Search Results (5,006)

This study investigates the modification of bitumen using mechanochemically devulcanized crumb rubber. The objective of this research is to enhance the performance characteristics of bituminous binders while addressing the inherent limitations associated with conventional crumb rubber (CCR), such as insufficient dispersion, elevated viscosity, and phase instability. Preliminary chemical activation of the crumb rubber was performed using a planetary ball mill, followed by thermomechanical devulcanization on a two-roll open mixing mill. Structural features of the devulcanized crumb rubber were analyzed using infrared spectroscopy, which confirmed the breakdown of S–S bonds. This study presents a comparative analysis of the performance characteristics of rubber–bitumen binders produced using both conventional rubber crumb (CRC) and devulcanized rubber crumb (DRC). The use of DCR, obtained mechanochemically from rubber waste, improved penetration, Fraass breaking point and the ring and ball softening point on average at high concentrations (20; 25% crumb rubber) compared to conventional crumb rubber by 33%, 66% and 2.4%, respectively. Optical microscopy revealed the formation of a uniform mesh-like rubber structure within the bitumen matrix, which contributes to enhanced performance characteristics of the modified binder and improved mechanical strength of the material. The key contribution of this work lies in the development and experimental validation of an efficient approach to deep devulcanization of crumb rubber via mechanochemical activation using readily available nitrogen-containing reagents. Furthermore, the study establishes a direct correlation between the degree of devulcanization, the dispersion quality of rubber particles within the bitumen matrix, and the resultant performance characteristics of the modified binder. Full article

The interface between high-performance thermoelectric materials and electrodes critically governs the conversion efficiency and long-term reliability of thermoelectric generators under high-temperature operation. Here, we propose Al_xCoCrFeNi high-entropy alloys (HEA) as barrier layers to bond Cu-W electrodes with p-type skutterudite (p-SKD) thermoelectric materials. The HEA/p-SKD interface exhibited excellent chemical bonding with a stable and controllable reaction layer, forming a dense, defect-free (Fe,Ni,Co,Cr)Sb phase (thickness of ~2.5 μm) at the skutterudites side. The interfacial resistivity achieved a low value of 0.26 μΩ·cm² and remained at 7.15 μΩ·cm² after aging at 773 K for 16 days. Moreover, the interface demonstrated remarkable mechanical stability, with an initial shear strength of 88 MPa. After long-term aging for 16 days at 773 K, the shear strength retained 74 MPa (only 16% degradation), ranking among the highest reported for thermoelectric materials/metal joints. Remarkably, the joint maintained a shear strength of 29 MPa even after 100 continuous thermal cycles (623–773 K), highlighting its outstanding thermo-mechanical stability. These results validate the Al_xCoCrFeNi high-entropy alloys as an ideal interfacial material for thermoelectric generators, enabling simultaneous optimization of electrical and mechanical performance in harsh environments. Full article

We hypothesized that compounds containing ether linkages within their backbone structures, when exposed to hydroxyl radicals (•OH), can generate ultra-weak photon emission (UPE) as a result of the formation of triplet excited carbonyl species (³R=O*). To evaluate this hypothesis, we investigated the UPE of four compounds, each at a final concentration of 185.2 µmol/L: EGTA (ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid), a potent chelator of divalent cations, and three crown ethers—12-crown-4, 15-crown-5, and 18-crown-6—containing two, four, five, and six ether bonds, respectively. •OH was generated using a modified Fenton reagent—92.6 µmol/L Fe²⁺ and 2.6 mmol/L H₂O₂. The highest UPE was recorded for the Fe²⁺–EGTA–H₂O₂ (2863 ± 158 RLU; relative light units), followed by 18-crown-6, 15-crown-5, and 12-crown-4 (1161 ± 78, 615± 86, and 579 ± 109 RLU, respectively; p < 0.05), corresponding to the number of ether groups present. Controls lacking either H₂O₂ or Fe²⁺ exhibited no significant light emission compared to the buffer medium. These findings support the hypothesis that ether bonds, when oxidatively attacked by •OH, undergo chemical transformations resulting in the formation of ³R=O* species, the decay of which is associated with UPE. In crown ethers exposed to Fe²⁺-H₂O₂, the intensity of UPE was correlated with the number of ether bonds in their structure. Full article

The development of miniaturized sensors has become relevant for the detection of chemical/biological substances, since they use and detect low concentrations, such as flocculants based on amines for the mining industry. In this study, buckypaper (BP) films based on carboxylic acid functionalized multi-walled carbon nanotubes (f-MWCNTs) were produced through vacuum filtration on cellulose filter paper to carry out sensory function in samples containing ether-amine (volumes: 1%, 5%, 10% and 100%). The morphological characterization of the BPs by scanning electron microscopy showed f-MWCNT aggregates randomly distributed on the cellulose fibers. Vibrational analysis by Raman spectroscopy indicated bands and sub-bands referring to f-MWCNTs and vibrational modes corresponding to chemical bonds present in the ether-amine (EA). The electrical responses of the BP to the variation in analyte concentration showed that the sensor differentiates deionized water from ether-amine, as well as the various concentrations present in the different analytes, exhibiting response time of 3.62 ± 0.99 min for the analyte containing 5 vol.% EA and recovery time of 21.16 ± 2.35 min for the analyte containing 10 vol.% EA, revealing its potential as a real-time response chemiresistive sensor. Full article

The photocatalytic performance of heterojunctions is often restricted by inferior contact interface and low charge transfer efficiency. In this work, Ti₃C₂O MXene was crafted with AgI/MoS₂ to produce a Z-scheme heterojunction (AgI/MoS₂/Ti₃C₂O). Interfacial electric fields and chemical bonds were proven to exist in the heterojunction. The interfacial electric fields supplied a powerful driving force, and the interfacial Ti-O-Mo bonds served as an atomic-level channel for synergistically expediting the vectorial transfer of photogenerated carriers. As a result, AgI/MoS₂/Ti₃C₂O exhibited significantly improved photocatalytic activity, demonstrating a high H₂O₂ production rate of 700 μmol·g⁻¹·h⁻¹ and a rapid degradation of organic pollutants. Full article

Silicon has a striking similarity to carbon and is found in plant cells. However, there is no specific role that has been assigned to silicon in the life cycle of plants. The amount of silicon in plant cells is species specific and can reach levels comparable to macronutrients. Silicon is used extensively in artificial intelligence, nanotechnology, and the digital revolution, and thus can serve as an informational molecule such as nucleic acids. The diverse potential of silicon to bond with different chemical species is analogous to carbon; thus, it can serve as a structural candidate similar to proteins. The discovery of large amounts of silicon on Mars and the moon, along with the recent development of enzyme that can incorporate silicon into organic molecules, has propelled the theory of creating silicon-based life. The bacterial cytochrome has been modified through directed evolution such that it could cleave silicon–carbon bonds in organo-silicon compounds. This consolidates the idea of utilizing silicon in biomolecules. In this article, the potential of silicon-based life forms has been hypothesized, along with the reasoning that autotrophic virus-like particles could be used to investigate such potential. Such investigations in the field of synthetic biology and astrobiology will have corollary benefits for Earth in the areas of medicine, sustainable agriculture, and environmental sustainability. Full article

Iridium, with its excellent high-temperature chemical inertness, is a preferred cladding material for radioisotope batteries. However, its inherent room-temperature brittleness severely restricts its application. In this research, pure Ir and six Ir-W solid solutions (Ir₃₁W₁ to Ir₂₆W₆) were modeled. The effects of W on the elastic properties, generalized stacking fault energy, and bonding properties of Ir solid solution alloys were investigated by first-principles simulation, aiming to find a way to overcome the intrinsic brittleness of Ir. With the W concentration increasing from 0 to 18.75 at %, the calculated Cauchy pressure (C₁₂–C₄₄) increases from −22 to 5 GPa, Pugh’s ratio (B/G) increases from 1.60 to 1.72, the intrinsic stacking fault energy reduces from 337.80 to 21.16 mJ/m², and the unstable stacking fault energy reduces from 636.90 to 547.39 mJ/m². According to these results, it is predicted that the addition of W improves the toughness of iridium alloys. The alloying of W weakens the covalency properties of the Ir-Ir bond (the ICOHP value increases from −0.8512 to −0.7923 eV). These phenomena result in a decrease in the energy barrier for grain slip. Full article

Macrocyclic organic nanostructures have emerged as crucial components of functional supramolecular materials owing to their unique structural and chemical features, such as their distinctive “infinite” cyclic topology and tunable topology-dependent properties, attracting significant recent attention. However, the controlled synthesis of macrocyclic compounds with well-defined compositions and geometries remains a formidable challenge. On-surface synthesis, capable of constructing nanostructures with atomic precision on various substrates, has become a frontier technique for exploring novel macrocyclic architectures. This review summarizes the recent advances in the on-surface synthesis of macrocycles. It focuses on analyzing the synthetic mechanisms and conformational characterization of macrocycles formed through diverse bonding interactions, including both covalent and non-covalent linkages. This review elucidates the intricate interplay between the thermodynamic and kinetic factors governing macrocyclic structure formation across these bonding types and clarifies the critical influence of the reaction temperature and external conditions on the cyclization efficiency. Ultimately, this study offers design strategies for the precise on-surface synthesis of larger and more flexible macrocyclic compounds. Full article

Using density functional theory (M06-2X-D3/def2-TZVP), we investigated the 1,2-addition reactions of NH₃ with a series of heavy imine analogues, G13=P-Rea (where G13 denotes a Group 13 element; Rea = reactant), featuring a mixed G13–P–Ga backbone. Theoretical analyses revealed that the bonding nature of the G13=P moiety in G13=P-Rea molecules varies with the identity of the Group 13 center. For G13=B, Al, Ga, and In, the bonding is best described as a donor–acceptor (singlet–singlet) interaction, whereas for G13=Tl, it is characterized by an electron-sharing (triplet–triplet) interaction. According to our theoretical studies, all G13=P-Rea species—except the Tl=P analogue—undergo 1,2-addition with NH₃ under favorable energetic conditions. Energy decomposition analysis combined with natural orbitals for chemical valence (EDA–NOCV), along with frontier molecular orbital (FMO) theory, reveals that the primary bonding interaction in these reactions originates from electron donation by the lone pair on the nitrogen atom of NH₃ into the vacant p-π* orbital on the G13 center. In contrast, a secondary, weaker interaction involves electron donation from the phosphorus lone pair of the G13=P-Rea species into the empty σ* orbital of the N–H bond in NH₃. The calculated activation barriers are primarily governed by the deformation energy of ammonia. Specifically, as the atomic weight of the G13 element increases, the atomic radius and G13–P bond length also increase, requiring a greater distortion of the H₂N–H bond to reach the transition state. This leads to a higher geometrical deformation energy of NH₃, thereby increasing the activation barrier for the 1,2-addition reaction involving these Lewis base-stabilized, heavy imine-like G13=P-Rea molecules and ammonia. Full article

The sustainable recovery of valuable metals such as Cu and Co from ores is a pressing need considering environmental and economic challenges. Therefore, this study evaluates the effectiveness of deep eutectic solvents (DESs) as alternative leaching agents for Cu and Co extraction. Four DESs were prepared using choline chloride (ChCl) as a hydrogen bond acceptor (HBA) and oxalic acid (OA), ethylene glycol (EG), urea (U) and thiourea (TU) as hydrogen bond donors (HBDs). Leaching experiments were conducted with DESs supplemented with 30 wt.% water at varying temperatures, various solid-to-liquid ratios, and time durations. The ChCl:OA DES demonstrated the highest leaching efficiencies among the DESs tested on pure CuO and CoO, achieving 89.2% for Cu and 92.4% for Co (60 °C, 400 rpm, 6 h, −75 + 53 µm particle size, and 1:10 solid-to-liquid ratio). In addition, the dissolution kinetics, analysed using the shrinking core model (SCM), showed that the leaching process was mainly controlled by surface chemical reactions. The activation energy values for Cu and Co leaching were 46.8 kJ mol⁻¹ and 51.4 kJ mol⁻¹, respectively, supporting a surface chemical control mechanism. The results highlight the potential of ChCl:OA as a sustainable alternative for metal recovery. Full article

Ozone is a powerful destructive agent in the oxidative process of polymer composites. The destructive ability of ozone depends primarily on its concentration, duration of exposure, the type of polymer, and its matrix structure. In this work, nonwoven PLA/NR fibers with natural rubber contents of 5, 10, and 15 wt.% were obtained, which were then subjected to ozone oxidation for 800 min. The effect of ozone treatment was estimated using various methods of physicochemical analysis. The visual effect was manifested in the form of a change in the color of PLA/NR fibers. The method of differential scanning calorimetry revealed a change in the thermophysical characteristics. The glass transition and cold crystallization temperatures of polylactide shifted toward lower temperatures, and the degree of crystallinity increased. It was found that in PLA/NR fiber samples, the degradation process predominates over the crosslinking process, as an increase in the melt flow rate by 1.5–1.6 times and a decrease in the correlation time determined by the electron paramagnetic resonance method were observed. The IR Fourier method recorded a change in the chemical structure during ozone oxidation. The intensity of the ether bond bands changed, and new bands appeared at 1640 and 1537 cm⁻¹, which corresponded to the formation of –C=C– bonds. Full article

Electrostatic adsorption plays a crucial role in nanoparticle-based drug delivery, enabling the targeted and reversible loading of biomolecules onto nanoparticles. This review explores the fundamental mechanisms governing nanoparticle–biomolecule interactions, with a focus on electrostatics, van der Waals forces, hydrogen bonding, and protein corona formation. Various functionalization strategies—including covalent modification, polymer coatings, and layer-by-layer assembly—have been employed to enhance electrostatic binding; however, each presents trade-offs in terms of stability, complexity, and specificity. Emerging irradiation-based techniques offer potential for direct modulation of surface charge without the addition of chemical groups, yet they remain underexplored. Accurate characterization of biomolecule adsorption is equally critical; however, the limitations of individual techniques also pose challenges to this endeavor. Spectroscopic, microscopic, and electrokinetic methods each contribute unique insights but require integration for a comprehensive understanding. Overall, a multimodal approach to both functionalization and characterization is essential for advancing nanoparticle systems toward clinical drug delivery applications. Full article

This study explores the self-healing properties of polyurethane nanocomposites enhanced by multiple hydrogen bonds from ureido-pyrimidinone and the incorporation of 1–3 wt.% graphene nanoparticles, based on polyol α,ω-dihydroxy[oligo(butylene-ethylene adipate)]diol, which, according to our knowledge, has not been previously used in such systems. These new materials were synthesized via a two-step process and characterized by their thermal, mechanical, chemical, and self-healing properties. The mechanical analysis revealed that all nanocomposites exhibited high self-healing efficiencies (88–91%). The PU containing 2% graphene stands out as it exhibits the highest initial mechanical strength of ~5 MPa compared to approximately 2MP for a pristine PU while maintaining excellent self-healing efficiency (88%). A cut on the PU nanocomposite with 2% graphene can be completely healed after being heated at 80 °C for 1 h, which shows that it has a fast recovery time. Moreover, 3D printing was also successfully used to assess their processability and its effect on self-healing behavior. Three-dimensional printing did not negatively affect the material regeneration properties; thus, the material can be used in a variety of applications as expected in terms of dimensions and geometry. Full article

Glass enjoys a wide range of applications thanks to its superior optical properties and chemical stability. Conventional glass bonding techniques suffer from low efficiency, limited precision, and high cost. Moreover, for multilayer glass bonding, repeated alignment is often required, further complicating the process. These limitations have become major constraints on the advancement of microfluidic chip technologies. Laser bonding of microfluidic chips offers high precision and efficiency. This research first uses an ultrafast laser system to investigate how processing parameters affect weld morphology, identifying the optimal parameter range. Then, this paper proposes two methods for ultrafast-laser bonding of multilayer glass with different thicknesses and performs preliminary experiments to demonstrate their feasibility. The research in this paper could expand the fabrication method of microfluidic chips and lay a foundation for the wider application of microfluidic chips. Full article

Canvas paintings are prone to biodeterioration due to their complex chemical composition, which can support fungal growth even under controlled conditions. This study evaluated the susceptibility of common synthetic restoration materials—Lascaux glues (303 HV, 498 HV), Acrylharz P550, BEVA 371, Laropal A81, and Regalrez 1094—to degradation by fourteen xerotolerant/xerophilic fungal strains. All tested Aspergillus and Penicillium species extensively colonized, especially artificially aged materials. FTIR-PAS analysis revealed chemical changes in carbonyl and C–H bonds in Laropal A81 and Regalrez 1094 colonized by Aspergillus spp. Scanning electron microscopy (SEM) imaging showed thinning of Lascaux glues and deformation of Regalrez 1094. Transcriptomic profiling of A. puulaauensis grown on Lascaux 498 HV and Regalrez 1094 identified altered expression of genes coding for esterases and oxidases, enzymes involved in synthetic polymer degradation. Esterase activity assays using 4-nitrophenol-based substrates confirmed significant enzymatic activity correlating with the presence of ester bonds. These findings highlight the vulnerability of synthetic restoration materials, specifically Laropal A81, Regalrez 1094, and Lascaux glues, to extremophilic fungi thriving in environments with low water activity. The results emphasize the urgent need for specific knowledge on fungi and their metabolic pathways to use/develop more durable conservation materials and strategies to protect cultural heritage objects from biodeterioration. Full article