Search Results (69)

Conventional amine-based solvents such as monoethanolamine (MEA) and diethanolamine (DEA) are widely used for CO₂ removal from natural gas but this technology suffers from drawbacks including high regeneration energy, solvent degradation, and corrosion issues. To overcome these limitations, this study investigates the use of newly synthesized hydrophobic protic ionic liquids (HPILs) composed of ammonium cations coupled with the bis(trifluoromethane)sulfonylimide ([Tf₂N]⁻) anion for CO₂ absorption using the pressure-drop method. The results show that CO₂ solubility increases with pressure but decreases with temperature. Among the studied ionic liquids (ILs), [BEHA][Tf₂N] exhibits the highest CO₂ capacity at 298.15 K within the pressure range of 1–20 bar, which is consistent with its free volume (V_f) value. Furthermore, a comparison study indicates that all ILs demonstrate superior CO₂ selectivity over methane (CH₄) at 298.15 K. The recyclability study shows that [BEHA][Tf₂N] maintains its structural integrity over two CO₂ absorption cycles at 20 bar across all tested temperatures. Full article

A chemical platform for post-polymerization methods was developed, starting from the ecodesign and enzymatic synthesis of safe and sustainable bio-based polyesters containing discrete units of itaconic acid. This unsaturated bio-based monomer enables the covalent linkage of molecules that can impart desired properties such as hydrophilicity, flexibility, permeability, or affinity for biological targets. Molecular descriptor-based computational methods, which are generally used for modeling the pharmacokinetic properties of drugs (ADME), were employed to predict in silico the hydrophobicity (LogP), permeability, and flexibility of virtual terpolymers composed of different polyols (1,4-butanediol, glycerol, 1,3-propanediol, and 1,2-ethanediol) with adipic acid and itaconic acid. Itaconic acid, with its reactive vinyl group, acts as a chemical platform for various post-polymerization functionalizations. Poly(glycerol adipate itaconate) was selected because of its higher hydrophilicity and synthetized via solvent-free enzymatic polycondensation at 50 °C to prevent the isomerization or crosslinking of itaconic acid. The ecotoxicity and marine biodegradability of the resulting oligoester were assessed experimentally in order to verify its compliance with safety and sustainability criteria. Finally, the viability of the covalent linkage of biomolecules via Michael addition to the vinyl pendant of the oligoesters was verified using four molecules bearing thiol and amine nucleophilic groups: N-acetylcysteine, N-Ac-Phe-ε-Lys-OtBu, Lys-Lys-Lys, and glucosamine. Full article

In this study, a solvent-free, slow-curing, inherently flame-retardant polyurea coating was successfully developed through an optimized formulation. The novel polyurea was synthesized using mixed Schiff base latent curing agents derived from terminal polyether amines with different-number average molecular weights (D2000 and D400), methyl isobutyl ketone, and polyethyl phosphate glycol ester (OP550). Subsequently, polyurea/meta-aramid (PUA/AF) composite fabrics were fabricated via a scraping coating technique. Thermogravimetric analysis revealed enhanced char formation and reduced decomposition temperatures due to the incorporation of OP550. Comprehensive flame retardant performance was demonstrated through vertical flame testing, limiting oxygen index, and micro-scale combustion calorimetry, with results showing significantly reduced heat release rates, lower total heat release, and increased residual char. Mechanical evaluations indicated marked improvements in tearing, tensile, single-yarn tensile, and bursting forces, attributed to strong fiber–polyurea interfacial interactions, as confirmed by detailed SEM morphological analyses. Moreover, the PUA/AF composites exhibited excellent static puncture resistance and effective self-healing capability. Collectively, these advancements highlight the potential of PUA/AF composite fabrics as promising candidates for advanced protective textiles, integrating superior flame retardancy, mechanical strength, puncture resistance, and self-repairing functionality. Full article

The enzyme ω-transaminase (ω-TA) has garnered significant attention due to its capacity to catalyze the synthesis of chiral amines with high efficiency. Nevertheless, the lack of stability of ω-TA and the difficulty of recycling and reuse are still challenges that limit its application. This study developed a novel magnetic nanocellulose composite carrier (NNC@Fe₃O₄@Ni), synthesized from microcrystalline cellulose via low-eutectic solvent treatment, amine modification, and metal hybridization. The NNC@Fe₃O₄@Ni was characterized by FTIR, XPS, XRD, BET, and VSM. Additionally, the performance and catalytic behavior of the immobilized enzyme were investigated. The results revealed that NNC@Fe₃O₄@Ni exhibited a high specific surface area, superparamagnetism, and dual-site functionality (amine/Ni²⁺). Response Surface Methodology (RSM) optimized the carrier-enzyme interaction parameters, yielding optimal immobilization conditions: a mass ratio of 50.8 mg g⁻¹, temperature of 12.5 °C, and duration of 58.6 min, achieving 82.91% enzyme activity recovery. Compared to free enzymes, the immobilized variant demonstrated enhanced catalytic stability, with expanded optimal pH (9.0) and temperature (30 °C). Thermal stability assessments showed 84.39% activity retention after 5 h at 30 °C and 90.30% residual activity post-120 h storage. The catalyst maintained >80% efficiency over 10 reuse cycles. These findings confirm the efficacy of magnetic nanocellulose carriers in enhancing ω-TA stability, reusability, and catalytic performance, offering a viable strategy for industrial biocatalytic processes. Full article

Polyhydroxyurethanes (PHUs) synthesized from cyclic carbonates are promising alternatives to conventional polyurethanes due to their advantageous isocyanate-free synthesis and reprocessability characteristics. While many studies focus on PHUs derived from five-membered cyclic carbonates (5CCs) for more sustainable synthesis routes, PHUs from six-membered cyclic carbonates (6CCs) exhibit enhanced reactivity towards amines. Their reprocessability is facilitated by the presence of hydroxyl groups along the polymer chain, enabling transcarbamoylation reactions. However, since non-catalyzed transcarbamoylation is typically a sluggish reaction, catalysts are often required to enhance network reprocessability. This study presents a life cycle assessment (LCA) of PHU-5CC and PHU-6CC syntheses, with catalysts, for recycling applications targeting end-of-life scenarios. Environmental impact categories, including climate change, particulate matter, fossil resource depletion, mineral and metal resource use and freshwater eutrophication, were evaluated. Sensitivity analyses were also conducted to assess key variables. Our results indicate that PHUs from 6CCs show a higher environmental footprint due to their solvent-intensive synthesis process. Despite the increased reactivity and shorter reaction times associated with the 6CC monomer, these benefits do not fully offset the environmental impacts of the synthesis process. In conclusion, this study highlights potential improvements for future PHU synthesis, such as solvent-free processes, metal-free catalysts and optimized reaction monitoring. Full article

In the 21st century, sustainable agriculture is expected to become a major contributor to food security and improved nutrition. Amine–epoxide-based materials have great potential for use in agriculture due to their tunable physicochemical features, which are dependent on the concentration and composition of the monomers. In this work, catalyst-free green synthesis, using only water as a solvent, was performed to obtain a nanocarrier (TGel) capable of transporting nutrients after seed priming. The synthesis was based on the opening of the epoxy ring by nucleophile attack, using an amine-terminated polyether. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques showed the spherical morphology of the particles, which ranged in size from 80 nm (unloaded TGel) to 360 nm (zinc-loaded TGel), respectively. Theoretical bonding analysis revealed that Zn cation species from the ZnSO₄ source interact with the polymer via σ-bonds, whereas EDTA forms hydrogen bonds with the polymer, thereby enhancing noncovalent interactions. Micro X-ray fluorescence (μ-XRF) and energy-dispersive X-ray fluorescence spectroscopy (EDXRF) provided details of the distributions of Zn in the seed compartments and shoots of cucumber plants after seed priming and plant growth, respectively. The use of the Zn-loaded TGels did not affect the physiology of the cucumber plants, as indicated by the photosynthetic efficacy, chlorophyll, and anthocyanin indices. Full article

A simple one-pot reaction of LiAlH₄, AlCl₃, and a secondary amine HNR₂ [R = Et, ⁱPr, ⁱBu, cyclo-C₆H₁₁, (CH₂)₄, and (CH₂)₅] in hydrocarbon solvents results in the formation of exogenous Lewis-base-free amidoalanes [H₂Al(NR₂)]_n (n = 2 or 3) as crystalline solids (35–85% yield). In the solid state (seven X-ray structures), all the amidoalanes exist as dimers, with the exception of the pyrrolidine-derived alane which exists as a trimer. As solids, these amidoalanes exhibit significant kinetic stability towards oxygen/moisture allowing the brief (ca. 5 min.) handling of [H₂Al(NⁱPr₂)]₂ in air. Full article

Magnetic ionic liquid (MIL) based on alkyl phosphonium cation was used as a curing agent for developing epoxy nanocomposites (ENCs) modified with a graphene nanoplatelet (GNP)/carbon nanotube (CNT) hybrid filler. The materials were prepared by a solvent-free procedure involving ball-milling technology. ENCs containing as low as 3 phr of filler (GNP/CNT = 2.5:0.5 phr) exhibited electrical conductivity with approximately six orders of magnitude greater than the system loaded with GNP = 2.5 phr. Moreover, the use of MIL (10 phr) resulted in ENCs with higher conductivity compared with the same system cured using conventional aliphatic amine. The filler dispersion within the epoxy matrix was confirmed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electromagnetic interference shielding effectiveness (EMI SE), evaluated in the X- and Ku-band frequency range, revealed a great contribution of the absorption mechanism for the ENC containing the hybrid filler and cured with MIL. Moreover, the best microwave-absorbing response was achieved with the ENC containing GNP/CNT = 2.5/0.5 phr, and cured with ML, which a minimum RL of −23.61 dB and an effective absorption bandwidth of 5.18 GHz were observed for thickness of 1.5 mm. In summary, this system is a promising material for both civilian and military applications due to its simple and scalable nanocomposite preparation method, the lightweight nature of the composites resulting from the low filler content, the commercial availability and cost-effectiveness of GNP, and its high electromagnetic wave attenuation across a broad frequency range. Full article

This work discusses the synthesis and properties of nonisocyanate polyurethanes (NIPUs) as an environmentally friendly alternative to traditional polyurethanes. NIPUs are made without the use of toxic isocyanates, reducing the environmental impact and safety concerns associated with their production. However, their synthesis reactions often require longer time and more energy to be completed. The sustainability of NIPUs is considered from various angles; the main methods for the synthesis of NIPUs, including rearrangement reactions, transurethanization, and ring-opening polymerization of cyclic carbonates with amines, are examined. Another part focuses on renewable sources, such as vegetable oils, terpenes, tannins, lignins, sugars, and others. The synthesis of waterborne and solvent-free NIPUs is also discussed, as it further reduces the environmental impact by minimizing volatile organic compounds (VOCs) and avoiding the use of harmful solvents. The challenges faced by NIPUs, such as lower molecular weight and higher dispersity compared to traditional polyurethanes, which can affect mechanical properties, were also addressed. Improving the performance of NIPUs to make them more competitive compared to conventional polyurethanes remains a key task in future research. Full article

Selenoxide syn elimination is a widely used method for the synthesis of alkenes because it proceeds under exceptionally mild conditions, typically with excellent regio- and stereoselectivity. Surprisingly, hetero-selenoxide eliminations, where one or both olefinic carbon atoms are replaced with heteroatoms, have been little investigated, and their selenonyl counterparts even less so. A variety of such reactions, where the heteroatoms included combinations of O, N and S, as well as C, were investigated computationally. Selenoxides typically have lower activation energies and are slightly endothermic, while the corresponding selenones display higher activation energies and are exothermic in the gas state. The results are consistent with concerted, five-centre processes, leading to the formation of dioxygen, aldehydes, diazenes and imines from seleninyl or selenonyl peroxides, esters, hydrazines and amines, respectively. The more acidic selenenyl hydrodisulfide analogue undergoes proton transfer to the basic selenoxide oxygen atom instead of concerted elimination, resulting in the formation of a zwitterion. However, the formation of the corresponding selenonyl zwitterion is disfavoured compared to concerted syn elimination. The effects of solvents were also computed along with changes in enthalpy, entropy and free energy. Solvent effects were variable, while free energy calculations indicated overall ΔG values ranging between 3.60 and −32.12 kcal mol⁻¹ for the syn eliminations of methyl methanethioseleninate and methaneperoxyselenonic acid, respectively. These computations suggest that the olefin-forming selenoxide syn elimination may be more general than currently understood and that replacement of the two carbon atoms with heteroatoms can lead to viable processes. Full article

Organic compounds with antibacterial and antiparasitic properties are gaining significance for biomedical applications. This study focuses on the solvent-free synthesis (green synthesis) of 1,4-naphthoquinone or 2,3-dichloro-1,4-naphthoquinone with different phenylamines using silica gel as an acid solid support. The study also includes in silico PASS predictions and the discovery of antibacterial and antiparasitic properties of phenylaminonaphthoquinone derivatives 1–12, which can be further applied in drug discovery and development. These activities were discussed in terms of molecular descriptors such as hydrophobicity, molar refractivity, and half-wave potentials. The in vitro antimicrobial potential of the synthesized compounds 1–12 was evaluated against a panel of six bacterial strains (three Gram-positive: Staphylococcus aureus, Proteus mirabilis, and Enterococcus faecalis; and three Gram-negative bacteria: Escherichia coli, Salmonella typhimurium, and Klebsiella pneumoniae). Six compounds (1, 3, 5, 7, 10, and 11) showed better activity toward S. aureus with MIC values between 3.2 and 5.7 μg/mL compared to cefazolin (MIC = 4.2 μg/mL) and cefotaxime (MIC = 8.9 μg/mL), two cephalosporin antibiotics. Regarding in vitro antiplasmodial activity, compounds 1 and 3 were the most active against the Plasmodium falciparum strain 3D7 (chloroquine-sensitive), displaying IC₅₀ values of 0.16 and 0.0049 μg/mL, respectively, compared to chloroquine (0.33 μg/mL). In strain FCR-3 (chloroquine-resistant), most of the compounds showed good activity, with compounds 3 (0.12 μg/mL) and 11 (0.55 μg/mL) being particularly noteworthy. Additionally, docking studies were used to better rationalize the action and prediction of the binding modes of these compounds. Finally, absorption, distribution, metabolism, excretion, and toxicity (ADMET) predictions were performed. Full article

Three Fe₃O₄ magnetic solvent-free nanofluids with different amine-based coronal layer structures are synthesized and characterized by using magnetic Fe₃O₄ as the core, silane coupling agent as the corona, and polyether amines with different graft densities and chain lengths as the canopy. The concentration of heavy metal ions after adsorption is measured by atomic absorption spectrometry (AAS) to study the effect of Fe₃O₄ magnetic solvent-free nanofluids on the adsorption performance of the heavy metal ions lead (Pb(II)) and copper (Cu(II)) in water. The adsorption of Fe₃O₄ magnetic solvent-free nanofluid was explored by changing external condition factors such as adsorption contact time and pH. Additionally, the adsorption model is established. The magnetic solvent-free nanofluid is separated from water by applying an external magnetic field to the system, and desorption and cyclic adsorption tests are carried out. Based on the adsorption mechanism, the structure design of Fe₃O₄ magnetic solvent-free nanofluid was optimized to achieve optimal adsorption performance. Full article

In the present study, citrus peels were extracted using various conventional and deep eutectic solvents (DESs). Compared to other citrus peel extracts, the DES extract based on choline chloride showed notably higher total phenolic and flavonoid content levels, along with superior antioxidant activity, among these extracts. Consequently, this study aimed to further investigate the inhibitory effects of the choline chloride based DES extract on the production of both free and bound heterocyclic amines (HAs) and advanced glycation end products (AGEs) in roast pork meat patties. The results indicated that the addition of choline chloride-based DES extracts, particularly the choline chloride-carbamide based DES extract, can effectively reduce the oxidation of lipids and proteins by quenching free radicals. This approach proves to be the most efficient in reducing the formation of both HAs and AGEs, leading to a significant reduction of 19.1–68.3% and 11.5–66.5% in free and protein-bound HAs, respectively. Moreover, the levels of free and protein-bound AGEs were reduced by 50.8–50.8% and 30.5–39.8%, respectively, compared to the control group. Furthermore, the major phenolics of citrus peel extract identified by UHPLC-MS were polymethoxylated flavonoids (PMFs) including hesperidin, isosinensetin, sinensetin, tetramethoxyflavone, tangeretin, and hexamethoxyflavone, which inferring that these compounds may be the main active ingredients responsible for the antioxidant activity and inhibition effects on the formation of HAs and AGEs. Further research is needed to explore the inhibitory effects and mechanisms of PMFs with different chemical structures on the formation of HAs and AGEs. Full article

4-substituted aminopyrido [2,3-d]pyrimidines derivatives 1a–f were synthesized via the multicomponent reaction of 2-aminopyridines, triethyl orthoformate, and diverse primary amines under solvent-free conditions. The present work creates a variety of fluorescent heterocyclic compounds in a short time and with good yields. The structures of all synthesized compounds were established by IR, ¹H, and ¹³C NMR analysis. Full article

Solid-phase microextraction (SPME) is a sample preparation technique which utilizes small amounts of an extraction phase for the extraction of target analytes from investigated sample matrices. Its simplicity of use, relatively short sample processing time, and fiber reusability have made SPME an attractive choice for many analytical applications. SPME has been widely applied to the sampling and analysis of environmental, food, aromatic, metallic, forensic, and pharmaceutical samples. Solid phase microextraction is used in horticultural crops, for example, to determine water and soil contaminants (pesticides, alcohols, phenols, amines, herbicides, etc.). SPME is also used in the food industry to separate biologically active substances in food products for various purposes, for example, disease prevention, determining the smell of food products, and analyzing tastes. SPME has been applied to forensic analysis to determine the alcohol concentration in blood and that of sugar in urine. This method has also been widely used in pharmaceutical analysis. It is a solvent-free sample preparation technique that integrates sampling, isolation, and concentration. This review focuses on recent work on the use of SPME techniques in the analysis of food and horticultural crops. Full article