growth of MOF fillers, integration of liquid plasticizers forming gel-like ionic conductor, and design of composite electrode to enhance interfacial compatibility and stability. Finally, the significant challenges and future research directions of MPCEs are outlined. This review provides valuable insights into the rational design of MPCEs and offers guidance for the development and practical application of high-performance SSBs. Full article

In this study, patch-structured C₈/CHO template microspheres were successfully synthesized through in situ reduction and sol–gel reactions, providing a reusable platform for subsequent modifications. Based on these templates, temperature-responsive PW₁₂O₄₀³⁻-PILs/PNIPAM Janus nanosheets were prepared via sequential Schiff-base coupling and ATRP. Structural characterizations (XRD, SEM, TEM, FTIR, and TGA) confirmed successful functionalization and nanosheet formation. The PNIPAM moiety endowed the nanosheets with temperature responsiveness, while the incorporation of polymerized ionic liquids and phosphotungstate anions further enhanced amphiphilicity and dispersion stability. When applied as particulate emulsifiers in water/toluene systems, the Janus nanosheets formed stable Pickering emulsions at elevated temperatures and underwent reversible emulsification–demulsification upon temperature cycling. These findings demonstrate the potential of PW₁₂O₄₀³⁻-PILs/PNIPAM Janus nanosheets as smart emulsifiers for responsive separation and formulation technologies. Full article

Owing to multiple non-covalent interactions, ionic groups impart unique chemical and physical properties into polymers including ion conductivity/mobility, permeation, and intrinsic healability. Ionenes contain ionic groups in their polymer backbone, which offer great versatility in polymer design. Herein, selected aliphatic and aromatic imidazoles were synthesized, which were used as monomeric building blocks for the preparation of thermoplastic ionenes by following a Sn2 step growth reaction across organic halides. The structure and molecular weight of the polymers was characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) techniques. Once polymerized, anion-exchange reactions were carried out to replace the halides with four other counter-anions. Subsequently, the effect of the nature of the anion and the cation on the polymers’ thermal and hygroscopic properties was studied in detail by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and FTIR spectroscopy. Depending on the chemical structures of the polymeric cations and the related anions, tailored polymers with a glass transition temperature (T_g) in the range of 30 °C to 131 °C and a thermal stability varying between 170 °C and 385 °C were obtained. Full article

Enhancing the safety of lithium-ion batteries (LIBs) by replacing flammable electrolytes is a key challenge. Ionic liquid (IL)-based electrolytes are considered an interesting alternative due to their thermal and chemical stability, high voltage stability window, and tunable properties. This study investigates the electrochemical behavior of two newly synthesized ILs, comparing them to conventional alkyl carbonate-based electrolytes. Nitrogen-doped carbon silicon oxycarbide (NC-SiOC), used as the active material in negative electrodes, was combined with two polymeric binders: poly(acrylic acid) (PAA) and poly(acrylonitrile) (PAN). NC-SiOC/PAN electrodes exhibited a significantly higher initial charge capacity—approximately 25–30% greater than their PAA-based counterparts in the first cycle at 0.1 A g⁻¹ (850–990 mAh g⁻¹ vs. 600–700 mAh g⁻¹), and demonstrated an improved initial Coulombic efficiency (67% vs. 62%). Long-term cycling stability over 1000 cycles at 1.6 A g⁻¹ retained 75–80% of the initial 0.1 A g⁻¹ capacity. This outstanding performance is attributed to the synergistic effects of nitrogen-rich carbonaceous phases within the NC-SiOC material and the cyclized-PAN binder, which facilitate structural stability by accommodating volumetric changes and enhancing solid electrolyte interphase (SEI) stability. Notably, despite the lower ionic transport properties of the IL electrolytes, their incorporation did not compromise performance, supporting their feasibility as safer electrolyte alternatives. These findings offer one of the most promising electrochemical performances reported for SiOC materials to date. Full article